Photoactivation method and use of catalyst through inverted two-stage procedure

FIELD: chemistry.

SUBSTANCE: invention relates to a method of photoactivation of a photocatalyst by irradiating a composition containing the said catalyst. The method of using a photolatent catalyst (a) in which a composition containing said catalyst is irradiated before subsequent treatment is characterised by that, the photolatent catalyst is: (a1) a compound selected from a group consisting of a photolatent acid, an aromatic iodonium salt or oxime-based photolatent acid; (a2) a photolatent base compound. Also described is a substrate on which a coating made from the composition is deposited in accordance with the above described method. Also described is a method of using photolatent catalyst (a), in which a composition containing said catalyst is irradiated before subsequent treatment, characterised by that subsequent treatment is preparation of foam material and the composition contains polyol and isocyanate components and photolatent base (a2) as photolatent catalyst.

EFFECT: provision for solidification of the system.

13 cl, 10 tbl, 16 ex

 

The present invention relates to a method of photoactivation of the photocatalyst by irradiation of a composition containing a specified catalyst, prior to its further processing, i.e. before application to the substrate.

Curing compositions comprising focoltone catalysts, by irradiation is known. Radiation curing is most heavily used in cases when you can use a radically curable composition. For these radically curing systems developed a large number potyatinnik catalysts.

In addition, the above blended compositions comprising focoltone acid and a suitable crosslinking components, and the removal of protective groups by using eye-catching when exposed to radiation acids, for example, in the technology of photoresists.

In all these cases, the application of irradiation and thereby activation potyatinnik catalysts is carried out after deposition of the composition on a substrate.

All these technologies are difficult or even impossible curing throughout the thickness of the thick layers of coatings and coatings that are opaque due to the inclusion of pigments, glass fibers or other fillers that absorb or scatter radiation.

In addition, the curing shaded or poorly exposed areas, particularly three-dimensional about what yackov, is difficult, and in such cases, a radiating unit must be adapted to the size and shape of the object, which is applied to the coating, which requires complex and expensive design of the lamp.

Must have effective tools to protect the environment, safety and labour protection, in particular protection of the personnel in charge of applying and curing of these compositions.

In EP 1002587 proposed a method of applying a lacquer coating using a gun for spraying, in which irradiation is carried out prior to contact of the composition of the lacquer to the substrate. As appropriate for this method of composition indicated a well-known radiation-curable system, i.e. radically curable acid and base, but not the specific example of implementation and the efficiency of the method.

In WO 04/069427 shows an example of a similar method using a gun for spraying, in which the radiation source is located outside from the nozzle and is used by base catalyzed system hardening and special votolatino base, meaning that 2-benzyl-2-(dimethylamino)-1-[3,5-acid]-1-butanone.

According to the invention it was found that these drawbacks can be overcome by using ineradicable fototfreddie systems in combination with facing the eat this procedure of coating compositions with subsequent exposure to radiation to provide curing and using special compositions.

The object of the present invention is the method of application votolatino catalyst (a), in which a composition including a specified catalyst, is subjected to irradiation before further processing, characterized in that photolents catalyst is (A1) fotolenta acid of formula VI

in which

Ra2denotes a direct bond, S, O, CH2, (CH2)2WITH or NR96;

Ra3, RA4, RA5and RA6independently of one another denote H, C1-C20alkyl, C3-C8cycloalkyl,1-C20alkoxygroup,2-C20alkenyl, CN, IT, halogen, C1-C6allylthiourea, phenyl, naphthyl, phenyl-C1-C7alkyl, naphthyl-C1-C3alkyl, fenoxaprop, naphthyloxy, phenyl-C1-C7alkyloxy, naphthyl-C1-C3alkyloxy, phenyl-C2-C6alkenyl, naphthyl-C2-C4alkenyl, S-phenyl, (CO)Ra8, O(CO)Ra8, (CO)ORa8, SO2Ra8, OSO2Ra8;

Ra7stands With1-C20alkyl, C1-C20hydroxyalkyl,,or

Ra8denotes H, C1-C12alkyl, C1-C12hydroxyalkyl, phenyl, naphthyl and the and biphenylyl;

Ra9denotes a direct bond, S, O or CH2;

Ra10, Ra11, Ra12and Ra13independently of one another have one of the meanings indicated for Ra3; or Ra10and Ra12associated with the formation of a condensed ring system with the benzene rings to which they are attached;

Ra14does,

Z denotes an anion, preferably F6, SbF6AsF6BF4, (C6P5)4In, CL, Br, HSO4, CF3-SO3F-SO3,,

CH3-SO3, ClO4, RHO4, NO3, SO4CH3-SO4,

;

or in which fotolenta acid (A1) is a compound selected from the group comprising aromatic postname salts, aromatic itaniemi salt and based on the oximes focoltone acid; or (A2) votolatino connection base, provided that the excluded (3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane, if the composition includes an isocyanate in combination with thiols.

For the method proposed in the present invention, characterized by the fact that activation votolatino catalyst by irradiation of a composition containing a specified catalyst, is carried out before th is blowing processing, for example, deposition on a substrate, and that are special composition and the catalyst.

In the method proposed in the present invention, odnoupakovochnye or both supplied in two packages compositions optionally can be activated before the application without immediate course of curing. Regulation delays the start of the curing compositions in accordance with the requirements of the application can be performed by modifying the components of the resin, the catalyst activity or through the use of appropriate inhibitors. Because activation is separated from the stage of application, to activate the composition, you can use any source of radiation, regardless of the requirements of the application. For example, in the method proposed in the present invention, the UV radiation from a high energy can be used for the effective release of the catalyst without the use of precautions that are needed when you use the default method. When using high energy emission is possible to eliminate the use of chromophores characterized by a bathochromic shift, which lead to undesirable yellowing utverzhdenii film or can be activated natural light environment.

Due to the fact that in the method proposed in the present invention, between the activation of the cat who lyst and curing of the composition is the sequence of the respective stages of the method, before or after coating can optionally include other stages of the method (e.g., education facility with a coating, the formation of a layered type, and so on). In the method proposed in the present invention, it is possible to convert conventional two-component system in a simple to use one-component system in the presence of a blocked catalyst that provides easy application and extended service life easy to use compositions. Vysokoreaktsionnye is capable of two-component system currently difficult to use in industrial technology, which can happen downtime, because immediately after mixing begins stitching material in equipment for painting. This can lead to loss of material and/or equipment damage if the downtime composition thickens in apparatus for drawing.

In the method proposed in the present invention, in the form of radiation-curable systems easy to use and apply a variety of catalyzed compositions. Advantages are adjustable reactivity after activation of the catalyst and, consequently, curing at lower temperatures.

Depending on which song you want to sew or further processed photolents catalyst (a), for example, is the connection votolatino acid (A1) or the compound votolatino base (A2). Connection votolatino acid is a compound that when exposed produce acid, and the connection votolatino reason, you should understand how compound by irradiation with electromagnetic radiation emitting base.

It is therefore of interest the above-described method, in which (A) photolents catalyst (a) is fotolenta acid (A1) and the composition includes cured under acid catalysis compounds (b);

or in which

(B) photolents catalyst (a) is votolatino base (A2) and the composition includes cured at catalysis a ground connection ();

or in which

(C) photolents catalyst (a) is a mixture of at least one votolatino basic catalyst (A2) is at least one votolatino acid catalyst (A1) and in which the composition includes a mixture cured at catalysis acid compounds (b) and cured at catalysis based compounds (C), provided that (A1) and (A2) selectively activated.

Suitable photoinitiators (A1) for slivaushiesia component (b) are, for example, focoltone acid Lewis and Bronsted, cationic photoinitiator, such as aromatics the e sulfonate salt, described, for example, in WO 03/072567 and WO 03/00840; postname or itaniemi salts, such as described, for example, in US 4950581, from column 18, line 60 to column 19, line 10, WO 01/09075, WO 98/46647, US 6306555 or WO 01/44343; nonionic focoltone acid, for example focoltone sulfonic acid, such as based on the oximes focoltone acid, as described, for example, in GB 2348644, US 4450598, US 4136055, WO 00/10972, WO 00/26219, WO 02/25376, WO 02/98870, WO 03/067332 and WO 04/074242; α-sulfonyloxy described in the publication Berner et al., J. Radiat. Curing 1986, 13(4), 10; α-hydroxymethylphosphonate described in EP 89922; ortho-nitrobenzenesulfonate described in the publication Houlihan et al. Macromolecules 1988, 21, 2001; 4-nitrobenzylamine esters of sulfonic acids described in the publication Naitho et al, J. Phys. Chem. 1992, 96, 238, pentafluorobenzenesulfonyl described in the publication Barclay et al. 10thInt. Conf. On Photopolyme., Abstracts Session II PISPE, 1994, aryldiazonium-4-sulfonates described in the publication Buhr et al. Polym. Mat. Sci. Eng. 1989, 61, 269; α-sulfenylation described in the publication LiBassi et al, Conf. Proc. Radcure 86, 4/27 1986, methanesulfonate esters of 2-hydroxy - or 2,4-dihydroxybenzophenone described in the publication Pappas et al, J. Radiat. Curing 1980, 71(1), 2, sulphonate esters pyrogallol and its analogues is described in the publication Ueno et al. Polym. Eng. Sci. 1992, 32, 1511; veridicality described in the publication Aoai et al., J. Photopolym. Sci. Tenol. 1990, 3, 389, N-sulfonylamide described in the publication Rener et al. in US Patent 4371605, or sulfonated N-hydroxylamine described in US 4371605. You can also use other types of non-ionic potyatinnik acids, such as derivatives trichlorotriazine described, for example, in EP 332044, α-halogenated derivatives of acetophenone, described in the publication Peeters et al., Polym. Paint. Colour J. 1989, 179. 304, the vicinal dibromide described in the publication Gannon et al, J. Org. Chem. 1993, 58, 913, triarylphosphite described in the publication Givens et al. Chem. Rev. 1993, 93, 55, or ortho-nitrobenzisoxazole ethers in combination with the complexes of aluminum, is described in the publication Hayase et al, Macromolecules 1985, 18, 1799.

Preferred fotostendami acids are, for example, the compounds of formula V, VI, VII and/or VIIa

in which

Ra0and Ra1all independently of one another denote hydrogen, C1-C20alkyl, C1-C20alkoxygroup, HE is replaced With1-C20alkoxygroup, halogen, C2-C12alkenyl, cycloalkyl, preferably methyl, isopropyl or isobutyl; and Z represents an anion, preferably F6, SbF6AsF6BF4, (C6P5)4In, CL, Br, HSO4, CF3-SO3F-SO3,,

CH3-SO3, lO4, RHO4, NO3, SO4CH3-SO4,;

in which

Ra2denotes a direct bond, S, O, CH2, (CH2)2, CO or NR96;

Ra3, Ra4, Ra5and Ra6independently of one another denote H, C1-C20alkyl, C3-C8cycloalkyl,1-C20alkoxygroup,2-C20alkenyl, CN, IT, halogen, C1-C6allylthiourea, phenyl, naphthyl, phenyl-C1-C7alkyl, naphthyl-C1-C3alkyl, fenoxaprop, naphthyloxy, phenyl-C1-C7alkyloxy, naphthyl-C1-C3alkyloxy, phenyl-C2-C6alkenyl, naphthyl-C2-C4alkenyl, S-phenyl, (CO)Ra8, O(CO)Ra8, (CO)ORa8, SO2Ra8, OSO2Ra8;

Ra7stands With1-C20alkyl, C1-C20hydroxyalkyl,,or

Ra8denotes H, C1-C12alkyl, C1-C12hydroxyalkyl, phenyl, naphthyl or biphenylyl;

Ra9denotes a direct bond, S, O or CH2;

Ra10, Ra11, Ra12and Ra13independently of one another have one of the meanings indicated for RA3; or Ra10and Ra12associated with the formation of a condensed ring system with the benzene rings to which they are connec the us;

Ra14does,;

Z is as defined above;

or

where

Ra15does,

(CO)O-C1-C4alkyl, CN or C1-C12halogenated;

Ra16has one of the meanings indicated for Ra15or does;

Ra17stands With1-C18alkylsulfonyl, C1-C10halogenallylacetic, comparisonthis, phenyl-C1-C3alkylsulfonyl, C3-C30cycloalkylcarbonyl, phenylsulfonyl, naphthylmethyl, anthracenesulfonic or ventriculitis, and cycloalkyl, phenyl, naftalina, anthracyline and phenanthroline group of radicals With3-C30cycloalkylcarbonyl, phenyl-C1-C3alkylsulfonyl, phenylsulfonyl, naphthylmethyl, anthracenesulfonic and financialthe are unsubstituted or substituted by one or more halogen, C1-C4halogenation, CN, NO2With1-C16Akilov, fanilow,1-C4alkylthio,1-C4alkoxygroup, fenoxaprop,1-C4alkyl-O(CO)-, WITH1-C4alkyl-(CO)O-, Ra27OSO2- and/or-NRa20Ra21; Il the R a17represents C2-C6halogenoalkanes, halogenmethyl,,or;

X1, X2and X3all independently of one another denote O or S;

q is 0 or 1; and

Ra18stands With1-C12alkyl, cyclohexyl, Campari, unsubstituted phenyl, or phenyl substituted by one or more halogen, C1-C12Akilov, ORa19, SRa19or NRa20Ra21;

Ra19stands With1-C12alkyl, phenyl, phenyl-C1-C4alkyl or C1-C12hydroxyalkyl;

Ra20and Ra21all independently of one another denote hydrogen, C1-C4alkyl, C2-C6hydroxyalkyl, or Ra20and Ra21together with the N atom to which they are bound, form a 5 - or 6-membered ring which may also contain atoms Of the group or NRa22;

Ra22denotes hydrogen, phenyl, phenyl-C1-C4alkyl, C1-C12alkyl or C2-C5hydroxyalkyl;

Ra23, Ra24, Ra25and Ra26all independently of one another denote C1-C6alkyl, C1-C6halogenated; or phenyl, unsubstituted or substituted C1-C4by alkyl or halogen; and

Ra27denotes hydrogen, C1-C4 alkyl, phenyl or tolyl.

Specific values radicals described above.

Compounds of formulas V, VI, VII and VIIa are usually known and in some cases are commercially available. Obtaining them known to the specialist in the art and is often described in the literature.

Suitable iodonium salts are, for example, telelcommunications(pentafluorophenyl)borate, 4-[(2-hydroxyethylacrylate)phenyl]phenylethylenediamine and-hexaphosphate (SarCat CD®1012; Sartomer), telelcommunications, 4-isobutylphenyl-4'-methylenedithiocarbazate (IRGACURE®250, Ciba Spezialitätenchemie), 4-activatefailedexception and-hexafluoroantimonate, bis(dodecylphenyl)yoonikornproductions and-hexaphosphate, bis(4-were)stonyhearted, bis(4-methoxyphenyl)stonyhearted, 4-were-4'-ethoxytrimethylsilane, 4-were-4'-dodecylbenzenesulfonate, 4-were-4'-phenoxybenzenesulfonyl. From all iodonium these salts, of course, also suitable connections with other anions. Getting iodonium salts known to the specialist in the art and described in the literature, for example, in US 4151175, US 3862333, US 4694029, EP 562897, US 4399071, US 6306555, WO 98/46647 J.V.Crivello, "Photoinitiated Cationic Polymerization" in: UV Curing: Science and Technology, Editor S.P.Pappas, pages 24-77, Technology Marketing Corporation, Norwalk, Conn. 190, ISBN No. 0-686-23773-0; J.V.Crivello, J.H.W.Lam, Macromolecules, 10, 1307 (1977) and in J.V.Crivello, Ann. Rev. Mater. Sci. 1983, 13, pages 173-190 and J.V.Crivello, Journal of Polymer Science, Part A: Polymer Chemistry, Vol.37, 4241-4254 (1999).

Preferred iodonium salts are telelcommunications and 4-isobutylphenyl-4'-methylenedithiocarbazate.

Suitable oxysulphate and obtaining them are described, for example, in WO 00/10972, WO 00/26219, GB 2348644, US 4450598, WO 98/10335, WO 99/01429, EP 780729, EP 821274, US 5237059, EP 571330, EP 241423, EP 139609, EP 361907, EP 199672, EP 48615, EP 12158, US 4136055, WO 02/25376, WO 02/98870, WO 03/067332 and WO 04/074242.

Summary other donors potyatinnik acids are given in the form of a review in the publication .Shirai and M.Tsunooka in Prog. Polym. Sci., Vol.21, 1-45 (1996) and in the publication J.Crivello, K.Dietliker, "Photoinititiators for Free Radical Cationic &Anionic Photopolymerisation", 2" Edition, Volume III in the Series "Chemistry &Technology of UV &EB Formulation for Coatings, Inks &Paints", John Wiley/SITA Technology Limited, London, 1998, chapter III (p.329-463).

Preferred fotostendami acids in the method proposed in the present invention are 4-activatefailedexception, 4-(2-hydroxytetrazole-1 oksifenil)-phenylethylenediamine, 4-declaregraphicsrule, 4-dellpointingdevicetype, 4-isopropylphenyl-4'-methylphenylacetonitrile(pentafluorophenyl)borate, 4-isopropylphenyl-4'-methylenedithiocarbazate, 4-isobutylphenyl-4'-methylphenylacetonitrile(pentafluorophenyl)borate, 4-isobutylphenyl-'-methylenedithiocarbazate, in particular telelcommunications and 4-isobutylphenyl-4'-methylenedithiocarbazate.

Examples of suitable oxysulphate are α-(methylsulfonylamino)-4-methoxybenzylidene, α-(octyltriethoxysilane)-4-methoxybenzylidene, α-(methylsulfonylamino)-3-methoxybenzylidene, α-(methylsulfonylamino)-3,4-dimethylaniline, α-(methylsulfonylamino)-thiophene-3-acetonitrile, α-(isopropylthioxanthone)-thiophene-2-acetonitrile, CIS/TRANS-α-(dodecylsulfonate)-thiophene-2-acetonitrile,

,

where Rcdenotes halogenated, preferably-CF3and alkyl, preferably propyl;,

where Rddenotes alkyl, preferably methyl, and Redenotes alkyl, preferably methyl, propyl, octyl, Campari, p-tolyl or; etc. are Also suitable oximes, which give acid, non-sulphonic, and they are disclosed, for example, in WO 00/26219.

In the context of the present invention the above list should be considered, as presented merely as examples and not as limiting.

In the method proposed in the present invention, excluded the use of. In the method proposed in the present invention, and is clucene application. η6-isopropylbenzene) (η5-cyclopentadienyl)iron(II)hexaphosphate.

Of particular interest is the way in which votolatino acid (A1) is a compound of formula V, VII and/or VIIa

in which

Ra0and Ra1all independently of one another denote hydrogen, C1-C20alkyl, C1-C20alkoxygroup, HE is replaced With1-C20alkoxygroup, halogen, C2-C12alkenyl, cycloalkyl, preferably methyl, isopropyl or isobutyl; and Z represents an anion, preferably PF6, SbF6AsF6, F4, (C6F5)4In, CL, Br, HSO4, CF3-SO3F-SO3,,

CH3-SO3, lO4, RHO4, NO3, SO4CH3-SO4,;

orwhere

Ra15does,

(CO)O-C1-C4alkyl, CN or C1-C12halogenated;

Ra16has one of the meanings indicated for Ra15or does;

Ra17stands With1-C18alkylsulfonyl, C1-C10halogenallylacetic, comparisonthis, phenyl-C1-C3alkylsulfonyl, C3-C30cycloalkyl sulfonyl, phenylsulfonyl, naphthylmethyl, anthracenesulfonic or ventriculitis, and cycloalkyl, phenyl, naftalina, anthracyline and phenanthroline group of radicals With3-C30cycloalkylcarbonyl, phenyl-C1-C3alkylsulfonyl, phenylsulfonyl, naphthylmethyl, anthracenesulfonic and financialthe are unsubstituted or substituted by one or more halogen, C1-C4halogenation, CN, NR2With1-C16Akilov, fanilow,1-C4alkylthio,1-C4alkoxygroup, fenoxaprop,1-C4alkyl-O(CO)-, WITH1-C4alkyl-(CO)O-, Ra27OSO2- and/or-NRa20Ra21; or Ra17stands With2-C6halogenoalkanes, halogenmethyl,,or;

X1, X2and X3all independently of one another denote O or S;

q is 0 or 1; and

Ra18stands With1-C12alkyl, cyclohexyl, Campari, unsubstituted phenyl, or phenyl substituted by one or more halogen, C1-C12Akilov, ORa19, SRa19or NRa20Ra21;

Ra19stands With1-C12alkyl, phenyl, phenyl-C1-C4alkyl or C1-C12hydroxyalkyl;

Ra20and R a21all independently of one another denote hydrogen, C1-C4alkyl, C2-C6hydroxyalkyl, or Ra20and Ra21together with the N atom to which they are bound, form a 5 - or 6-membered ring which may also contain atoms Of the group or NRa22;

Ra22denotes hydrogen, phenyl, phenyl-C1-C4alkyl, C1-C12alkyl or C2-C5hydroxyalkyl;

Ra23, Ra24, Ra25and Ra26all independently of one another denote C1-C6alkyl, C1-C6halogenated; or phenyl, unsubstituted or substituted C1-C4by alkyl or halogen; and

Ra27denotes hydrogen, C1-C4alkyl, phenyl or tolyl.

Preferred fotostendami acids in the method proposed in the present invention are itaniemi salts and esters oxysulphate acids, preferably esters oxysulphate acid.

Especially preferred as component (A1) are the compounds of formula VII and VIIa.

Other interest method proposed in the present invention is the method described above in which photolents catalyst (a) is votolatino base (A2) and the composition includes cured at catalysis a ground connection (s).

As Votolato the data bases (A2) are included in the review, for example, blocked amines, for example, conventional focoltone base known in the art. Examples are compounds of the following classes: o-nitrobenzenesulfonamide, 3,5-dimethoxy-α,α-dimethylaminocarbonylmethyl, benzonatate, derivatives anilides, focoltone guanidine, normal focoltone tertiary amines, such as ammonium salts of α-ketocarboxylic acids and other carboxylates, benzhydrylamine salt, N-(benzophenone)-tri-N-trialkylamethylammoniumachloride, focoltone reason-based metal complexes, for example, amine complexes of cobalt, pyridinecarboxylic complexes of tungsten and chromium, forming anions photoinitiator based metals, such as complexes of chromium and cobalt salts Reineke and metalloporphyrins. Their examples are described in the publication J.V.Crivello, .Dietliker "Photoinitiators for Free Radical, Cationic &Anionic Photopolymerisation", Vol.III of "Chemistry & Technology ofUV & EB Formulation for Coatings, Inks &Paints", 2nd Ed., J.Wiley and Sons/SITA Technology, London, 1998.

As votolatino the main catalyst for the compositions proposed in the present invention are also suitable base, as described in WO 97/31033. They preferably are latent grounds on the basis of secondary amines, guanidines or amidines. Examples are the compounds of formula (A)

in which

X10, X20, X30, X40, X50, X60, X70X80X90, X100and X110all independently of one another denote hydrogen, C1-C20alkyl, aryl, arylalkyl, halogen, alkoxygroup, alloctype, arylalkylamine, aryl-N-alkyl-N-, arylalkyl-N-, allylthiourea, killigrew, arylalkylamine, NO, CN, a radical of the ether carboxylic acid, an amide radical of carboxylic acid or the radical of a ketone or aldehyde, or X10, X20, X30and X40may form a ring structure, and X50, X60, X70X80, X90, X100and X110regardless of X10, X20, X30and X40can form one or more additional ring structures.

Other suitable focoltone foundations are described in EP 764698. They are blocked amines, for example, of formula (In)

in which

Y10denotes the radicalor;

Y20denotes hydrogen or NO2;

Y30denotes hydrogen or C1-C8alkyl;

Y40, Y50, Y60, Y70and Y80all independently of one another denote hydrogen or F;

and

s is a number equal to from 15 to 29.

The can is about to use the connection on the basis of α-aminoketones, described in EP 898202 and WO 98/32756, based on the α-ammonium, iminium or amidaniel ketones and ariberto described in WO 98/38195, and on the basis of α-aminoalkenes described in WO 98/41524.

In the compositions proposed in the present invention, it is preferable to use compounds which when exposed to radiation in the visible part of the spectrum or UV radiation is removed medinova group. They contain the structural element of the formula

orin which

R1denotes an aromatic or heteroaromatic radical, capable of absorbing radiation in the wavelength from 200 to 650 nm and thus lead to the splitting of the adjacent carbon-nitrogen.

Of particular interest are compounds of the formula (C1) and (D1)

in which

R1denotes an aromatic or heteroaromatic radical which is capable of absorbing radiation in the wavelength from 200 to 650 nm and thus lead to the splitting of the adjacent carbon-nitrogen.

r is 0 or 1;

R2and R3independently of one another denote hydrogen, C1-C18alkyl, C3-C18alkenyl,3-C18quinil or phenyl, and, if R2denotes hydrogen or C1-C18alkyl, R3additionally denotes the group-C-R 14;

or R1and R3together with the carbonyl group and the atom that is attached to R3form benzocyclobutene radical;

R5stands With1-C18alkyl or NR15R16;

R4, R6, R7, R15and R16independently of one another denote hydrogen or C1-C18alkyl; or

R4and R6together form a2-C12Allenby bridge or

R5and R7together, irrespective of R4and R6form2-C12Allenby bridge

or, if R5denotes NR15R16, R16and R7together form a2-C12Allenby bridge; and

R14stands With1-C18alkyl or phenyl.

Examples R1as the aromatic or heteroaromatic radicals are phenyl, naphthyl, tenantry, antril, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl, oil[2,3-b]thienyl, thianthrene, dibenzofuran, bromanil, xantener, thioxanthen, femoxetine, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazoles, purinol, hemolysins, ethanolic, hinely, phthalazine, naphthyridine, honokalani, hintline, cinnoline, pteridine, carbazolyl, β-carboline is, phenanthridines, acridines, pyrimidinyl, phenanthrolines, phenazines, isothiazolin, phenothiazinyl, isoxazolyl, furutani, terphenyl, stilbene, fluorenyl and phenoxazines, these radicals are unsubstituted or mono - or polyamideimide1-C18the alkyl, C3-C18alkenyl,3-C18the quinil,1-C18halogenation, NO2, NR6R7N3HE, CN, OR8, SR8C(O)R9C(O)OR10or halogen,

or R1denotes a radical of the formula A1 or B1

;

R6and R7are as defined above;

R8, R9, R10, R11and R12denote hydrogen or C1-C18alkyl;

R13represents C1-C18alkyl, C2-C18alkenyl,2-C18quinil, C1-C18halogenated,

NO2, NR8R9HE, CN, OR10, SR10C(O)R11C(O)OR12or halogen; and

n is 0 or a number equal to 1, 2 or 3.

Other interest compounds potyatinnik grounds applicable in the method proposed in the present invention are the compounds of formula (C2) and (D2)

in which

R1is as defined above;

R10, R and R40all independently of one another denote hydrogen, C1-C18alkyl, C3-C18alkenyl,3-C18quinil or phenyl, or R20and R30and/or R40and R30every independently of each form With2-C12Allenby bridge; or R20, R30, R40together with the associated nitrogen atom form phosphazene the base type of P1, R2, P <t/4> or a group of structural formula (a), (b), (C), (d), (e), (f) or (g)

,,,,,,

k and l each independently from each other is a number equal to from 2 to 12;

R35denotes hydrogen or C1-C18alkyl;

R50denotes hydrogen or C1-C18alkyl; or

R50and R1together with their associated carbon atoms denote benzocyclobutene radical;

R11stands With1-C18alkyl, C2-C18alkenyl, C2-C18quinil,1-C18halogenated, NO2, NR60R70HE, CN, OR80, SR80C(O)R90C(O)OR100or halogen;

R60, R70, R80, R90and R100denote hydrogen or C1 18alkyl;

n is 0 or 1, 2 or 3; and m denotes the number of positively charged N atoms in the molecule.

"Anion" is any anion capable of forming a salt, preferably a halide such as CL, Br or I, borates, such as, for example,

,

where R120, R130and R140denote phenyl or another aromatic hydrocarbon radical, these radicals are unsubstituted or mono - or polyamideimide1-C18the alkyl, C3-C18alkenyl,3-C18the quinil,1-C18halogenation, NO2HE, CN, OR8, SR8C(O)R90C(O)OR100or halogen; R150stands With1-C18alkyl, phenyl or another aromatic hydrocarbon radical, phenyl and aromatic hydrocarbon radicals are unsubstituted or mono - or polyamideimide1-C18the alkyl, C3-C18alkenyl,3-C18the quinil,1-C18halogenation, NO2HE, CN, OR80, SR80C(O)R90C(O)OR100or halogen, or R150denotes the radical

;

or R120, R130, R140and R150denote halogen; and XZstands With1-C20alkylen,2-C20alkylen, which includes-O-, -S - or-NR80/sub> or XZdenotes phenylene, biphenylene, terminalen, naftilan, entrylen or phenylene-CO-phenylene. The anion may be any of the anions, as defined above for Z, i.e. F6, SbF6AsF6, F4, (C6F5)4In, CL, Br, HSO4, CF3-SO3F-SO3,

,

CH3-SO3, ClO4, RHO4, NO3, SO4CH3-SO4,.

Preferred are the compounds of formula C1 and D1, in which R4and R6together form a2-C12Allenby bridge and R5and R7together, irrespective of R4and R6form2-C12alkilinity the bridge.

Preferred are the compounds of formula C2 and D2, in which R20denotes a group of formula (a), (b) or (C).

Of particular interest focoltone base having the structure of type,,,,,,,,,,,,

where r, R1, R2, R3and R50are such that ka is defined above.

R1preferably denotes phenyl, naphthyl, pyrenyl, thioxanthen or phenothiazinyl, and these radicals are unsubstituted or mono - or polyamideimide1-C18the alkyl, C1-C18halogenation, NR60R70, CN, NO2, SR80or or80. Preferably, if R1denotes unsubstituted or mono - or politeley phenyl.

R50preferably signifies hydrogen or C1-C4alkyl, more preferably hydrogen or methyl.

Preferred fotostendami bases are, for example, compounds of formula VIII, VIIIa and VIIIb

,

in which

r is 0 or 1;

X4denotes CH2or;

R2and R3all independently of one another denote hydrogen or C1-C20alkyl;

R1denotes unsubstituted or1-C12alkyl or C1-C12alkoxy-substituted phenyl, naphthyl or biphenylyl;

R20, R30and R40together with the associated nitrogen atom denote a group of the structural formula (a), (b) or (C),,;

R35denotes hydrogen or C1-C18alkyl;

anion represents any anion which can form a salt; and m denotes the number of positively charged N atoms in the molecule.

C1-C18Alkyl group (s) preferably denotes methyl.

Obtaining compounds of formula (C), (C1), (C2), (D), (D1), (D2), (VIII) and (VIIIa) is known and described in WO 98/32756, WO 98/38195, WO 98/41524, WO 00/10964 and EP 1436297. These descriptions also contain more specific examples of such compounds and are included in the present invention by reference.

The exact values of the radicals R1-R16in formula C, C1, D, D1 and VIII in the context of the present invention are similar to that shown for the corresponding radicals in WO 98/32756. This description is included in the present invention by reference.

The exact values of the radicals R1, R20, R30, R40, R50, R60, R70, R80, R90, R100, R120, R130, R140XZgroups (a), (b), (C), (d), (e), (f), (g) and phosphazene bases of P1P2, P<t/4> in the formula C2, D2 and VIIIa in the context of the present invention are similar to that shown for the corresponding radicals in WO 00/10964. This description is included in the present invention by reference.

As donors potyatinnik grounds are also suitable α-aminoketone described in EP 898202, for example (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane or (4-methylthiophenyl)-1-methyl-1-morpholino the tan.

In the embodiment, the method proposed in the present invention, the use of α-aminoketones as votolatino reason excluded in compositions containing both thiol and isocyanate.

In the embodiment, the method proposed in the present invention, the use of α-aminoketones as votolatino grounds are excluded, if the composition is a composition for coating.

In the embodiment, the method proposed in the present invention, the use of α-aminoketones as votolatino grounds are excluded.

In the embodiment, the method proposed in the present invention, using (3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane excluded in compositions containing both thiol and isocyanate.

In the embodiment, the method proposed in the present invention, using (3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane excluded, if the composition is a composition for coating.

In the embodiment, the method proposed in the present invention, using (3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane excluded.

Examples of preferred potyatinnik bases in the method proposed in the present invention are,, ,,,,,,,,and

In some cases it may be useful to use mixtures of two or more photoinitiators. They may be mixtures of several potyatinnik acids, mixtures of several potyatinnik grounds, as well as mixtures of free radical photoinitiators with fotostendami acids (for example, for use in so-called hybrid systems) or mixtures of free radical photoinitiators with fotostendami bases or mixtures of free radical photoinitiators with fotostendami acids and fotostendami bases.

In the context of the present invention the above list should be considered, as presented merely as examples and not as limiting.

Summary of other donor fotonovelas given in the form of a review in the publication M.Shirai and M.Tsunooka in Prog. Polym. Sci., Vol.21, 1-45 (1996) and in the publication J.Crivello, K.Dietliker, "Photoinititiators for Free Radical Cationic &Anionic Photopolymerisation", 2" Edition, Volume III in the Series "Chemistry &Technology of UV &EB Formulation for Coatings, Inks &Paints", John Wiley/SITA Technology Limited, London, 1998, chapter IVI (p.479-544).

Photopolymerizing compositions include f is tolerantly catalyst (a), ie (A1) and/or (A2), preferably in amounts of from 0.01 to 20 wt.%, for example, from 0.05 to 15 wt.%, preferably from 0.1 to 20 wt.%, for example, from 1 to 15 wt.%, more preferably from 1 to 5 wt.% in terms of composition. The specified number of photoinitiator means the sum of all added photoinitiators, if you are using a mixture thereof.

Cured under the catalysis of the acid component (b) is a compound that when exposed to acid is able to react polymerization, polycondensation or polyaddition.

The composition proposed in the present invention comprise as component (b), for example, resins and compounds that are capable of cationic polymerization when exposed to alkyl - or arylesterase cations or protons. Their examples are cyclic ethers, preferably epoxides and oxetane, and vinyl ethers, and hydroxycobalamin connection. You can also apply the lactones and cyclic simple thioethers, as well as simple vinyl thioethers. Other examples are the aminos and phenolic rezol resin. They preferably are melamine, urea, epoxy, phenolic, acrylic, complex polyester and alkyd resins, and more preferably a mixture of acrylic, complex polyesters or alkyd resins with melamine resins. So what s included modified resin, intended for use as coatings for surfaces, such as modified acrylic compounds of polyester and alkyd resins. Examples of specific types of resins, which are included in the concept acrylic, complex polyester and alkyd resins are described, for example, Wagner, Sarx/Lackkunstharze (Munich, 1971), pages 86 to 123 and 229 to 238, or in publishing Ullmann/Encyclopadie der techn. Chemie, 4th edition. Vol.15 (1978), pages 613 to 628, or in the publication Ullmann''s Encyclopedia of Industrial Chemistry, Verlag Chemie, 1991, Vol.18, 360 ft, Vol.A19, 371 ff. Preferably, if the component contains amine resin (particularly if the connection is used as a coating to the surface). Their examples are melamine, urea, guanidine and biuret resin, formed or not formed ethers. Acid catalysts are particularly important for curing coatings for surfaces that contain amine resin, formed ethers, for example methylated or bottled melamine resins (N-methoxymethyl - or N-butoxyethylene) or methylated/bottled glycoluril. Amide and amine resins are described, for example, in the publication Stoye Freitag, Lackharze, Carl Hanser Verlag München 1996, p.104-126 and nowelcome resins are described, for example, in the publication Stoye Freitag, Lackharze, Carl Hanser Verlag München 1996, p.150-152.

You can also use, for example, all the usual epoxides, such as aromati the definition, aliphatic or cycloaliphatic epoxy resin. They are compounds containing in the molecule at least one apachegroup, preferably at least two epoxypropyl. Their examples are Picadilly ethers and β-methylpyridine ethers of aliphatic or cycloaliphatic diols and polyols, for example ethers of ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, diethylene glycol, polyethylene glycol, polypropyleneglycol, glycerol, trimethylolpropane and 1,4-dimethylcyclohexane or 2,2-bis(4-hydroxycyclohexyl)propane and N,N-bis(2-hydroxyethyl)aniline; glycidyloxy ethers, di - and polybasic phenols, such as resorcinol, 4,4'-dihydroxyphenyl-2,2-propane, nofollow or 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples are phenylglycidyl ether, p-tert-BUTYLPEROXY ether, o-crazyholiday ether, polytetrahydrofuran esters, n-butylpyridinium ether, 2-Ethylhexylglycerin broadcast12/S15alkylglycerol esters, cyclohexenyltrichlorosilane esters. Additional examples are N-Picadilly connection, for example Picadilly connection ethylenoxide, 1,3-propylenimine and 5-dimethylhydantoin and 4,4'-methylene-5,5'-tetramethylguanidine and such compounds as tripyridyltriazine.

Updat the comparative examples glycidyloxy ethers - component (b)used in the method proposed in the present invention are glycidyloxy esters of monohydroxy phenols, obtained by the reaction of polyhydric phenols with an excess of chlorohydrin, such as epichlorohydrin (e.g glycidyloxy ethers of 2,2-bis(2,3-epoxypropoxyphenyl)propane. Additional examples glycidyloxy esters of epoxides that can be applied in the context of the present invention are described, for example, in US 3018262 and in the publication "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967).

A large number of commercially available glycidyloxy ethers epoxides suitable for use as component (b), for example glycidylmethacrylate, diglycidyl ethers of bisphenol a, for example marketed under the trade names EPON 828, EPON 825, EPON 1004 and EPON 1010 firm Shell; DER-331, DER-332 and DER-334, produced by Dow Chemical company; 1,4-potentialization ether of phenol novolak, such as DEN-431, DEN-438 manufactured by Dow Chemical company; and diglycidyl ether of resorcinol; allylglycidyl ethers, for example, C8-C10glycidyloxy ethers, e.g. HELOXY Modifier 7, p12-C14glycidyloxy ethers, e.g. HELOXY Modifier 8, butespecially ether, e.g. HELOXY Modifier 61, crazyholiday ether, e.g. HELOXY Modifier 62, p-tert-butyleneglycol ether, e.g. HELOXY Modifier 65, polyfunctional glizid the gross esters, for example diglycidyl ether of 1,4-butanediol, for example, HELOXY Modifier 67, diglycidyl ether of neopentyl glycol, e.g. HELOXY Modifier 68, diglycidyl ether cyclohexanedimethanol, for example, HELOXY Modifier 107, triglycerol ether trimethyloctane, for example, HELOXY Modifier 44, triglycerol ether of trimethylolpropane, for example, HELOXY Modifer 48, polyglycidyl ethers of aliphatic polyols, e.g. HELOXY Modifier 84 (all glycidyloxy esters HELOXY are issued by the company Shell).

Suitable also are simple glycidyloxy esters, which contain copolymers of acrylic esters, for example, styrene/glycidylmethacrylate and methyl methacrylate/glycidylmethacrylate. Examples are 1:1 styrene/glycidylmethacrylate, 1:1 methyl methacrylate/glycidylmethacrylate, 62.5:24:13.5 methacrylate/acrylate/glycidylmethacrylate.

The polymers of simple glycidyloxy esters can also, for example, can contain other functional groups, provided that they do not inhibit cationic curing.

Other simple glycidyloxy ethers used as component (b) and sold by the company Vantico, are polyfunctional liquid and solid nowelcome glycidylether resin, for example, PY 307, EPN 1179, EPN 1180, EPN 1182 and ECN 9699.

It should be understood that as the component (b) can also be used mixtures of different simple glycidyloxy esters.

Simple glycidyloxy esters, the use of the are as the component (b), represents, for example, compounds of formula XX

in which

x is a number equal to from 1 to 6; and

R85denotes a monovalent - hexavalent alkyl or aryl radical.

Preference is given, for example, a simple glycidyloxy esters of the formula XX, in which x is a number equal to 1, 2 or 3; and

R85when x=1, denotes unsubstituted or1-C12alkyl substituted phenyl, naphthyl, antracol, biphenylyl,1-C20alkyl or C2-C20alkyl, in which is included one or more oxygen atoms, or

R85when x=2, denotes 1,3-phenylene, 1,4-phenylene, C6-C10pelaaminen, unsubstituted or halogen-substituted C1-C40alkylen,2-C40alkylen, which includes one or more oxygen atoms, or the groupor

R85when x=3, denotes the radical,or;

y is a number equal to from 1 to 10; and

R81stands With1-C20alkylene, oxygen, or.

Simple glycidyloxy esters are, for example, compounds of formula HHA

in which

R82denotes unsubstituted or1 -C12alkyl substituted phenyl; naphthyl; intracel; biphenylyl; C1-C20alkyl, C2-C20alkyl, in which is included one or more oxygen atoms; or a group of the formula

;

R85denotes phenylene, C1-C20alkylen,2-C20alkylen, which includes one or more oxygen atoms, or the group; and

R81stands With1-C20alkylene or oxygen.

The preference for a simple glycidyloxy esters of the formula bin which

R85denotes phenylene, C1-C20alkylen,2-C20alkylen, which includes one or more oxygen atoms, or the group; and

R81represents C1-C20alkylene or oxygen.

Additional examples of the component (b) are polyglycidyl ethers, and poly(β-methylpyridine) ethers obtained by the reaction of compounds containing at least two free alcoholic and/or phenolic hydroxy-group in one molecule with the corresponding epichlorohydrin under alkaline conditions or, alternatively, in the presence of an acid catalyst with subsequent treatment with alkali; it is also possible to use mixtures of different poly is fishing.

Such ethers can be obtained by using poly(epichlorohydrin) from acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly(oksietilenom)glycols, propane-1,2-diol and poly(oxypropylene)glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetracyline)glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol and sorbitol, from cycloaliphatic alcohols, such as resorcinol, hinit, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane and 1,1-bis(hydroxymethyl)cyclohex-3-ene, and from alcohols containing aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline and p,p'-bis(2-hydroxyethylamino)difenilmetana. They can also be obtained from managernew phenols, such as resorcinol and hydroquinone, and from multi-core phenols, such as bis(4-hydroxyphenyl)methane, 4,4-dihydroxydiphenyl, bis(4-hydroxyphenyl)sulfon, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol a) and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.

Other hydroxidealuminum, suitable for polyglycidyl ethers and poly-(β-methylglycerol) ethers are novolak obtained by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral and furfural, with phenols, such as phenol, o-cresol, m-cresol, p-cresol, 3,5-dimethyl is Nole, 4-chlorophenol and 4-tert-butylphenol.

Poly(N-Picadilly) compounds can be obtained, for example, by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least two amine hydrogen atoms, such as aniline, n-butylamine, bis(4-AMINOPHENYL)methane, bis(4-AMINOPHENYL)propane, bis(4-methylaminophenol)methane and bis(4-aminophenoxy) ether, sulfon and sulfoxide. Other suitable poly(N-glitzymimimimi) compounds are triglyceriderich and N,N'-diglycidyl derivatives of cyclic etkilenmenin, such as etilenmocevina and 1,3-propylenimine, and hydantoins, such as 5,5-dimethylhydantoin.

Poly(S-Picadilly) compounds are also suitable. Their examples are di-S-Picadilly derivatives developed, such as ethane-1,2-dithiol and bis(4-mercaptoethanol) ether.

As component (b) in consideration also includes epoxy resin, in which Picadilly group or β-methylpyridine groups are associated with different types of heteroatoms, such as N,N,O-triglycidyl derivative of 4-aminophenol, glycidyloxy simple ether pilgramage of ester of salicylic acid and p-hydroxybenzoic acid, N-glycidyl-N'-(2-glycidyloxy)-5,5-dimethylhydantoin and 2 glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylester-3-yl)propane.

Diglycidyl esters of bispen the crystals are preferred. Their examples are diglycidyl ether of bisphenol a, such as ARALDIT GY 250, produced by the company Huntsman, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S. Special preference is given diglycidylether ether of bisphenol A.

Other important industrial Picadilly compounds suitable for use in component (b) are glycidyloxy esters of carboxylic acids, preferably two - and polybasic carboxylic acids. Their examples are glycidyloxy esters of succinic acid, adipic acid, azelaic acid, sabatinovka acid, phthalic acid, terephthalic acid, Tetra - and hexahydrophthalic acid, isophthalic acid and trimellitic acid and demonizovana fatty acids.

Examples of polyepoxides that are not glitzymimimimi compounds are the epoxides of vinylcyclohexane and Dicyclopentadiene, 3-(3',4'-epoxycyclohexyl)8.9bn-epoxy-2,4-dioxaspiro[5.5]undecane, 3',4'-epoxycyclohexylmethyl ether of 3,4-epoxycyclohexanecarboxylate acid, (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), diepoxide butadiene and diepoxide isoprene, epoxydecane derivatives of linoleic acid and epoxydecane polybutadiene.

Other suitable epoxy compounds are, for example, limonene monoxide, epoxydecane soybean oil, Epoque is ednie resin of bisphenol a and bisphenol F, for example, Araldit®GY 250 (A), Araldit®GY 282 (F), Araldit®GY 285 (F) (Huntsman), and fotoliausa siloxanes that contain epoxypropyl.

Other suitable undergoing cationic polymerization or blending components (b) are, for example, in patents US 3117099, 4299938 and 4339567.

From the group of aliphatic epoxides are suitable, for example, in particular monofunctional epoxides of α-olefins containing unbranched chain, including 10, 12, 14 or 16 carbon atoms.

Because currently there are a large number of different apocynoideae, characteristics of the binder can vary significantly. One possible change, for example, depending on the purpose of the composition is the use of mixtures of various epoxy compounds and the addition of plasticizers and reactive diluents.

Epoxy resin can be diluted with a solvent for ease of application, for example, when the deposition is performed by sputtering, but it is preferable to use epoxysilane without solvent. Resins, which are viscous or solid at room temperature, can be applied, for example, hot.

Also suitable for use as component (b) all ordinary vinyl ethers, such as aromatic, aliphatic or cycloaliphatic vinyl is rostie esters, and silicon-containing vinyl ethers. They are compounds containing in the molecule at least one vinyl ether group, preferably at least two vinyl ether groups. Examples of vinyl ethers which are suitable for use in the method proposed in the present invention are divinely ether of triethylene glycol, divinely ether of 1,4-cyclohexanedimethanol, 4-hydroxybutylidene ether, propenyloxy ether of propylene carbonate, dodecylphenyl ether, tert-butylvinyl ether, tert-millinery ether, cyclohexylaniline ether, 2-ethylhexylacrylate ether, monomineralic ether of ethylene glycol, monomineralic ether of butanediol, monomineralic ether hexandiol, monomineralic ether of 1,4-cyclohexanedimethanol, monomineralic ether of diethylene glycol, divinely ether of ethylene glycol, butylmalonate ether of ethylene glycol, butanediol-1,4-divinely ether, divinely ether hexandiol, divinely ether of diethylene glycol, divinely ether of triethylene glycol, metronomically ether of triethylene glycol, divinely broadcast tetraethyleneglycol, divinely ether Pluriol E 200, divinely broadcast polytetrahydrofuran 290, timeoverlay ether of trimethylolpropane, divinely broadcast dipropyleneglycol, octadecylammonium ether, methyl ester (4-cyclohexyl who ethylenoxide)of glutaric acid and (4-butoxyethyl)isophthalic acid.

Examples of hydroxyl-containing compounds are complex polyether polyols, for example polycaprolactones and complex preferredability, glycols and simple polyether polyols, castor oil, hydroxy-group containing vinyl and acrylic resins, esters of cellulose, such as acetylbutyrate cellulose, and proximally.

Other suitable undergoing cationic curing of the composition described, for example, in EP 119425.

Preferred as component (b) are cycloaliphatic epoxides and epoxies based on bisphenol A.

1) coating for surfaces based on stitched in cold or hot condition alkyd, acrylate, complex, polyester, epoxy, urea or melamine resins or mixtures of such resins, optionally with the addition of a curing catalyst;

2) one-component polyurethane coatings for surfaces based on aliphatic or aromatic urethaneacrylate or polyurethanecoated containing free amino groups in the urethane structure and melamine resins or complex polyester resins, optionally with the addition of a curing catalyst;

3) thermoplastic polyacrylate coating for surfaces based on thermoplastic acrylate resins or externally stitched acrylate resins in combination with formed simple EPE is s melamine resins;

4) coating for surfaces based on acrylate resins modified with fluorine or siloxanes;

5) coating for surfaces, preferably transparent coatings for surfaces based on the locked malonate isocyanates with melamine resins (for example, hexamethoxymelamine) as a crosslinking agent (acid catalysis);

6) the system is a dual-cured, which first utverjdayut thermally, and then using a UV - or Vice versa - in which the components of the composition coating for surfaces include double bonds, which are injected into the reaction by means of UV-radiation and photoinitiators and/or by electron beam irradiation.

As confirmed during the catalysis of the acid component (b) are of special interest

1) coating for surfaces based on stitched in cold or hot condition alkyd resins in combination with urea or melamine resins, with the addition of a curing catalyst;

2) coating for surfaces based on stitched in cold or hot condition hydroxy-group containing acrylate and/or a complex of the polyester in combination with urea or melamine resins, with the addition of a curing catalyst;

3) coating for surfaces based on stitched in cold or hot condition epoxide in whom is inali with urea or melamine resins, with the addition of a curing catalyst.

Cured at the base catalysis by component (C) is a compound that when exposed to a base able to react polymerization, polycondensation or polyaddition.

Catalyzed by base reaction polymerization, addition condensation or substitution can be performed with low molecular weight compounds (monomers), oligomers, polymer compounds or mixtures of such compounds. Examples of reactions that can be performed with monomers or oligomers/polymers using the method proposed in the present invention are the reaction Knowingly and accession by Michael. For the reaction may be useful or required the presence of additional components. This is disclosed, for example, in EP 1092757.

Of particular interest are compositions in which component (C) is subjected to anionic polymerization or blending organic matter.

Undergoing anionic polymerization or blending organic material [component (C)] may be in the form of mono - or polyfunctional monomers, oligomers or polymers.

Particularly preferred oligomeric/polymeric systems (C) are binding, normal for the paint industry.

Two-component system consisting of α,β-ethyl is unsaturated carbonyl compound and a polymer, containing activated group SN2in which the activated group of CH2are either a main chain or side chain or both chains are described, for example, in EP 161697 for the case of (poly)malonate groups. In polyurethane, complex, polyester, polyacrylate, epoxy resin, polyamide or polyvinyl polymer maloata group may be linked to the main chain or side chain. Used α,β-Ethylenediamine carbonyl compound can be any compound with double bonds, activated carbonyl group. Examples are the esters and amides of acrylic acid and methacrylic acid. In the ester groups can also contain additional hydroxy-group. You can also use complex di - and treatery. Typical examples are hexaniacinate and trimethylolpropane. Instead of acrylic acid is also possible to use other acids and their esters and amides, such as cretonne easy acid or cinnamic acid.

Other compounds containing activated group SN2are (poly)acetoacetate and (poly)cyanoacetate.

Additional examples are two-component systems comprising a polymer containing activated group SN2in which activated group CH2are or core the main chain, or in the side chain or both chains, and a polymer containing activated group SN2such as (poly)acetoacetate and (poly)cyanoacetate, and polulegalny cross-linking reagent, for example, terephthalic aldehyde. Such systems are described, for example, in the publication Urankar et al., Polym. Prepr. (1994), 35, 933.

System components enter into reaction with each other at the base catalysis at room temperature and form a cross-linked system for coatings, suitable for use in various cases. Due to its good weather resistance the system is also suitable for use outdoors and, if necessary, it can be additionally stabilized by absorbers of UV radiation and other light stabilizers.

As component (C) in the compositions proposed in the present invention, in consideration also included epoxy system. Epoxy resin, suitable for receiving the curable mixtures proposed in the present invention containing the epoxy resin as component (C)are the usual technology of epoxy resins. Examples of such epoxy resins described above for the component (b).

Suitable examples are preferably polyglycidyl and poly(β-methylpyridine) esters obtained by the reaction of compounds containing in the molecule at minicamera two carboxypropyl, and of epichlorohydrin and β-methylephedrine respectively. The reaction is preferably carried out in the presence of bases.

As compounds containing in the molecule at least two carboxypropyl, it is possible to use aliphatic polybasic carboxylic acid. Examples of such aliphatic polybasic carboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, Emelyanova acid, cork acid, azelaic acid and diarizonae or trimmeresana linoleic acid. However, it is also possible to use cycloaliphatic polybasic carboxylic acids, for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid. You can also use aromatic polybasic carboxylic acids, for example phthalic acid, isophthalic acid or terephthalic acid.

Polyglycidyl or poly(β-methylpyridine) ethers receive by the reaction of compounds containing at least two free alcoholic hydroxy-group and/or phenolic hydroxy-group, with epichlorohydrin or β-methylephedrine in an alkaline medium or in the presence of an acid catalyst with subsequent treatment with alkali.

Glycidyloxy ethers of this type on ucaut, for example, from acyclic alcohols such as ethylene glycol, diethylene glycol or higher poly(oksietilenom)glycols, propane-1,2-diol or poly(oxypropylene)glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetracyline)glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, and polyepichlorohydrins. However, they can also be obtained, for example, from cycloaliphatic alcohols, such as 1,4-cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane or 2,2-bis(4-hydroxycyclohexyl)propane, or they contain aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)difenilmetana. Glycidyloxy ethers may also be obtained from managernew phenols, such as resorcinol or hydroquinone, or they are based on polynuclear phenols, for example bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfon, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and novolak obtained by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfural, with phenols, such as phenol, or with phenols that are substituted in the nucleus by chlorine atoms or With1-C9alkyl groups, for example 4-chlorophenol, 2-METHYLPHENOL or 4-tert-butylphenol, or by condens the tion with bisphenolate, such as bisphenol the specified type.

Poly(N-Picadilly) compounds obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amine hydrogen atoms. Such amines are, for example, aniline, n-butylamine, bis(4-AMINOPHENYL)methane, m-xylylenediamine and bis(4-methylaminophenol)methane.

Poly(N-Picadilly) compounds also include triglyceriderich, N,N'-diglycidyl derivatives cycloalkylation, such as etilenmocevina and 1,3-propylenimine, and diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin.

Poly(S-Picadilly) compounds, for example di-S-Picadilly derivatives, obtained from dithioles, for example ethane-1,2-dithiol or bis(4-mercaptomethyl) ether.

Cycloaliphatic epoxy resins such as bis(2,3-amoxicillinbuy) ether, 2,3-amoxicillingeneric ether, 1,2-bis(2,3-amoxicillincheap)ethane or 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

However, it is also possible to use epoxy resins in which the 1,2-epoxypropyl associated with different heteroatoms or functional groups; these compounds include, for example, N,N,O-triglycidyl derivative of 4-aminophenol, glycidyloxy simple ether pilgramage of ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxy is propyl)-5,5-dimethylhydantoin and 2 glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylester-3-yl)propane.

As component (C) can also be used mixtures of epoxy resins. Therefore, the present invention also relates to compositions, as component (C) comprising an epoxy resin or a mixture of different epoxy resins.

Component (C) may also include compounds that transform into another form by exposure bases. They, for example, are compounds which, when catalyzed by bases, such as the removal of the protective groups, change their solubility in suitable solvents.

As can be seen from the above description, for use as component (b) or (C) apply some monomers, oligomers and polymers, because they both are blended by free radicals and are blended with an acid or a base. For example, two-component system described above as cured during the catalysis of base components, you can also sew by adding photoinitiator, forming free radicals.

Other interest components (C) are

1) two-component polyurethane coatings based surface containing hydroxyl groups acrylate, complex polyester or easy polyester resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

2) the two-component polyure the new coatings for surfaces based on containing tirinya acrylate group, complex polyester or easy polyester resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

3) one-component polyurethane coatings for surfaces based on blocked isocyanates, isocyanurates or polyisocyanates, which are released during heating; if appropriate, it is also possible to add melamine resins;

4) two-component coatings for surfaces based on (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

5) two-component coatings for surfaces based on (poly)ketimines and an unsaturated acrylate resin or polyacetate resin, or methyl ether of methacrylamides;

6) two-component coatings for surfaces based on containing carboxyl or amino group of the polyacrylates and polyepoxides, preferably based on containing the carboxyl group of the polyacrylates and polyepoxides;

7) two-component coatings for surfaces based on containing anhydrite group of acrylate resins and polyhydroxylated or polyamino component, preferably polyhydroxylated component;

8) two-component coatings for surfaces based on galatsaray anhydrides and polyepoxides;

9) two-component on which rite for surfaces based on (poly)oxazolines and containing anhydrite group of acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

10) two-component coatings for surfaces based on an unsaturated (poly)acrylate and (poly)malonate;

11) one-component coating for surfaces of epoxy resins;

12) two-component coatings for surfaces based on containing tirinya acrylate group, a complex of the polyester or easy polyester resins and polyepoxides;

13) the system is a dual-cured, which first sew thermally using basic catalysis, and then utverjdayut using UV - or Vice versa - in which the components of the composition coating for surfaces include double bonds, which are injected into the reaction by means of UV-radiation and photoinitiators and/or by electron beam irradiation.

As cured at the base catalysis of components (C) are of special interest

1) two-component polyurethane coatings based surface containing hydroxyl groups acrylate, complex polyester or easy polyester resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

2) two-component polyurethane coatings for surfaces based on containing tirinya acrylate group, a complex of the polyester or easy polyester resins and aliphatic or aromatic isocyanates, from which Anurov or polyisocyanates;

3) two-component coatings for surfaces based on containing carboxyl or amino group of the polyacrylates and polyepoxides, preferably based on containing the carboxyl group of the polyacrylates and polyepoxides;

4) one-component coating for surfaces of epoxy resins;

5) two-component coatings for surfaces based on containing tirinya acrylate group, a complex of the polyester or easy polyester resins and polyepoxides.

In the method proposed in the present invention, as a composition, you can apply the mixture of (b) and (C), and the mixture potyatinnik catalysts (A1) and (A2), provided that the catalyst is activated by radiation of different wavelengths (i.e. selectively activated).

Of interest, the method described above in which photolents catalyst (a) is a mixture of at least one votolatino basic catalyst (A2) and at least one votolatino acid catalyst (A1) and in which the composition includes a mixture cured at catalysis acid compounds (b) and cured at catalysis based compounds (C), provided that (A1) and (A2) selectively activated.

In addition, the composition proposed in the present invention may contain a radically polymerizable whom onent. Examples are

(Meth)acrylate compounds which can be mentioned are (meth)acrylic esters and preferably acrylic esters of polyfunctional alcohols, preferably such that in addition to the hydroxy groups or do not contain other functional groups, or contain only simple ester groups. Examples of such alcohols are bifunctional alcohols, such as ethylene and propylene glycol and the representatives of the same class with higher degrees of condensation, such as dietilen, triethylene, DIPROPYLENE and tripropyleneglycol etc., butanediol, pentanediol, hexanediol, neopentylglycol, alkoxysilane phenolic compounds, such as ethoxylated and propoxycarbonyl bisphenola, cyclohexanedimethanol, alcohols containing three or more functional groups, such as glycerin, trimethylolpropane, butanetriol, trimethylacetyl, pentaerythritol, ditrimethylol, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxysilane alcohols, preferably ethoxylated and propoxycarbonyl alcohols.

Products alkoxysilane can be obtained by known methods by the reaction of the above alcohols with acceleratedly, preferably ethylene or propylene oxide. Preferably, if the degree of alkoxysilane in terms of the hydroxy-group Rav is and 0-10; in other words, 1 mol of hydroxyl groups preferably can be alkoxylated with up to 10 moles of alkalisation.

Other (meth)acrylate compounds are complex polyester(meth)acrylates, which are acrylic esters of complex polifenoles.

Examples of suitable complex polifenoles are such that can be obtained by the esterification of polybasic carboxylic acids, preferably dicarboxylic acids, with polyols, preferably dialami. The source of the substance to obtain a hydroxy-group containing polyesters of this type are known to the person skilled in the art. As dicarboxylic acids preferably succinic, glutaric, adipic, Sabatino and o-phthalic acid, their isomers and hydrogenation products and are capable of forming esters derivatives, such as anhydrides or dialkyl ethers of these acids. Suitable polyols are the abovementioned alcohols, preferably ethylene glycol, 1,2-and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, cyclohexanedimethanol and polyglycols type ethylene glycol and propylene glycol.

Complex polyester(meth)acrylates can be obtained in several stages or even in a single phase, as described, for example, in EP 279303, from acrylic acid, polybasic karbonvansty and polyol.

Other examples are epoxy and urethane(meth)acrylates.

Examples of the epoxy(meth)acrylates are those who get reactions epoxydecane olefins or poly - and/or diglycidyl esters, such as obtained by the reaction diglycidylether ether of bisphenol a with (meth)acrylic acid.

This reaction is well-known specialist in the art and described, for example, in the publication R.Holmann, U.V. and E.B.Curing Formulation for Printing Inks and Paints. London 1984.

The urethane(meth)acrylates are preferably the reaction products, hydroxyalkyl(meth)acrylate with poly - and/or diisocyanates (see also R.Holmann, U.V. and E.B.Curing Formulation for Printing Inks and Paints. London 1984).

Of course, it is also possible to use mixtures of different radically polymerizable compounds described above, in particular, including mixtures of the above (meth)acrylic compounds.

In addition to votolatino the catalyst (a) polymerizable mixture may include various additives (h).

Their examples are inhibitors of thermal effects, which are intended to prevent premature polymerization, for example, hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol and steric employed phenols, for example 2,6-di(tert-butyl)-p-cresol and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (p-hydroxy-tempo), bis(2,2,6,6-tetramethyl-1-oxyl-4-piperidinyl)-is ebcat and 1-methyl-8-(2,2,6,6-tetramethyl-1-oxyl-4-piperidinyl)-sebacate. To improve the stability during storage in the dark can be used, for example, compounds of divalent copper, such as the naphthenate, stearate or octoate copper, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethylphosphine, triphenylphosphine or tribenzylphosphine, Quaternary ammonium compounds, such as Tetramethylammonium or trimethylphenylammonium, or derivatives of hydroxylamine, for example N-diethylhydroxylamine.

As additional additives in the composition may be added to the light stabilizers (e). Examples are absorbers of UV radiation, for example, type hydroxyphenylacetate, hydroxyphenylpropionic, amide of oxalic acid or hydroxyphenyl-SIM-triazine. Such compounds can be applied by themselves or as mixtures with or without the use of sterically obstructed amines (HALS).

Specific examples of such absorbers of UV radiation and light stabilizers (e) are

1. 2-(2'-Hydroxyphenyl)benzotriazole, for example, 2-(2'-hydroxy-5'-were-benzotriazol, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-TETRAMETHYLBUTYL)-phenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-were)-5-chlorobenzotriazole, 2-(3'-sec-BU the Il-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)-benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)-benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-were-benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctylmercaptoacetate)-phenylbenzothiazole, 2,2'-Methylenebis[4-(1,1,3,3-TETRAMETHYLBUTYL)-6-benzotriazol-2-infenal]; the product of transesterification of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-benzotriazole polyethylene glycol 300; [R-CH2CH2-COO(CH2)3]2-where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2. 2-Hydroxybenzophenone, for example 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy - and 2'-hydroxy-4,4'-dimethoxypropane.

3. Esters of substituted and unsubstituted benzoic acids. for example, 4-tert-butylanisole, is uninsalled, antifederalist, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylation, 2,4-di-tert-BUTYLPEROXY ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecylamine ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecenoic ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid and 2-methyl-4,6-di-tert-BUTYLPEROXY ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid.

4. Acrylates, such as ethyl ether and isooctyl ester, α-cyano-β,β-diphenylacetone acid, methyl ester of α-methoxycarbonylamino acid, methyl ester and butyl ester α-cyano-β-methyl-p-methoxycatechol acid, methyl ester α-methoxycarbonyl-p-methoxycatechol acid and N-(β-carbomethoxy-β-lanvins)-2-methylindolin.

5. Steric employed amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethylpiperidin)sebacate, bis(1,2,2,6,6-pentamethylpiperidine) ether n-butyl-3,5-di-tert-butyl-4-hydroxybenzylidene acid, condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-tert-octylamine-2,6-dichloro-1,3,5-triazine, Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetriol, 1,1'-(1,2-atandi the l)bis(3,3,5,5-tetramethylpiperidine), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-sterilox-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidin)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)succinate, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidine)-1,3,5-triazine and 1,2-bis(3-aminopropylene)ethane, condensation product of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin)-1,3,5-triazine and 1,2-bis(3-aminopropyl)aminoethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidin-2,5-dione, 2,4-bis[N-(1-cyclohexyloxy-2,2,6-6-tetramethylpiperidine-4-yl)-n-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine and the product of condensation of 2,4 bis[1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-6-chloro-SIM-triazine and N,N'-bis(3-aminopropyl)Ethylenediamine.

As known to a person skilled in the art if a method proposed in the present invention, is carried out using votolatino acid as votolatino catalyst, to prevent the Oia inhibition of curing should carefully choose the type and concentration of sterically constrained Amin.

6. Dimity oxalic acid, for example 4,4'-distractionware, 2,2'-diethoxyaniline, 2,2'-dioctyloxy-5,5'-di-tert-butylanisole, 2,2'-didodecyl-5,5'-di-tert-butylanisole, 2-ethoxy-2'-ethyloxazole, N,N'-bis(3-dimethylaminopropyl)oxalate, 2-ethoxy-5-tert-butyl-2'-ethyloxazole and their mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxyaniline and mixtures of o - and p-methoxy - and of o - and p-ethoxybenzylidene of oxanilide.

7. 2-(2-Hydroxyphenyl)-1,3,5-triazine, for example 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-proproxyphene)-6-(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-were)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butylenediamine)phenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxyphenyl)phenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine and 2-[4-(dodecyloxy/tridecylamine-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine.

and 2-[4-dodecyloxy/tridecylamine-(2-hydroxypropyl)oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine.

8. The phosphites and phosphonites, for example triphenylphosphite, diphenylacetate, phenyldichlorophosphine, Tris(nonylphenyl)FOSFA, trilaureth shit, trioctadecyl, distearyldimethylammonium, Tris(2,4-di-tert-butylphenyl)FOSFA, diisodecylphthalate, bis(2,4-di-tert-butylphenyl)pentaerythrityl, bis(2,6-di-tert-butyl-4-were)pentaerithritol, bis-isodecyloxypropylamine, bis(2,4-di-tert-butyl-6-were)pentaerithritol, bis(2,4,6-tri-tert-butylphenyl)pentaerythrityl, traceability, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediisocyanate, 6-isooctane-2,4,8,10-Tetra-tert-butyl-N-dibenz[d,g]-1,3,2-dioxaphospholane, 6-fluoro-2,4,8,10-Tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphospholane, bis(2,4-di-tert-butyl-6-were)metaltastic and bis(2,4-di-tert-butyl-6-were)ethylphosphate.

9. Other inorganic compounds, such as nanometer titanium dioxide.

Examples of absorbers of UV radiation and light stabilizers, applicable as components (e)include "Krypto-UVA", described for example in EP 180548. You can also use latent absorbers of UV radiation, as described, for example, in the publication of Hida et al in RadTech Asia 97, 1997, page 212.

The content of the light stabilizers (e) in the compositions is, for example, from 0.01 to 10 wt.%, for example from 0.05 to 5 wt.%, preferably from 0.1 to 5 wt.% in terms of solid binder. Used concentration varies depending on the thickness of the coating layer. The thinner the layer, the more the more should be the concentration of the selected component (s). This should be known to the specialist in the art and are described in detail in the literature.

You can also use other additives commonly used in the art, such as antistatic agents, substances that improve fluidity, and amplifiers adhesion.

The composition can also be added to the reagents transmitter circuit, commonly used in the art. Examples are mercaptans, amides and benzotriazol.

The operation of curing, in particular pigmented compositions (e.g., pigmented with titanium dioxide) can be facilitated by adding as additional additives (h) component, which when heated forms free radicals, for example, uzasadnienie, such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), Triesen, dissolved, pentadien, or peroksosoedinenii, for example, hydroperoxide or peroxocarbonate, for example, tert-butylhydroperoxide described, for example, in EP 245639.

As an additive (h) you can also add supplements designed to increase mechanical stability, for example, to improve resistance to scratching, in the form of nanoparticles. Examples are disclosed in EP 114917.

Other conventional additives (h) in accordance with the purpose of are fluorescent whitening agents, fillers, pigments, white and colored PI the cops, dyes, antistatic agents, wetting agents and additives that improve the fluidity.

For curing thick and pigmented coatings suitable addition of glass beads or powdered glass fibers, as described, for example, in US 5013768.

The choice of additives depends on the scope and characteristics required for this area. The above-described additives (h) normal to the art and accordingly are used in amounts customary for this area of technology.

The content of additional additives (h) in the compositions proposed in the present invention is, for example, from 0.01 to 10 wt.%, for example from 0.05 to 5 wt.%, preferably from 0.1 to 5 wt.%.

The stitching can be accelerated by the addition of photosensitizers (f), which shift or broaden the spectral sensitivity. Such photosensitizers are preferably aromatic carbonyl compounds, for example, derivatives of benzophenone, derivatives of thioxanthone, preferably, isopropylthioxanthone, derivatives of anthraquinone and derivatives 3-acicularis, terphenyls, tirikatene, and 3-(koimeterion)-thiazoline, comparison and eosinophile, rodnikovye and erythrosine dyes.

The above amines, for example, can also be viewed as photosensitizers.

Updat the comparative examples of such photosensitizers are

1. Thioxanthone

Thioxanthone, 2-isopropylthioxanthone, 3 isopropoxytitanium, 2,4-dietitican, 2,4-dimethyldioxanes, 1 methoxycarbonylamino, 2-ethoxycarbonylmethoxy, 3-(2-methoxyethoxymethyl)-thioxanthone, 4-butoxycarbonylamino, 3-butoxycarbonyl-7-methylthionine, 1-cyan-3-chlorothioxanthone, 1-etoxycarbonyl-3-chlorothioxanthone, 1-etoxycarbonyl-3-etoxification, 1-etoxycarbonyl-3-aminothiazole, 1-etoxycarbonyl-3-phenylsulfonylacetate, 3,4-di[2-(2-methoxyethoxy)etoxycarbonyl]thioxanthone, 1-etoxycarbonyl-3-(1-methyl-1-morpholinoethyl)-thioxanthone, 2-methyl-6-dimethoxymethylsilane, 2-methyl-6-(1,1-dimethoxybenzyl)-thioxanthone, 2-morpholinoethoxy, 2-methyl-6-morpholinoethoxy, N-allithiamine-3,4-dicarboximide, N-artisticchardon-3,4-dicarboximide, N-(1,1,3,3-TETRAMETHYLBUTYL)-thioxanthone-3,4-dicarboximide, 1 renoxification, 6-etoxycarbonyl-2-detoxification, 6-etoxycarbonyl-2-methylthionine, thioxanthen-2-polietilenglikolya ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-N-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium.

2. Benzophenone

Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 3-methyl-4'-phenylbenzophenone, 2,4,6-trimethyl-4'-phenylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzoate is h, 4-methylbenzophenone, 2,4,6-trimethylbenzene, 4-(4-methylthiophenyl)-benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate, 4-(2-hydroxyethylthio)-benzophenone, 4-(4-tolylthio)benzophenone, 4-benzoyl-N,N,N-trimethylmethanaminium, 2-hydroxy-3-(4-benzoylperoxy)-N,N,N-trimethyl-1-propanimidamide, 4-(13-acryloyl-1,4,7,10,13-intoximeter)-benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethylbenzyltoluidines, 2,4,6-trimethyl-4'-phenylbenzophenone, 3-methyl-4'-phenylbenzophenone.

3. 3-Acicularis

3-Benzoyltartaric, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichloroaniline, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-isobutylamino, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxyaniline, 3-benzoyl-5,7-diputaciones, 3-benzoyl-5,7-di(methoxyethoxy)-coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyryl-7-diethylaminocoumarin, 5,7-dimethoxy-3-(1-naphtol)-coumarin, 5,7-dimethoxy-3-(1-naphtol)-coumarin, 3-benzoylbenzene[f]coumarin, 7-diethylamino-3-tenormin, 3-(4-lebensohl)-5,7-dimethoxycoumarin.

4. 3-(Koimeterion)-thiazoline

3-Methyl-2-benzoylmethylene-□-negotiaiton, 3-methyl-2-benzoylmethylecgonine is, 3-ethyl-2-propionitrile-□-negotiaiton.

5. Other carbonyl compounds

The acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylation, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)Cyclopentanone, □-(para-dimethylaminobenzylidene)ketones, such as 2-(4-dimethylaminobenzylidene)-indan-1-he and 3-(4-dimethylaminophenyl)-1-indan-5-ispropanol, 3-phenylthiophene, N-methyl-3,5-di(ethylthio)phthalimide.

The content of the sensitizers (f) in the compositions proposed in the present invention is, for example, from 0.01 to 10 wt.%, for example from 0.05 to 5 wt.%, preferably from 0.1 to 5 wt.%.

The composition can also contain dyes and/or white or colored pigments (g). It is possible to use inorganic or organic pigments. Such additives are known to the specialist in the art, some examples are pigments based on titanium dioxide, such as rutile or anatase, carbon black, zinc oxide, such as zinc white, iron oxides, such as yellow iron oxide, red iron oxide, chrome yellow, chrome green, Nickel-titanium yellow, ultramarine blue, cobalt blue, bismuth Vanadate, cadmium yellow and cadmium red. Examples of organic pigments are mono - and bis-azo pigment, as well as their complexes with metals, phthalocya the new pigments, polycyclic pigments, such as Pereladova, antrahinonovye, thioindigo, chinaredorbit and triphenylmethane pigments, and diketopiperazine, isoindolines, for example tetrachlorotoluene, isoindoline, dioxazine, benzimidazolone and hinaplanon pigments.

Pigments can be used in the compositions separately or in a mixture.

Depending on the destination pigments are added in the composition in amounts customary for this technical field, for example in a quantity of from 0.1 to 60 wt.%, from 0.1 to 30 wt.% or from 10 to 30 wt.% in terms of total mass.

The composition can also, for example, contain organic dyes of different classes. Examples are azo dyes, methine dyes, antrahinonovye dyes and metal complex dyes. Typical concentrations are, for example, from 0.1 to 20 %, preferably from 1 to 5 % in terms of total mass.

The method proposed in the present invention, is particularly suitable for curing and subsequent processing of pigmented compositions. Accordingly, a preferred method in which a composition comprising a photocatalyst, further includes a dye or pigment (g). Preferably, if the composition otverzhdajutsja using catalytic base.

In may the STI from the applied compositions as stabilizers can also be used to neutralize acid compounds, preferably amines. Suitable systems are described, for example, in JP-A 11-199610. Examples are pyridine and its derivatives, N-alkyl - and N,N-dialkylanilines, derivatives pyrazine, derivatives of pyrrole, etc.

The present invention also relates to a method, described above, in which the composition in addition to votolatino component (a) includes other additives (h), sensitizing compounds (f) and/or dyes or pigments (g).

Also interested in the way described above, in which the composition as an additional additive (s) includes at least one light and/or at least one absorber of UV radiation.

In addition, the composition may include fillers transparent and optically opaque. In this context, optically transparent means transparent with respect to radiation, which is used to activate the catalyst. Examples are materials, canvas, fabrics, fibers, threads of natural or synthetic origin, for example plastics, nylon, polyesters, and the like, hardened materials, putty, glass, carbon black, etc.

In the method proposed in the present invention, the said composition comprising fatalaty the catalyst is activated by exposure to additional processing and curing.

However, you can also cure to the position, containing one or more of the above-described fillers or pigments, dyes or other additives, and optional fatalaty catalyst, by mixing the specified "full" and not necessarily optically opaque composition, i.e. opaque paste, with the formation of a transparent composition, which includes fatalaty catalyst and activated by irradiation to the mix.

In other words, in the method proposed in the present invention, after exposure of the composition (optically transparent to radiation), including fatalaty the catalyst, it is mixed with other cured composition, for example comprising optically opaque fillers or additives, and the resulting mixture is cured using pre-activated composition.

After activating composition containing fatalaty catalyst, by using the stage of irradiation, it is also possible to admix other additives or components.

Suitable radiation sources for irradiating the compositions are radiation sources that emit radiation with a wavelength of approximately from 150 to 1500, for example from 180 to 1000, or preferably from 190 to 700 nm, electron beam and the electromagnetic radiation of high energy, such as x-ray radiation, and microwave radiation. The approach is concerned are point sources and plane projectors (arrays of lamps). Examples are: coal arc lamps, xenon arc lamps, mercury lamps, medium pressure, high pressure and low pressure, optionally with the addition of metal halides (metallogenesis lamp), lamp discharge metal vapor with microwave excitation, an excimer lamp, overactivity fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flash lamps, strobing light sources, photographic projectors, cold flat paleobasin sources of radiation in the UV-visible region of the spectrum (such as EXFO Photonic solutions), electron beams and beams of x-rays formed by synchrotrons or laser plasma. The distance between the radiation source and the irradiated composition may vary, for example, from 2 to 150 cm depending on the purpose and type and/or power source. Suitable radiation sources are preferably mercury lamps, more preferably a mercury lamp, medium-pressure and high-pressure of radiation which, if necessary, you can filter line emission at other wavelengths. This applies in particular to the relatively short-wave radiation. However, it is possible to use lamps low energy (for example, fluorescent tubes), which can radiate in a suitable range is not wavelength, for example lamp Philips TL03. Other types of radiation sources that can be used are light-emitting diodes (LEDs)that emit at different wavelengths across the spectrum or narrow-band emitting source, or in the form of a broadband emitting source (white light). Also suitable laser radiation sources, for example excimer lasers, such as lasers Kr-F for radiation at a wavelength of 248 nm, lasers Ar-F at 193 nm, or a laser F2at 157 nm. You can also use lasers in the visible region and the infrared range. The source is also suitable source is, for example, argon ion laser, which emits at wavelengths 454, 458, 466, 472, 478, 488 and 514 nm. You can also use Nd-YAG lasers doped with neodymium yttrium aluminum garnets), emitting at 1064 nm and its second and third harmonics (532 and 355 nm, respectively). Also suitable, for example, helium/cadmium laser, emitting at 442 nm, and the laser emitting in the UV range. In addition, suitable radiation of relatively low intensity. These types of radiation include, for example, fluorescent light (sunlight) and the radiation sources equivalent to daylight. Sunlight on the spectral composition and intensity differs from artificial sources of radiation, commonly used in UV-curing. Ha is acteristic absorption compounds, proposed in the present invention, also suitable for use sunlight as a natural source of radiation for curing. Equivalent to daylight artificial radiation sources that can be used to activate the compounds proposed in the present invention, it should be understood, the emitters of low intensity, such as certain fluorescent lamps, such as fluorescent lamp Philips TL05 or special fluorescent lamp Philips TL09.

You can also carry out curing by using a gaseous plasma. Possible methods of obtaining plasma in vacuum is described in detail in the literature.

Irradiation of the composition can, for example, to carry out directly, and also can provide a back-side transparent layer (for example, through a sheet of glass or plastic).

Irradiation of the composition before applying the specified composition on a substrate or subsequent to processing the compositions can, for example, by direct irradiation of the composition in the container or vessel in which it is prepared or stored.

In this case, the radiation source include, for example, over the vessel, for example, on a mixer. Another possibility is to use a transparent container, for example, made of glass or plastic and exposure to the notizie directly through the container. In the context of the present invention, "transparent" means that the radiation used to activate, can pass through the material. In this case, the radiation sources are placed outside of the container. The container can, for example, cover the outside of the panel with lamps.

Another option irradiation of the composition is the inclusion of the lamp directly into the composition, for example, by protecting the lamp transparent container and introducing the container into the container containing the irradiated composition. You can also include a radiation source in the node equipment used for the preparation of compositions, for example, in the mixer. In addition, the irradiation can be performed using fiber that is immersed in the composition.

In addition, the container with irradiated composition can be placed in the camera, fitted with a suitable radiation source or multiple light sources arranged, for example, from the top, or one on top or some or all of the side walls of the chamber, or even all of the side walls, even including the location under the bottom of the camera if the container containing the composition is transparent.

Irradiation can also be carried out shortly before application of the composition on a substrate, for example, using a spray device with a transparent inlet tube and the placement is receiving radiation source over the transparent portion of the specified tube. The radiation source can also be placed after the exit of the spray gun to irradiate sprayed pair. In addition, the radiation source can be positioned inside or outside from the nozzle of the spray device.

Suitable irradiating devices known to the person skilled in the art are, for example, submersible sump type, such as, for example, reactors ACE, produced, for example, Sigma-Aldrich, photoreactor drum type, irradiating apparatus annular shape, such as photochemical reactor Rayonette, flow-through photochemical reactor (for example, J.Cooke, G.Austin, M.J.McGarrity, WO 9635508), camera for exposure, such as produced by the firm Luzchem Inc. with irradiation from above (for example, Luzchem LZC-1/LCZ-PAP), with irradiation side (for example, Luzchem LZC-5/LCZ-ORG), or with irradiation from above and from the side (for example, Luzchem LZC-4V); multivalve three-phase lighting apparatus, photoreactor tank type, photoreactor with light-emitting devices, suspended in the reaction mixture (for example, JP 59059246 A2), steel photochemical reactors (for example, L.Teodorescu, G.Musca, E.Mocanu, H.Culetu, N.Rada, RO 93292 B1), flow-through reactors (for example, D.W. Clark et al Icarus 200, 147, 282), photoreactor with a falling film (for example, H.Ehrich et al., Chimia 2002, 56, 647), fountain photoreactor, photoreactor with pulsating flow photoreactor with a guide tube and reflectors, ring fo reactor continuous action, photochemical reactors semi-continuous action (for example, .Herbert, J.Ollivier, G.Fremy, WO 202081080 A1), tubular photoreactor (for example, A. Tkac, CS 249894 B1), thin-film cascade photoreactor, laser photochemical reactors with a large fluence (for example, L..Gantayet, S. Sethi, Adv. Chem. Eng. Nucl. Process Ind. 1994, 146), microphotometry H. Lu et al, Lab on a Chip 2001, 1, 22), small reactors (James E. Gano, Andrew J. Gano, Patricia Garry, and Padmanabhan Sekher, J. Chem Edu. 2002, 79(11) 1361), platform reactors.

Review of existing photoreaction see, for example, in the publications A.M.Braun, M.-T.Maurette, E. Oliveros, "Photochemical Technology", Wiley, Chchester, West Sussex, England/New York 1993; A.M.Braun, M.-T.Maurette, E.Oliveros, D.F.Oilis, N.Serpone, "Industrial Photochemistry", M.L.Viriot, J.C.André, A.M.Braun, eds., CPIC-ENSIC, Nancy, 1990, Vol.A, 253-301 "Photochemical reactors"; and "Chemical Reactor Design and Technology: Overview of the New Developments of Energy and Photochemical Reactor Technologies. Projections for the 90's" by NATO Advanced Study Institute on "Chemical Reactor Design and Technologies, Hugo I. De Lasa (Editor), North Atlantic Treaty Organization Scientific Affairs Division. Fundamentals of photoreactor engineering are reported in J. Costa Lopez, Afinidad 1977, 34(343), 19. Discussion of the main provisions technologies photochemical reactions are also described in the publication L. Rizzuti, A. Brucato, NATO ASI Series, Series C: Mathematical and Physical Sciences (1988), 237, 623.

The embodiment of the present invention is also a method in which irradiation is carried out in a vessel, reservoir, pumping cycle, continuous irradiation device at the outlet of the evaporator, inside or outside of the spray gun, advogada pipes or inkjet printer.

In particular, the composition is irradiated directly in the storage tank and then sent for further processing.

Photochemical activation can be periodic or continuous manner.

Accordingly, another object of the present invention is a method characterized in that it is carried out continuously by pumping the composition comprising fatalaty catalyst (a) from the storage tank through the inlet pipe past the radiation source directly into the application device.

The time from exposure to the curing of the composition, which allows you to perform additional processing stage can be adjusted in the range from 0.1 s up to several days, e.g. 7 days, preferably from 1 to 24 hours, most preferably from 2 to 8 hours

The time interval can be adjusted in accordance with the need by appropriate selection and combination votolatino catalyst, sensitizer, the radiation source and the components of the composition.

Therefore, the way in which additional treatment is carried out for from 0.5 to 7 days after exposure of the composition is also an object of the present invention.

The method proposed in the present invention preferably takes place in the form of a method of applying a coating to mean the LCD in which

(A) a composition including

(b) curing during the catalysis of the acid component and

(A1) connection votolatino acid as defined above;

or

(B) a composition including

(c) curing during the catalysis of the base component and

(A2) connection votolatino base as defined above;

or a mixture of (a) and (b)

are irradiated by electromagnetic radiation, in particular UV radiation, and

then applied to the substrate.

Preferably, if the composition in the method proposed in the present invention, is a composition of varnish or optional adhesive composition comprising a polyol in combination with isocyanate and as votolatino catalyst - votolatino base (A2) of the formula VIII, VIIIa and VIIIb

,,,

in which r is 0 or 1;

X4denotes CH2or;

R2and R3all independently of one another denote hydrogen or C1-C20alkyl;

R1denotes unsubstituted or1-C20alkyl or C1-C12alkoxy-substituted phenyl, naphthyl or biphenylyl;

R20, R30and R40together with the associated nitrogen atom denote a group of the structural formulaor

anion represents any anion capable of forming a salt; and m denotes the number of positively charged N atoms in the molecule.

Suitable polyols and isocyanates are usually such as described above. Suitable polyols and isocyanates are preferred for the composition of the adhesive, described below in the present description.

Also of interest is the method of application votolatino catalyst (a) in which a composition including a specified catalyst, is subjected to irradiation before further processing, in which the composition is the composition of varnish or optional adhesive composition comprising an epoxy component and as votolatino catalyst - votolatino base (A2) of the formula VIIIa,

in which

r is 0 or 1;

X4denotes CH2or;

R1denotes unsubstituted or1-C12alkyl or C1-C12alkoxy-substituted phenyl, naphthyl or biphenylyl;

R20. R30and R40together with the associated nitrogen atom denote a group of the structural formula (a), (b) or (C),,,;

R35denotes hydrogen or C1-C18alkyl;

anion represents any anion capable of forming a salt; and m on the mean number of positively charged N atoms in the molecule.

Suitable epoxy components described above. Preferred epoxides are the type of bisphenol A.

The composition in the manner described above relating to the composition of varnishes and adhesives, preferably is an adhesive.

As mentioned above, the method proposed in the present invention is also applicable for the coating of adhesive, such as laminating, installation or compression bonding adhesives, such as, for example, compression bonding hot melt adhesives. In particular, it is applicable in the technology of laminating non-transparent substrates, in which the activation of the adhesive composition by irradiation with light may occur before the connection of two layup parts.

The adhesive composition is typically cured under catalysis by acid or base catalysis composition based on epoxy component or the isocyanate component, forming the polyurethanes. Suitable components of the epoxy and isocyanate type, as well as appropriate focoltone base and focoltone acid already described above.

Examples of suitable polyurethane adhesives are also suitable for use in the method proposed in the present invention, shown in US 2005/027091. These compositions comprise (a) an aliphatic or alicyclic polyisocyanate, containing ≤3 funktsionalnykh, and (b) the mixture is ≥1 polypropylenglycol and polypropylenglycol (the ratio of the number of diol groups by the number trialing groups IS<10 and the ratio of NCO groups to the number of groups HE 0,95<n<1,05 where diols having molecular weight ≤1000, used in conjunction with triodes, with a molecular weight ≥1000, and diols having a molecular weight of >1000, used in conjunction with trioligy, having a molecular weight of <1000. To these compositions add fatalaty the catalyst described above, in the above stated amount.

More suitable polyurethane compositions of the type disclosed, for example, in US 2004/265529, US 2005/019560, WO 04/055087, US 6596787.

In addition, one-component polyurethane adhesives disclosed in WO 03/050155, can be obtained by the method proposed in the present invention, using as the amine catalyst votolatino reasons described above.

Accordingly, also of interest is the method of application votolatino catalyst (a), in which the composition is an adhesive. Also interested in the way described above, in which photolents catalyst is votolatino base (A2) and the composition is cured at catalysis a ground connection (s).

The method proposed in the present invention, it is also possible note is measured repeatedly. In this case, first, the composition proposed in the present invention, activated by irradiation and then further subjected to necessary processing. Then activate the second composition, and processed in the same application. This procedure can be repeated a necessary number of times. It is commonly known as the wet deposition of the composition on a wet material. Focoltone catalysts, applied at different stages, may be the same or different and at each stage can be independently represent votolatino acid or votolatino basis. In addition, at different stages cured under catalysis by base or acid catalysis components may be the same or different. An example of this application is, for example, multilayer coating, in which, for example, the first coating layer is applied as a primer on the material of the carrier, and then put the second layer, which may contain a pigment, and on top put the third layer, which is transparent protective coating. After application of all layers of the system utverjdayut, for example, by heating. Because when applying the next layer previous layer is not yet fully hardened, the boundary layers can occur a certain mix of different materials, coatings, resulting in improved ADG is Ziya different layers.

In such a multi-stage procedure does not require that each layer represented the activated coating obtained by the method proposed in the present invention. For example, you can add only one active layer and the other layer without catalyst. Then the activated layer can act as a binder or adhesive, as noted above.

In another embodiment, the present invention method repeatedly and at every stage, the catalyst is the same as at the other stages, or different and independently represents votolatino acid and/or votolatino base.

In the specified way repeated next stage of processing, for example, the curing is not necessarily performed immediately after activation and coating compositions. Every single song activate and put one after the other and finally curing all coatings carried out in one stage. However, it is possible to carry out the curing each coating immediately after activation and coating before applying the next activated coating.

"Activated" in the context of this invention means that the composition comprising fatalaty the catalyst is subjected to irradiation, which then activates fatalaty the catalyst contained in the composition.

In the way that is written above, one stage or more stages can be carried out with compositions comprising fatalaty catalyst (activated prior to application), and one or more compositions containing low fillers and/or pigments, and optionally including fatalaty catalyst. This means that the first composition comprising fatalaty catalyst, activated by irradiation and then applied to the substrate, and the second composition, the same or different from the first and optionally including fatalaty catalyst, is applied on top of the first, etc. After applying all the necessary coatings conduct curing, for example, by heating and/or additional exposure.

The method proposed in the present invention, for example, repeated from 2 to 10 times, for example from 2 to 5 times or 2 to 3 times. These compositions containing large amounts of opaque fillers and/or pigments, can be used in the form of a paste, i.e. opaque paste.

The object of the present invention is also a method in which the subsequent processing is an additional step of curing using UV radiation and/or heat.

Another embodiment of the present invention is a substrate on which is deposited the composition according to paragraph 1 of the claims.

Comp the positions, used in the way proposed in the present invention, can be used for different purposes, for the manufacture of coatings for surfaces, printing inks, inks for screen printing inks for offset and flexographic printing, as a transparent finishing layer, as a white or colored topcoat, for example for wood or metal, as powder coatings, as a material for coating, in particular for paper, wood, metal or plastic, as cured when exposed to fluorescent light coating for the marking of buildings and road markings, as compositions for dental seals, as adhesives, as compression bonding adhesives, resins for laminating, to obtain three-dimensional products by curing in bulk or by injection molding, to obtain a composite material (for example, styrene polyesters, which optionally may contain fiberglass and/or other fibres and other auxiliaries) and other tolstolistyj composite materials, for coating electronic components and integrated circuits, or sealing, or as coatings for optical fibers, or for the manufacture of optical lenses, such as contact lenses or Fresnel lenses. It is notizie in the way, proposed in the present invention, also suitable for the manufacture of medical equipment, assistive devices and implants and for the manufacture of gels having thermotropic properties, as described, for example, in DE 19700064 and EP 678534.

The composition cured by the method proposed in the present invention can also be applied, for example, as materials for repair and plaster.

Structured objects can be created, if the processing stage includes a step of printing or embossing, in which the activated composition in the form of an image applied to a suitable substrate. It is possible, for example, by using lithography with soft contact developed G.Whitesides (for example, Xia, Y., and G.M.Whitesides, Extending microcontact printing as a microlithographic technique. Langmuir 1997, 13, 2059-67; Xia, Y., D.Qin, and G.M.Whitesides, Microcontact printing with a cylindrical rolling stamp: A practical step toward automatic manufacturing of patterns with submicrometer-sized features. Adv. Mater. 1996, 8, 1015-17). Then put thus the composition sew through acid catalyzed or base curing. Thus obtained microstructure can, for example, be used in the methods of reproduction, image recording, for the manufacture of printed forms, as resists for etching, for soldering resists, resists for deposition or temporary resists, both liquid and solid films, ka is estwe of resists for thin-film transistors, for printed circuits and electronic circuits, as resists to manufacture color filters, for example, for formation of pixels of red, green and blue colors and a black matrix; for different types of applications in displays or for the formation of structures in the manufacture of plasma displays and electroluminescent displays.

The method proposed in the present invention can also be used to obtain powder coatings.

The meaning of the terms "composition of powder coatings or powder coatings correspond to the definitions given in the publication "Ullmann''s Encyclopedia of Industrial Chemistry, 5th, Completely Revised Edition, Vol.A18", pages 438 to 444 (1991) in Section 3.4. The powder coating shall mean a thermoplastic or heat-resistant, slivaushiesia polymers, which are in powder form is applied mainly on the metal substrate. To ensure the interaction of the powder with the product that you want to apply the coating, use different methods of application, such as electrostatic spraying powder, electrostatic sintering in psevdoozhizhenom layer, sintering in a fixed bed, a rotary sintering or centrifugal sintering.

In the context of the present invention the powder coating composition to activate the application.

Preferred organic film-forming binder for HDMI the Nations of powder coatings, proposed in the present invention, systems are a hot drying, based on, for example, epoxy resins, complex polyesters-hydroxyalkylated, complex polyesters-glycoluril, epoxy-complex polyester resins, complex polyesters-triglyceriderich, hydroxy-group containing complex polyesters-blocked polyisocyanates, hydroxy-group containing complex polyesters-uretdione, acrylate resins with curing agents or mixtures of such resins.

Polyesters typically contain hydroxy or carboxypropyl and are typically prepared by condensation of diols with dicarboxylic acids. By adding polyols and/or polyhydric acids obtain branched polyesters, which upon further heat treatment in the presence of crosslinking agents provide a mesh structure, which give the coating the necessary physical characteristics, such as resistance to scratching, impact resistance and bending strength. Instead of multifunctional acids it is also possible to use anhydrides or acid anhydrides, such as maleic anhydride, itacademy anhydride, phthalic anhydride, terephthalic anhydride, hexahydroterephthalate anhydride, trimellitic anhydride, pyromellitic dianhydride, succinic anhydride, etc. you can Also use ordinary esters, such as imyinterface, in this case, for example, polymerization proceeds by transesterification with removal of volatile alcohol. It is also possible getting through a combination of transesterification and condensation. In addition, the polyesters can be obtained by polycondensation hydroxycarbonic acids such as 12-hydroxystearate acid and hydroxytrimethylene acid, or the corresponding lactones, such as ε-caprolactone. Examples of dicarboxylic and polybasic acids include terephthalic, isophthalic, adipic, azelaic, Sabatino, 1,12-dodecandioic, pyromellitate, 3,6-dichlorphenol, amber, 1,3-cyclohexanecarbonyl and 1,4-cyclohexanecarbonyl acid. Examples of diodes and polyols include ethylene glycol, propylene glycol, diethylene glycol, hexanetriol, hexane-2,5-diol, hexane-1,6-diol, pentaerythritol, sorbitol, neopentylglycol, trimethylacetyl, trimethylolpropane, Tris-1,4-cyclohexanedimethanol, trimethylpentanediol, 2,2-diethyl-1,3-propandiol, 2-methyl-2-butyl-1,3-propandiol, esterdiol 204 (ester hydroxytrimethylene acid and neopentyl glycol), hydrogenated bisphenol a, bisphenol a, hydroxytrimethylene acid esters hydroxytrimethylene acid, 2-butyl-2-ethyl-1,3-propandiol, 1,4-butanediol, 2-butene-1,4-diol, 2-butyn-1,4-diol and 2-methyl-1,3-propandiol.

For containing carboxypropyl complex pole is IRow suitable cross-linking reagents are epoxysilane, such as epoxy novolak®, diglycidyl ethers of bisphenol a, hydrogenated bisphenol a and bisphenol a, modified by reaction with, for example, aliphatic dicarboxylic acids. Also suitable are reactive to epoxysilane, such as tripyridyltriazine-3,5-dione, glycidyloxy esters of polybasic acids, such as diglycidylether and diglicidylmethylphosphonate, epoxides as (US 4402983) and, preferably, triglyceriderich, esters epoxydecane unsaturated fatty acids (for example, Uranox produced by the company DSM) and Araldit®PT 910 (Ciba Spezialitatenchemie AG). Other cross-linking reagents containing carboxypropyl polyesters are β-hydroxyethylamide (US 4076917), such as, for example, mainly containing four functional groups of β-hydroxyalkylated adipic acid (Primid®XL552 produced by the company Rohm & Haas). Also proved to be suitable derivatives of melamine, benzoguanamine and glycoluril, which is alkylated alcohols with low molecular masses. Examples are tetramethyleneglutaric (Powderlink®1174, produced by American Cyanamid). Furthermore, as cross-linking reagents known bis - and trimoxazole, such as 1,4-isoxazolidinone.

Recently discovered containing the carboxypropyl complex polyester, which contains chemically related epoxypropyl and therefore can be sumissive (Molhoek et al., 22nd Fatipec Congress, 15-19.5.95, Budapest, Vol.1, 119-132).

In all systems in which epoxypropan or Picadilly radical reacts with carboxypropyl or anhydride with the formation of crosslinking, it is possible to use catalysts. Examples are amines and metal compounds, such as, for example, aluminum acetylacetonate and octoate tin.

For containing carboxypropyl polyesters as cross-linking reagents are particularly important polyisocyanate crosslinking agents. To eliminate premature crosslinking, due to the high reactivity of isocyanates, and to ensure good alignment of the molten powder MDI block (internally, in the form of uretdione, or in the form of an adduct with a blocking reagent). Most commonly used blocking reagents are ε-caprolactam, methylethylketoxime and butanonoxime. Other suitable isocyanates blocking reagents are described in the publications G.B.Guise, G.N.Freeland and G.C.Smith, J. Applied Polymer Science, 23, 353 (1979) and by M.Bock and H.-U.Maier-Westhues in "Progress in Product Development for Powder Coating Technology, XIX th Int. Conf. on Organic Coatings, Science and Technol., Athens, 12-16 July", 1993. Examples of blocked and non-blocked polyisocyanates include 2-methylpentan-1,5-diisocyanate, 2-ethylbutane-1,4-diisocyanate, 3(4)isocyanatomethyl-1-methylcyclohexylamine, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, Tris(isocyanatomethyl)benzene, 4,4'-diisocyanatohexane, 1,4-bis(isocyanatomethyl)cyclohexane, m-tetramethyldisilane, p-tetramethyldisilane and, preferably, isophorondiisocyanate. To release, for example, polyisocyanate compositions usually add metal-containing catalyst, such as octoate zinc, dibutylamine or dibutyltindilaurate.

Other suitable crosslinking agents for hydroxy-group containing polyesters are anhydrides, such as trimellitic anhydride and the products of its reaction with dialami and diamines. Other examples of such cross-linking reagents are described in the publication .A.Misev in "Powder Coatings: Chemistry and Technology", published by J.Wiley &Sons, Chichester on pages 123 and 124.

The polyacrylates, which usually contain hydroxyl, carboxyl or Picadilly group, also used as binders for powder coatings. They are obtained by standard techniques mainly from such monomers as styrene and linear or branched C1-C8alkalemia esters of acrylic or methacrylic acid. In addition, you can add and subjected to copolymerization other ethyleneimine compounds such as divinylbenzene, acrylamide, methacrylamide, butoxyaniline, Acrylonitrile, bout the Dien etc. Hydroxy-group introduced by copolymerization with a hydroxy-group containing monomers, such as, for example, hydroxyethylmethacrylate, hydroxyethylmethacrylate, hydroxypropylmethacrylate, hydroxypropylmethacrylate. In the case of carboxylate use Ethylenediamine acids and anhydrides, such as acrylic, methacrylic, taconova and crotonic acid, and maleic, takenby, acrylic or methacrylic anhydrides (US-A-3836604). Picadilly group injected as described in EP-A-0256369 and US-A-3876578 by copolymerization of such monomers as glycidylmethacrylate and glycidylmethacrylate. For polyacrylates containing hydroxy-group or carboxypropyl, as cross-linking reagents, in principle, you can use the same connections that have already been specified for polyesters containing hydroxy-group or carboxypropyl. Other suitable cross-linking reagents are epoxysilane specified in US-A-0045040. For polyacrylates containing Picadilly group, suitable cross-linking reagents are dicarboxylic acids such as sabotinova acid and 1,12-dodecadienol acid, and anhydrides, such as, for example, bestiallity anhydride, and compounds described in US-A-3 880946. In DE-A-3310545, in addition, revealed smossyvesa the polyacrylates.

Epoxy resins for powder coatings usually PR is astavliaut an epoxy novolak ®or, preferably, based on aromatic polyols, more preferably based on bisphenol, such as bisphenol A. In JP-A-58187464 (1982) also described modified bisphenol epoxy resin. Epoxy resins are used in combination with cross-linking reagents of the classes of solid aliphatic amines, solid aromatic amines, adducts of amines, phenolic resins, polybasic acids and already described containing carboxypropyl polyesters. Hardeners, deserves to be specially noted are dicyandiamide, which is often used in conjunction with a catalyst, examples of which are Lewis acid, complexes of boron TRIFLUORIDE-amine complexes of metals, tertiary and Quaternary amines and imidazoline derivatives such as 2-methylimidazole.

Vodootvedenie is very important for printing, since the drying time of paint is a critical factor for the performance in the case of graphic products and should be on the order of a fraction of a second. Inks, UV curable by radiation, particularly important for screen and offset printing.

Such printing inks are known to the specialist in the art and are widely used in the art and described in the literature. They represent, for example, pigmented printing is or ink into the printing ink, colored dyes.

Printing ink is a liquid or paste-like dispersion, which includes colorants (pigments or dyes), binder, and optional solvents and/or optional water and additives. In the liquid printing ink binder and, if applicable, the additives are usually dissolved in the solvent. Typically the viscosity of liquid printing inks, measured using a Brookfield viscometer, are, for example, from 20 to 5000 MPa·s, for example from 20 to 1000 MPa·S. For pasty printing inks are, for example, from 1 to 100 PA·s, preferably from 5 to 50 PA·S.

Specialist in the art should be familiar with the ingredients and formulations of inks. Suitable pigments, as well as the composition of the printing inks, the normal techniques are generally known and are described in detail.

Printing ink can be used, for example, gravure printing, flexographic printing, screen printing, offset printing, lithography and continuous drip or inkjet printing on the material pretreated by the method proposed in the present invention, by using a well-known compositions, for example, in publishing, packaging, shipping, logistics, advertising, printing of securities and office equipment.

Suitable printing inks are printing inks, solvent-based, and printing of water-based paints. Of interest, for example, printing inks, water-based acrylate.

Printing inks or flexographic printing is usually prepared by diluting the concentrate, printing inks, and then, they can be used in accordance with the technologies, which are in themselves known.

Printing ink can also include, for example, alkyd systems that undergo oxidative drying.

Paints typically include a pigment or dye, or a combination of pigments or dyes, dispersing agent and a binder. It should be understood that the printing ink may include other excipients, which are conventional, such as preservatives, antioxidants, degassing/panagsama agents, viscosity regulators, thickeners, are substances that improve the fluidity, substances that prevent the precipitation of the substances, improving Shine, lubricants, enhancers adhesion, substances that prevent the formation of a surface film, matting agents, emulsifiers, stabilizers, hydrophobic agents, light stabilizers, substances that facilitate treatment, antistatic agents, buffer substances, surface-AK is active substances, water-retaining substances and substances that inhibit the growth of fungi and/or bacteria.

Printing ink can also be obtained in the usual manner by mixing the individual components with each other, for example, in the required amount of water.

Printing inks are also suitable, for example, for use in recording systems of this type, in which the printing ink is derived from small openings in the form of droplets directed to a substrate on which is formed the image. Suitable substrates are, for example, textile fibre materials, paper, plastics and aluminum foil, pre-treated by the method proposed in the present invention. Appropriate recording systems are, for example, a commercially available inkjet printers.

Printing ink for printing as votolatino catalyst preferably comprises (A1) votolatino acid, for example triarylsulfonium salt or aromatic sulfonate salt of formula VI described above;

or in which votolatino acid (A1) is a compound selected from the group comprising aromatic postname salts, aromatic itaniemi salt and focoltone acid-based Asimov; or (A2) connection votolatino Foundation.

Another area in to the second you can use the method fototerapia, proposed in the present invention, a coating for metals, in this case, for example, coatings on metal plates and tubes, lids, cans and bottles, cars and other vehicles, for example trains, bikes, planes, boats, ships, etc. and vodootvedenie polymer coatings, for example coatings for floors or wall coverings based on PVC.

Examples fototfreddie coatings for paper are colorless varnishes for labels, sleeves and book covers.

Also of interest is the use of a new method for curing molded parts made of composite systems. Composite system contains a self-sustaining matrix material, for example, glass or, alternatively, for example, vegetable fibers [see K.-Rmes, .Reussmann in Kunststoffe 85 (1995), 366-370], which has been impregnated activated, i.e. irradiated fototerapia composition. Molded articles consisting of composite systems have a high mechanical stability and strength. The new method can also be used for the manufacture of shaped materials or for impregnation or coating of the composite product, as described, for example, in EP 7086. Examples of such compositions are gel-like composition is La coatings, have to meet strict requirements regarding activity during curing and resistance to yellowing, and hardened profiled fiber materials, for example light-diffusing panels that are flat or corrugated in the longitudinal or transverse direction. The technology of such molded products, such as the technique of manual layering, stacking layers impregnated by spraying, centrifugal casting or molding the winding of the filament, as described, for example, in the publication ..Selden in Glasfaserverstärkte Kunststoffe", page 610, Springer Verlag Berlin-Heidelberg-New York 1967. Examples of products that can be produced by these technologies are boats, fibre and chipboard panels with double-sided coating of reinforced fiberglass, pipes, containers, surfboards, etc. are Other examples of compositions for molding, impregnation and coatings are polyurethane gel compositions of coatings for molded articles containing fiberglass (reinforced plastics), such as corrugated sheets and layered materials based on paper. Layered materials based on paper can be made on the basis of urea resins or melamine resins. To manufacture laminates gel-like composition for coating is irradiated and is applied on a substrate (e.g., film). New sposobuje can be used for the manufacture of molded resin or products with shading, for example, electronic components, etc.

A new method suitable for applying coatings to substrates of all types, for example, wood, textiles, paper, ceramics, glass, plastics, such as a complex polyester, polyethylene terephthalate, polyolefin and ultrafine cellulose acetate, preferably in the form of films, and also metals such as Al, si, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2that, for example, it is necessary to apply a protective layer.

The coating on the substrate can be performed by applying to the substrate a liquid composition, solution or suspension, which prior to the application should be irradiated. The choice of solvent and concentration mainly depends on the type of compositions and methods of coating. The solvent should be inert, i.e. it should not react chemically with the components, and after coating must be removed during drying. Examples of suitable solvents are ketones, ethers and esters, such as methyl ethyl ketone, isobutylmethylxanthine, Cyclopentanone, cyclohexanone, N-organic, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate, ethyl-3-ethoxypropionate, 2-methoxypropylacetate, methyl-3-methoxypropionate, 2-heptanone, 2-pentanone and ethyllactate.

The solution is evenly applied on podocopa well-known coating technologies, for example, using centrifugation, immersion, knife coating, pouring, brushing, spraying, preferably by electrostatic spraying and reverse roller, and by electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary, flexible substrate and then to coat the final substrate, for example, on plakirovannyy copper PCB or on a glass substrate by transferring layer by lamination.

The applied amount (coating thickness) and the nature of the substrate (layer substrate) depends on the application. The range of thickness of the coating is typically from about 0.1 to more than 100 microns, for example from 0.1 μm to 1 cm, preferably from 0.5 to 1000 microns.

The new method can also be used for emulsion polymerization, bead polymerization and suspension polymerization.

In the method described above, further processing includes applying irradiated composition to the substrate, optionally with subsequent additional steps of machining the substrate with a coating, such as bending, cutting, polishing; preparation of foam; the preparation of the polymer; preparing fibers; preparing a gel-like coating; preparation of a composite material; preparation of glue, cooking transparent cover Il is pigmented coating, printing ink, ink for inkjet printer or the preparation of a coating that contains more included material, such as sand for abrasive paper.

In the method proposed in the present invention, the subsequent processing stage can be a preparation of foam materials (flexible, rigid, integral or microporous foam).

Compositions intended for the manufacture of such foams are simply polyetherpolyols, complex polyetherpolyols or polyurethane composition.

Polyurethanes receive, for example, by the reaction of polyethers, polyesters and polybutadienes which contain terminal hydroxy-group, with an aliphatic or aromatic polyisocyanates.

Polyethers and polyesters containing terminal hydroxy-group are known for, and receive, for example, by polymerization of epoxides such as ethylene oxide, propylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, with themselves, with themselves, for example, in the presence of F3or the reactions of addition of these epoxides individually or in a mixture or successively to the starting components containing reactive hydrogen atoms such as water, alcohols, ammonia or amines, for example ethylene glycol, etc is pile-1,3 - and 1,2-glycol, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or Ethylenediamine. In the context of the present invention is also applicable polyether of sucrose. In many cases, preference is given to such simple polyethers which predominantly (up to 90 wt.%, in terms of all groups IT is contained in a simple polyester) contain the primary group IT. Also suitable are polyethers modified with vinyl polymers, which are formed, for example, by the polymerization of styrene and Acrylonitrile in the presence of polyethers and polybutadienes containing group, HE.

These compounds generally have a molecular mass equal to 40, and are polyatomic hydroxycodone, preferably compounds containing from 2 to 8 hydroxyl groups, preferably having a molecular weight equal to from 800 to 10,000, preferably from 1000 to 6000, for example, polyethers containing at least 2, generally from 2 to 8, but preferably 2 to 4 hydroxyl groups, as it is known to obtain a homogeneous microporous polyurethanes and polyurethanes.

Of course, you can use a mixture of the above compounds containing at least two reactive towards isocyanates hydrogen atom, preferably having a molecular weight, avnoj 400-10000.

Suitable polyisocyanates are aliphatic, cycloaliphatic, aromatic and heterocyclic polyisocyanates, such as atlantaatlanta, 1,4-tetramethyldisilane, 1,6-hexamethylenediisocyanate, 1,12-dodecanesulfonate, CYCLOBUTANE-1,3-diisocyanate, cyclohexane-1,3 - and -1,4-diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl, 2,4 - and 2,6-hexahydrotriazine, as well as any mixtures of these isomers, hexahydro-1,3 - and/or -1,4-delete the entry, perhydro-2,4'- and/or -4,4'-diphenylmethanediisocyanate, 1,3 - and 1,4-delete the entry, 2,4 - and 2,6-colorvision, as well as any mixtures of these isomers, difenilmetana 2,4'- and/or -4,4'-diisocyanate, naftilan-1,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, polyphenyl-polymethylenepolyphenylisocyanate who receive aniline-formaldehyde condensation followed by treatment with phosgene, m - and p-isocyanatopropyltrimethoxysilane, perchloroethane arylpropionate, polyisocyanates containing carbodiimide groups, polyisocyanates containing allophanate groups, polyisocyanates, which contain groups, polyisocyanates containing urethane groups, the polyisocyanates containing acetylated urea groups, polyisocyanates containing biuret groups, the polyisocyanate is, containing ester groups, reaction products of the aforementioned isocyanates with acetals, and polyisocyanates containing polymer radicals of fatty acids.

You can also use containing isocyanate group remains after distillation in the form in which they are received, or dissolved in one of the above polyisocyanates, which are formed during industrial production of isocyanates. It is also possible to use any desired mixtures of the aforementioned polyisocyanates.

Special preference is usually given to polyisocyanates which have already obtained industrially, for example, 2,4 - and 2,6-colordistance and any desired mixtures of these isomers, polyphenyl-polymethylenepolyphenylisocyanate who receive aniline-formaldehyde condensation followed by treatment with phosgene ("crude diphenylmethanediisocyanate (DHS)"), and polyisocyanates containing carbodiimide, urethane, allophanate, which, urea or biuret groups ("modified polyisocyanates").

Polyurethane foams, preferably obtained from a liquid starting components, or substances are introduced into reaction with each other, mix for one-step technology or first preparing a pre-adduct containing NCO group, which is derived from a polyol and an excess of MDI, and the ATEM its froth, usually by reaction with water.

In the method proposed in the present invention, the foam composition is irradiated before adding the isocyanate component.

Upon receipt of the foamed foaming is often held in the molds. In this case, the reaction mixture is placed in the mold, for example, after irradiation and the addition of water. Materials suitable for the manufacture of molds are metal, usually aluminum, or plastic, usually epoxy. In the mold foaming reaction mixture foams and forms a molded product. The formation of foam can hold so that the molded material had a porous surface structure, or, alternatively, so that the molded material contained dense surface layer and a porous core. For this mold, you can put the amount of foaming of the reaction mixture, sufficient to ensure that the resulting foam is just filled the mold. However, in the mold you can also put the amount of foaming of the reaction mixture, more needed to fill the foam inner part of the mold. Therefore, in the latter case, the operation is performed under excessive loading.

In the case of forming foams often simultaneously use a known external agents for the mouth is anemia adhesion during forming, usually silicone oil. However, you can also use the so-called internal agents to eliminate the sticking of the molded, optionally in a mixture with external agents to eliminate adhesion during forming. You can also use the foam cold hardening. Of course, foams alternative can be obtained by foaming in the block or using a known technique using a double belt conveyor. These technologies can be used to obtain an elastic, semi-solid or solid foam.

Foams are used, known for such products, such as mattresses and upholstery in the furniture and automotive industries, as well as for the manufacture of parts in the automotive industry and, finally, as the insulating compositions and compositions for thermal insulation and low-temperature insulation, for example, in the construction and refrigeration industries, as well as in the textile industry, for example, as the pads. These foams are of particular interest e.g. for the automotive industry for the manufacture of, for example, armrests, headrests, acoustic skin foams, seat made of elastic foam; or, for example, headlining, hangers, door is veneered panels, arm rests, dashboards, headrests, armrests from semi-rigid foams; or foams are used to fill cavities (hard foam); or for the manufacture of, for example, steering wheels, air filters, stick shift, linings, coatings, cables, head of flexible integral foams.

Another object of the present invention is the method of application votolatino catalyst (a), in which a composition including a specified catalyst, is subjected to irradiation before further processing, characterized in that subsequent processing is the production of foam and the composition includes a polyol as one and isocyanate components and as votolatino catalyst - votolatino base (A2).

The following additional examples illustrate the present invention but are not considered limiting the scope of the claims. In the rest of the description and in the claims, all expressed in units and percent content are mass, unless otherwise noted. If you specify alkyl and CNS radicals containing more than 3 carbon atoms without any indication isomeric form, refers to the normal isomers.

Example 1:

The following composition is prepared by cm is shivani respective ingredients:

Part a

54,78 parts of the hydroxy-group containing polyacrylate (Desmophen A VP LS 2350, produced by the firm Voeg AG)

0,70 parts of a leveling agent Byk 333 (10% in butyl acetate,

modified simple polyester polydimethylsiloxane,

produced by the company Byk Chemie)

0.50 parts of a leveling agent Byk 355 (solution polyacrylate produced by the company Byk Chemie)

0.55 parts protivovspenivayushchie additives Byk 141 (polysiloxane produced by the company Byk Chemie)

18,47 parts of a mixture of xylene/methoxypropylacetate/butyl acetate in a ratio of 1:1:1

The component In the

20,08 parts of n-aliphatic MDI (Desmodur N 3390, produced by Bayer AG)

2,8% Votolatino Foundation(PLB-1) is completely dissolved in component A. Before applying the samples add component b and homogenize. Then, the thus prepared composition for coating are placed in a Petri dish and in a device for curing a UV radiation is irradiated with a mercury lamp 2×80 W/cm at a linear speed equal to 3 m/min

Reactivity contained tracks explore with the help of the device to register drying, produced by the company Byk-Gardner. After exposure of the composition in a Petri dish on a glass plate with a length of 30 cm using a slotted device for applying the coating is applied coating thickness of 5 μm. Then, the glass plate coated is placed in a device for recording, which in the darkness on the vinyl floor with a constant velocity moves the needle. Along the length of the needle plate is moved for 24 hours after this time determine the phase of curing. Important is the time after which the coating becomes non-sticky (= phase 3).

The second sample is not exposed to the composition containing components a and b, examine the instrument for registration. Then the samples not containing votolatino catalyst examined by the method described above, i.e. with the stage of preliminary irradiation and without it. The results are shown in following table 1.

Table 1
Curing time before the formation of the non-stick coating
CatalystCuring in the dark without prior exposurePre-irradiation followed by curing in the dark
no8 h8 h
votolatino base (PLB-1)8 h 5 h

Example 2: Preparation of simple polyester/polyurethane soft foam.

0.08 g (0,05 % based on the polyol) of amine catalyst, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)

0.24 g (0.15 % based on the polyol) Votolatino catalyst PLB-1 is dissolved in 160 g of simple polyetherpolyols [Lupranol 2082 (RTM) hydroxyl number of 48 mg KOH/g, water content less than 0.1 %, acid number is less than 0.1 mg KOH/g)]. Then, the sample for 2 min irradiated Panacol UV lamp UVA Lamp UV F 450 watts using a blue filter.

Added 9.6 g of a solution containing 1.92 g of polysiloxane-polyoxyalkylene block copolymer as foam stabilizer (Tegostab®BF 2370; produced by the company Goldschmidt, Germany) and of 7.68 g of deionized water and the reaction mixture is vigorously stirred for 10 s at 2600 Rev/min Then added 0.32 g of octoate tin(II) (Kosmos®29; produced by the company Goldschmidt, Germany) and the reaction mixture is again vigorously stirred for 18 with at 2600 Rev/min Then add 94,54 g of isocyanate (Lupranat®T80, produced by BASF; a mixture of toluylene-2,4 - and toluylene-2,6-diisocyanate) with continuous stirring for 5-7 with at 2600 Rev/min the mixture is Then poured into 20×20×20 cm box for sintering and exothermic reactions receive a block of foam.

The second is issledovanii to the composition was added 0.08 g (0.05% in terms of polyol) votolatino catalyst (PLB-1). Preparation of foam carried out as described above. And in this case, get a block of foam.

Example 3: Preparation solvent free two-component polyurethane adhesive composition

Component a is prepared by mixing the ingredients listed below:

to 50.0 wt.% trifunctional polypropylene-simple polyetherpolyols (Desmophen®1380 W, produced by the firm Voeg)

20.0 wt.% linear polypropylene-simple polyetherpolyols (Desmophen®1112 BD produced by the firm Voeg)

of 0.21 wt.% sensitizer, isopropylthioxanthone (Darocure®ITX, produced by the company Ciba Specialty Chemicals)

2.1 wt.% votolatino base PLB-1

Component In:

Prepolymer aromatic isocyanate-based diphenylmethanediisocyanate (DHS), Desmodur® E21, produced by the firm Voeg.

(Components a and b are mixed in a ratio A:B=1:0,74.)

Example 3.1: 0.5 g of the Compound And placed in an open transparent glass mold (thickness about 1 mm) and irradiated with UV-fluorescent lamps TL 05 (Philips) for 10 minutes During irradiation, the liquid is continuously stirred using a magnetic stirring device.

After irradiation add 0,37 g connection and quickly mix with a spatula made of stainless steel. Homogeneous composition with a piece of wire nano is drawn to the crystal CVG, used in Fourier transform infrared spectroscopy (FTIR) (NT 34 μm). Immediately after applying for the crosslinking reaction of the isocyanate with the polyol monitored using FTIR using a spectrometer Perkin Elmer 1600.

Spectra shoot through 5; 15; 30; 60 and 120 min, setting the first range of zero time. The lower height of the isocyanate peak at 2271 cm-1over time use as a measure of the reactivity of the system. The results shown in the following table 2, characterized by the conversion of NCO, calculated according to studies using FTIR.

Example 3.2: 0.28 g of Compound a and 0.21 g connection is placed into the open transparent glass mold (thickness about 1 mm) and irradiated with UV-fluorescent lamps TL 05 (Philips) for 10 minutes During irradiation, the liquid is continuously stirred using a magnetic stirring device.

After irradiation of the composition with a piece of wire is applied to the crystal CVG used in FTIR (NT (the thickness of the wet coating) 34 μm). Immediately after the application of the reaction is monitored using FTIR described above. The results are shown in table 2.

Table 2
Time t[min]The NCO conversion [%]
Example 3.1Example 3.2
000
512,914,47
1532,0815,48
3046,4530,03
6064,7747,03
12077,6164,55

Remaining on the crystal after studies using FTIR film is non-sticky.

Example 4: Preparation of solvent free two-component polyurethane adhesive composition

0.5 g of Compound A (described in example 3) is placed in an open transparent glass mold (thickness about 1 mm) and irradiated with UV-fluorescent lamps TL 05 (Philips) for 10 minutes During irradiation, the liquid is continuously stirred using a magnetic stirring device.

After irradiation gain of 0.37 g of compound (as described in example 3) and rapidly stirred with a spatula made of stainless steel. The homogeneous composition is applied onto the polyethylene strip the new film (= strip (A). The second polyethylene film not covered with glue (= strip), press to strip And so was not among them air. Immediately after lamination strips and stripes on top of the strips are placed flat wooden bar, which then put a weight of 5 kg

After 5 h adhesion examined by stratification of the strips at the ends. When you try to stretch at both ends, found that the strips were glued together.

Example 5:

Repeat the procedure of example 4, instead of PLB-1 using(PLB-2). When you try to stretch at both ends, found that the strips were glued together.

Example 6: the composition of the pigmented coating

The composition And is prepared by mixing the ingredients listed below:

0.4 wt.% sensitizer of isopropylthioxanthone (Darocur®ITX,

produced by the company Ciba Specialty Chemicals)

to 59.6 wt.% butyl acetate as solvent

40.0 wt.% trimethylolpropane-Tris(3-mercaptopropionate) (manufactured by Aldrich company)

The composition is prepared by mixing the ingredients listed below:

to 9.0 wt.% transparent greenish-yellow organic pigment

(Chromophtal® Yellow 8GN (marketed by the company Ciba Specialty Chemicals)

76,0 wt.% epoxy resin of bisphenol A (Bakelite EPR 162, produced by the firm Bakelite AG)

8.0 wt.% the polymer dispersing agent (EFKA 4010, manufactured by the company Ciba Specialty Chemicas)

7.0 wt.% butyl acetate as solvent

to 0.011 g Votolatino base PLB-1 is dissolved in 0.4 g of composition a and composition for 10 min under vigorous stirring is irradiated with UV light (fluorescent lamp Philips TL 40 W/05 with the main emission in the range from 350 to 400 nm) in the mould size of 3.6, see Add 0,123 g of the composition and stirred for several seconds and obtain a homogeneous composition.

The reaction of the coating is monitored at room temperature using spectroscopy NGOs (frustrated total reflection) (spectrometer Nicolet Magna-IR 750), observing the decrease in the intensity of the bands SH (2564 cm-1) and epoxy group (912 cm-1). The results are shown in table 3.

Table 3
Time after irradiationThe SH content (%)The content of the epoxy resin (%)
The starting point100100
9 min7975
15 min6564

In addition, the full composition, i.e. the question is related components a+b, irradiated under the same conditions: reaction, as shown by the results in table 3A, is much slower, but the stitching also occurs.

Table 3A
Time after irradiationThe SH content (%)The content of the epoxy resin (%)
The starting point100100
10 min9786
19 min9380

Example 7: Preparation of a gel-like composition coating

The composition And is prepared by mixing the following ingredients:

0.4 wt.% sensitizer of isopropylthioxanthone (Darocur®ITX,

produced by the company Ciba Specialty Chemicals)

58,0 wt.% butyl acetate as solvent

to 42.0 wt.% trimethylolpropane-Tris(3-mercaptopropionate) (manufactured by Aldrich company)

The composition is prepared as described in example 4.

0.11 g Votolatino base PLB-1 is dissolved in 4.3 g of a composition a and a composition with vigorous stirring irradiated with UV light (fluorescent lamp Philips TL 40W/05 to Ref the main emission in the range from 350 to 400 nm) for 20 min in the mould size 6 see Add 1,43 g of the composition and stirred for several seconds and obtain a homogeneous composition.

The reaction is monitored at room temperature using spectroscopy NGOs (spectrometer Nicolet Magna-IR 750), watching 3A decrease the intensity of bands SH (2564 cm-1).

The results are shown in table 4.

Table 4
Time after irradiationThe SH content (%)
The starting point100
50 min49

After 50 min at room temperature the gel coating is sticky.

In addition, the full composition, i.e. the combined components a+b, is irradiated under the same conditions: reaction, as shown by the results in table 4A, is slower, but the stitching is still going on.

Table 4A
Time after irradiationThe SH content (%)
The starting point100
10 min100

In this case, after 50 min at room temperature the gel coating is still liquid.

Example 8: Preparation of fiberglass composite material Composition is prepared by mixing the following ingredients:

0.4 wt.% sensitizer of isopropylthioxanthone (Darocur®ITX, produced by the company Ciba Specialty Chemicals)

59,0 wt.% butyl acetate as a solvent was 41.0 wt.% trimethylolpropane-Tris(3-mercaptopropionate) (manufactured by Aldrich company)

0.33 g Votolatino base PLB-1 is dissolved in 12.8 g of the composition and the composition with the vigorous stirring is irradiated with UV light (fluorescent lamp Philips TL 40W/05 with the main emission in the range from 350 to 400 nm) for 40 min in the mould size 9 see Added 3.3 grams Bakelite EPR 162 (epoxy resin of bisphenol a) and stirred for several seconds and obtain a homogeneous composition.

Fiberglass moisten the song, then placed on top of another glass and also moisten composition. The procedure is repeated until the composition will not be dampened with three layers of optical fibers.

The reaction is monitored at room temperature using spectroscopy NGOs (spectrometer Nicolet Magna-IR 750), observing the decrease in intensity of the bands SH (2564 cm-1).

The results are shown in table 5.

Table 5
Time after irradiationThe SH content (%)
The starting point100
36 min50
60 min50

After 3 h at room temperature the composition is non-sticky.

In addition, the full composition, i.e. the combined components a+b, is irradiated under the same conditions: reaction, as shown by the results in table 5A, is much slower, but the stitching is still going on.

Table 5A
Time after irradiationThe SH content (%)
The starting point100
Time after irradiationThe SH content (%)
36 min73
60 min61

After 3 h at room temperature, this composition is still sticky.

Example 9: the Cure song NCO/OH to cover

Component a is prepared by mixing the following ingredients:

73,0 wt.% containing the hydroxy-group of polyacrylate,

70% in butyl acetate (Desmophen A VP LS 2350, produced by Bayer AG)

0.9 wt.% supplements, 10% in butyl acetate (Byk 333, produced by the company Byk)

0.7 wt.% supplements, 50% of the supplied form (Byk 335, produced by the company Byk)

0.7 wt.% supplements, 4% of the supplied form (Byk 141, produced by the company Byk)

of 24.7 wt.% a mixture of xylene/methoxypropylacetate/butalnital in the ratio of 1:1:1 as solvent

The composition contains 100 wt.% aliphatic MDI, 90% in n-butyl acetate, (Desmodur N 3390 BA, produced by Bayer AG) 0.14 g votolatino base PLB-1 is dissolved in 3,76 g component and the composition is irradiated with UV radiation at a dose equal to 4.5 j/cm (AETEC International), in a quartz cell with a size of 1 cm Then the composition is mixed with 1,03 g component In using the spray gun with the filing of two components and is applied to the crystal BaF2.

For the following reaction at 130°C using FTIR (spectrometer Perkin Elmer 1600 FTIR), observing the decrease in intensity of the band NCO (2270 cm-1). The results are shown in table 6.

Table 6
Aging time at 130°C after irradiation The NCO content (%)
The starting point100
Aging time at 130°C after irradiationThe NCO content (%)
4 min71
15 min32

Example 10: the Cure song NCO/OH to cover

0.14 g Votolatino base PLB-1 is dissolved in 3,76 g component, as described in example 9, and the composition is irradiated with UV radiation at a dose equal to 4.5 j/cm2(AETEK International) in a quartz cell with a size of 1 cm Then the composition is mixed with 1,03 g component, as described in example 9, using the spray gun with the filing of two components and is applied to an aluminum plate with a thickness in the dry state, equal to about 40 microns. Get fully utverjdenie a non-stick coating.

Example 11: the Cure song NCO/OH to cover

Repeat the procedure of example 10, but instead PLB-1 use PLB-2.

Example 12:

The following composition is prepared by mixing the respective ingredients:

56,16 parts Joncryl 510 (agripolis produced by the company Johnson Polymer)

MT 19 : 18 parts of Cymel 303 (hexamethoxymelamine produced by the company Cytec)

14,16 parts butyl alcohol

9.89 parts IU the of ipertensione

0,61 parts DC-57 (10% methylpentylamine) leveling agent, manufactured by the company Dow Corning

2% votolatino acid α-(4-methylphenylsulfonyl)-4-dimethylbenzylamine) (FLK-1) is completely dissolved in the specified composition. Then, the thus prepared composition for coating are placed in a Petri dish and in a device for curing a UV radiation is irradiated with a mercury lamp 2×120 W/cm at a linear speed of 5 m/min After irradiation, the composition for coating is applied to the containing white coating aluminum plate with a dry film thickness of 50 μm. This plate is heated for 30 minutes at 90°C. After 2 h and after cooling plates measure hardness by pendulum device according to könig (DIN 53157). The higher the hardness by pendulum device, the better the cure.

A second sample of the composition for coating are examined by the same procedure, but without prior exposure in a Petri dish.

Then the samples not containing votolatino catalyst examined by the method described above, i.e. with the stage of preliminary irradiation and without it. The results are shown in following table 7.

Table 7:
Hardness by pendulum device in seconds to block the fir coverings
CatalystCuring in the dark without prior exposurePre-irradiation followed by curing in the dark
nostickysticky
fotolenta acid (FLC)sticky31

Example 13: Glue, cation curing UV radiation

Component a is prepared by mixing the ingredients listed below, until a homogeneous state:

20.0 wt.% complex polyetherpolyols (Tone Polyol 0310, produced by DOW Chemical company)

5.0 wt.% butyl acetate as solvent

4.0 wt.% cationic photoinitiator(Irgacure® 250, produced by the company Ciba Specialty Chemicals - = FLK-2)

Component b: cycloaliphatic epoxy resin (Cyracure Resin UVR 6105, produced by DOW Chemical company)

Component a is applied to a strip of polycarbonate (2 cm × 12 cm, thickness about 1 mm) using a wire device for coating thickness wet film 4 μm)placed under UV light (Hoenie UVASPOT, a mercury lamp and irradiated for 10 min (strip A).

Component applied to the strip of polycarbonate (2 cm × 12 cm, thickness primer is 1 mm) using a wire device for coating thickness wet film 12 μm) (strip).

After exposure, the strips a and b are pressed to each other by the parties with the floor, so that between them there was air. Immediately after lamination strips and stripes on top of the strips are placed flat wooden bar, which then put a weight of 5 kg After 5 h adhesion examined by stratification of the strips at the ends. When you try to stretch at both ends, found that the strips were glued together.

Example 14: Preparation of solvent free epoxy adhesive

The composition is prepared by mixing the ingredients listed below: 97,0 wt.% epoxy resin based on bisphenol-A/bisphenol-F (Bakelite EPR 144, produced by the Bakelite company), 3.0 wt.% votolatino Foundation (PLB-2)

0.5 g of the Composition is placed in an open transparent glass mold (thickness about 1 mm) and irradiated with UV radiation at a dose equal to 4.5 j/cm2(AETEK international).

After irradiation, the composition is applied on a strip of plastic film (= strip (A). The second polyethylene film not covered with glue (= strip), press to strip And so was not among them air. Immediately after lamination strips and stripes on top of the strips are placed flat wooden bar, which then put a weight of 5 kg. Adhesion examined by stratification of the strips at the ends. When you try to stretch for both containerised, the strips were glued together.

Example 15: Preparation of epoxy coating

The composition is prepared by mixing the ingredients listed below:

80,0 wt.% diglycidylether simple ether of bisphenol-A (Bakelite EPR 162 produced by the Bakelite company), of 17.0 wt.% butyl acetate,

3.0 wt.% votolatino Foundation

(PLB-3)

0.5 g of the Composition is placed in an open transparent glass mold (thickness about 1 mm) and irradiated

UV radiation at a dose equal to 4.5 j/cm2(AETEK international).

After exposure, the layer composition thickness of 40 μm using a wire device for coating applied to an aluminum plate. Get fully utverjdenie a non-stick coating.

Example 16: Preparation of polyurethane foam

Simple polyetherpolyols (LupranolRTM2080, trifunctionally polypropylene-simple polyetherpolyols containing primary hydroxy-group; a hydroxyl number of 48 mg KOH/g, water content less than 0.1 %, acid number less than 0.1 mg KOH/g, containing 0.45 % of stabilizer Irgastab® PUR 55), votolatino base PLB-1 and isopropylthioxanthone (Darocur ITX) are mixed in a ratio of 100:5:0.5 in. 10 g of this mixture is irradiated with UV light (fluorescent lamp Philips TL 40W/05 with the main emission in the range from 350 to 400 nm) four times for 5 minutes

Then 7.5 g of the obtained solution is dissolved in 78,60 g of Lupranol 2080. Then add 4,96 g of a solution containing 0.96 g TegostabRTMBF 2370 (produced by the company Goldschmidt, Germany), was added 4 g of deionized water and the reaction mixture is vigorously stirred for 10 s at 2600 Rev/min Then added 1.6 g of a solution Kosmos 29 (produced by the company Goldschmidt, Germany)/Lupranol 2080 (ratio 1:9) and the reaction mixture is again vigorously stirred for 18 with at 2600 Rev/min

Then add 48,88 g of isocyanate (LupranatRTMT80, produced by BASF; a mixture of toluylene-2,4 - and toluylene-2,6-diisocyanate) with continuous stirring for 5-7 with at 2600 Rev/min the mixture is Then poured into 20×20×20 cm box for sintering and the reaction begins foaming, which leads to the formation of the block of foam.

1. Method of application votolatino catalyst (a), in which a composition including a specified catalyst, is subjected to irradiation before further processing, characterized in that photolents catalyst is
(A1) a compound selected from the group consisting of votolatino acid of formula VI
,
in which Ra2denotes a direct bond, S, O, CH2, (CH2)2WITH or NR96;
Ra3; Ra4, Ra5and Ra6independently of one another denote H, C1-C20alkyl, C3-C 8cycloalkyl,1-C20alkoxygroup,2-C20alkenyl, CN, IT, halogen, C1-C6allylthiourea, phenyl, naphthyl, phenyl-C1-C7alkyl, naphthyl-C1-C3alkyl, fenoxaprop, naphthyloxy, phenyl-C1-C7alkyloxy, naphthyl-C1-C3alkyloxy, phenyl-C2-C6alkenyl, naphthyl-C2-C4alkenyl, S-phenyl, (CO)Ra8, O(CO)Ra8, (CO)ORa8, SO2Ra8, OSO2Ra8;
Ra7stands With1-C20alkyl, C1-C20hydroxyalkyl,
,or
Ra8denotes H, C1-C12alkyl, C1-C12hydroxyalkyl, phenyl, naphthyl or biphenylyl;
Ra9denotes a direct bond, S, O or CH2;
Ra10; Ra11, Ra12and Ra13independently of one another have one of the meanings indicated for RA3; or Ra10and Ra12associated with the formation of a condensed ring system with the benzene rings to which they are attached;
Ra14does,
Z denotes an anion, preferably PF6, SbF6AsF6BF4, (C6F5)4In, Cl, Br, HSO4, CF3-SO3F-SO3,
CH3-SO3, ClO4, PO4, NO3, SO4CH3-SO4,;
the aromatic itaniemi salt of the formula (V)
,
in which Ra0and Ra1all independently of one another denote hydrogen, C1-C20alkyl, C1-C20alkoxygroup, OH-substituted C1-C20alkoxygroup, halogen, C2-C12alkenyl, cycloalkyl, preferably methyl, isopropyl or isobutyl; and Z is as described in formula VI;
or based on the oximes votolatino acid of the formula (VII) or (VIIa)

or

where Ra15does,
(CO)O-C1-C4alkyl, CN or C1-C12halogenated;
Ra16has one of the meanings indicated for Ra15or does
Ra17stands With1-C18alkylsulfonyl, C1-C10halogenallylacetic, comparisonthis, phenyl-C1-C3alkylsulfonyl, C3-C30cycloalkylcarbonyl, phenylsulfonyl, naphthylmethyl, anthracenesulfonic or ventriculitis, and cycloalkyl, phenyl, naftalina, anthracyline and phenanthroline group of radicals With3-C30cycloalkylcarbonyl, phenyl-C1- 3alkylsulfonyl, phenylsulfonyl, naphthylmethyl, anthracenesulfonic and financialthe are unsubstituted or substituted by one or more halogen, C1-C4halogenation, CN, NO2With1-C16Akilov, fanilow, C1-C4alkylthio,1-C4alkoxygroup, fenoxaprop,1-C4alkyl-O(CO)-, WITH1-C4alkyl-(CO)O-, Ra27OSO2- and/or-NRa20Ra21;
q is 0 or 1; and
Ra18stands With1-C12alkyl, cyclohexyl, Campari, unsubstituted phenyl, or phenyl substituted by one or more halogen, C1-C12Akilov, ORa19, SRa19or NRa20Ra21;
Ra19stands With1-C12alkyl, phenyl, phenyl-C1-C4alkyl or C1-C12hydroxyalkyl;
Ra20and Ra21all independently of one another denote hydrogen, C1-C4alkyl, C2-C6hydroxyalkyl, or Ra20and Ra21together with the N atom to which they are bound, form a 5 - or 6-membered ring which may also contain atoms Of the group or NRa22;
Ra22denotes hydrogen, phenyl, phenyl-C1-C4alkyl, C1-C12alkyl or C2-C5hydroxyalkyl;
Ra23; Ra24, Ra25and Ra26all independently each is denoted C 1-C6alkyl, C1-C6halogenated; or phenyl, unsubstituted or substituted C1-C4by alkyl or halogen; and
Ra27denotes hydrogen, C1-C4alkyl, phenyl or tolyl; or
(A2) votolatino connection of the base of formula (VIII), (VIIIa) or (VIIIb)
,,,
in which r is 0 or 1;
X4denotes CH2or;
R2and R3all independently of one another denote hydrogen or C1-C20alkyl;
R1denotes unsubstituted or1-C12alkyl or C1-C12alkoxy-substituted phenyl, naphthyl or biphenylyl;
R20, R30and R40together with the associated nitrogen atom denote a group of the structural formula
or;
anion represents any anion capable of forming a salt;
and m denotes the number of positively charged N atoms in the molecule.

2. The method according to claim 1, in which
(A) photolents catalyst (a) is fotolenta acid (A1) and the composition includes cured under acid catalysis compounds (b);
or
(B) photolents catalyst (a) is votolatino base (A2) and the composition includes cured at base catalysis is m connection ();
or
(C) photolents catalyst (a) is a mixture of at least one votolatino basic catalyst (A2) and at least one votolatino acid catalyst (A1), in which the composition includes a mixture cured at catalysis acid compounds (b) and cured at catalysis based compounds (C), provided that (A1) and (A2) selectively activated.

3. The method according to claim 1, wherein the composition comprising a photocatalyst, further includes a dye or pigment (g).

4. Method of application votolatino catalyst (a) according to claim 1, in which a composition including a specified catalyst, is subjected to irradiation before additional processing, in which the composition is the composition of a varnish comprising a polyol in combination with isocyanate and as votolatino catalyst - votolatino base (A2) of the formula VIII, VIIIa, or VIIIb
,,,
in which r is 0 or 1;
X4denotes CH2or;
R2and R3all independently of one another denote hydrogen or C1-C20alkyl;
R1denotes unsubstituted or1-C12alkyl-, or C1-C12alkoxy-substituted phenyl, naphthyl or biphenylyl;
R20, R30and R40together sowetany with them the nitrogen atom denote a group of the structural formula
or;
anion represents any anion capable of forming a salt; and m denotes the number of positively charged N atoms in the molecule.

5. Method of application votolatino catalyst (a) according to claim 1, in which a composition including a specified catalyst, is subjected to irradiation before additional processing, in which the composition is a composition varnish comprising an epoxy component and as votolatino catalyst - votolatino base (A2) of the formula VIIIa,
,
in which r is 0 or 1;
X4denotes CH2or;
R1denotes unsubstituted or1-C12alkyl-, or C1-C12alkoxy-substituted phenyl, naphthyl or biphenylyl;
R20, R30and R40together with the associated nitrogen atom denote a group of the structural formula
,or;
R35denotes hydrogen or C1-C18alkyl;
anion represents any anion capable of forming a salt; and m denotes the number of positively charged N atoms in the molecule.

6. Method of application votolatino catalyst (a) according to claim 1, in which the composition is an adhesive.

7. The method according to claim 6, in which Votolato Tim catalyst is votolatino base (A2) and the composition is cured at a catalysis a ground connection (s).

8. The method according to claim 1, wherein the subsequent processing includes applying irradiated composition to the substrate, optionally with subsequent additional steps of machining the substrate with the coating; preparation of foam; the preparation of the polymer; preparing fibers; preparing a gel-like coating; preparation of a composite material; preparation of glue, the preparation of a clear coating or pigmented coatings, printing ink, ink for inkjet printer or the preparation of a coating that contains more included material.

9. The method according to claim 1, which is repeated many times, photocatalysts at each stage of recurrence are the same or different and independently represent votolatino acid and/or votolatino base.

10. The method according to claim 1, wherein the composition is irradiated directly in the storage tank and then sent for further processing.

11. The method according to claim 1, in which the subsequent processing is an additional step of curing using UV radiation and/or heat.

12. The substrate on which a coating of the composition, corresponding to the method according to claim 1.

13. Method of application votolatino catalyst (a) according to claim 1, in which a composition including a specified catalyst, is subjected to the irradiation prior to subsequent processing, characterized in that subsequent processing is the production of foam and the composition includes a polyol as one and isocyanate components and as votolatino catalyst - votolatino base (A2) according to claim 1.



 

Same patents:

FIELD: physics.

SUBSTANCE: invention relates to instrument making. The invention has a flexible membrane for inflatable expanded structures, which has one layer of composite material and at least one polymer film which is permeable to visible radiation and covers one side of the said layer. The composite material is made from fibre material impregnated with a composition which contains epoxy or epoxy/acrylate resin and a photoinitiator which is a complex salt containing iron, an arene group and a non-nucleophilic anion.

EFFECT: optimisation of mechanical properties of the membrane.

17 cl, 7 dwg, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing heat-resistant positive photoresist, which is used as a protective coating in interlayer insulation in multilevel electronic devices. The method of producing heat-resistant positive photoresist involves polycondensation of dichloride of isophthalic acid with a mixture of 3,3'-dihydroxy-4,4'-diaminodiphenylmethane and bis-(3-aminopropyl)dimethylsiloxane in an amide solvent with ratio of amine components ranging from 9:1 to 1:9 mol %. A solution of the photosensitive component β,β-bis-naphthoquinondiazido-(1,2)-5-sulphoether-(4-hydroxyphenyl)propane in amide solvent is added directly to the reaction mass after completion of the polycondensation reaction. To obtain the phororesist, the following ratio of components is chosen, wt %: reaction solution of poly(o-hydroxyamide) - 80-90; β,β-bis-naphthoquinondiazido -(1,2)-5-sulphoether-(4-hydroxyphenyl)propane - 1.5-6.5; amide solvent - the rest.

EFFECT: obtained heat-resistant positive photoresist reliably provides for formation of high resolution, adhesive-strong, chemically stable positive microrelief on combined, including silicon-containing substrates.

3 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing heat-resistant positive photoresist, which is used as a protective coating in interlayer insulation in multilevel electronic devices. The method of producing heat-resistant positive photoresist involves polycondensation of dichloride of isophthalic acid with a mixture of 3,3'-dihydroxy-4,4'-diaminodiphenylmethane and bis-(3-aminopropyl)dimethylsiloxane in an amide solvent with ratio of amine components ranging from 9:1 to 1:9 mol %. A solution of the photosensitive component β,β-bis-naphthoquinondiazido-(1,2)-5-sulphoether-(4-hydroxyphenyl)propane in amide solvent is added directly to the reaction mass after completion of the polycondensation reaction. To obtain the phororesist, the following ratio of components is chosen, wt %: reaction solution of poly(o-hydroxyamide) - 80-90; β,β-bis-naphthoquinondiazido -(1,2)-5-sulphoether-(4-hydroxyphenyl)propane - 1.5-6.5; amide solvent - the rest.

EFFECT: obtained heat-resistant positive photoresist reliably provides for formation of high resolution, adhesive-strong, chemically stable positive microrelief on combined, including silicon-containing substrates.

3 cl, 3 ex

FIELD: physics; photography.

SUBSTANCE: invention relates to a photosensitive polymer composition, preferably used in a flexographic printing plate. A photosensitive polymer composition is proposed, which contains a thermoplastic elastomer (a), which contains at least a vinyl aromatic hydrocarbon link, a butadiene link and an alkylene link, where content the alkylene link is not less than 10 wt % and not more than 60 wt % of the total amount of butadiene and alkylene links; a photopolymerisable unsaturated monomer (b) and a photopolymerisation initiator (c).

EFFECT: photosensitive polymer composition provides for high reproducibility of thin lines, resistance to ether solvent and prevention of formation of cracks on the surface of the plate.

15 cl, 1 tbl, 7 ex

FIELD: printing industry.

SUBSTANCE: method is suggested for manufacturing of material for base of stencil printing. According to method, the first resist layer is applied onto one side of protective film, then the first layer of resist is dried, and additional layer of resist is applied into the first layer of resist. After that stencil grid is applied onto additional layer of resist, at the same time side of additional resist layer is moist. Stencil grid is pressed into additional layer of resist under pressure of pressing element, which directly contacts to stencil grid. Besides layer of resist contain additional layer of resist and the first layer of resist.

EFFECT: provision of method for manufacturing of base material, in which openings in material of stencil grid are homogeneously filled with light-sensitive material without losses of light-sensitive material.

15 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to new photosensitive organic systems based on chromone, designed for use in different photocontrolled devices in photonics. Description is given of new substituted or unsubstituted derivatives of 2-furyl-3-acetylchromones, which have photo-induced fluorescence. The method of producing the said compounds involves acylation of 2-hydroxyacetophenone or its corresponding derivative with acyl chloride with subsequent treatment of the reaction product with potassium tret-butoxide. The formed derivative of β-diketone is subjected to crotonic condensation with aldehyde at low temperature from (-)10 to 15°C and then oxidation with selenium dioxide. Described also is a photosensitive polymer material with photo-induced fluorescence based on the said chromone derivatives, production of the said material and use in photosensitive recording medium for three-dimensional archival optical memory.

EFFECT: use of proposed chromone derivatives in a polymer layer provide for irreversible photocontrol of their luminescent properties and rectify the problem of mismatch of absorption bands of photosensitive materials with radiation of semiconductor lasers due to bathochromic shift of absorption bands of photosensitive materials by 10 to 50 nm.

6 cl, 2 dwg, 2 tbl, 12 ex

FIELD: printing industry.

SUBSTANCE: invention relates to inks sensitive to infra-red radiation (IR), finding application for tracking and authentication of different objects. Inks with IR sensitivity fasten under the influence of ultraviolet is described, including: curing (UV) light matrix, which includes any number of epoxy and/or acrylate oligomers; UV photoinitiator, and IR-sensitive dye. System for the covering of said UV drying inks with IR sensitivity is also described.

EFFECT: offered inks in comparison with known not fasten infrared-sensitive inks possess durability and water resistance and improve the environment by excluding emissions of the solvent.

14 cl, 2 dwg, 2 tbl, 1 ex

FIELD: instrument engineering.

SUBSTANCE: present invention concerns nano-imprinting stamp designed for imprinting the millimicron (nano) and millimeter structures. Nano-imprinting stamp 1 has a major component and a first and second imprinting component 2, 3, with lithographic pattern 7 to be imprinted in a printable substrate. In first aspect, first and the second imprinting components 2, 3 can be displaced independently in a direction practically parallel to that of imprinting of the imprinting stamp. In the second aspect, first and second imprinting components 2, 3 are loosely coupled mechanically in a direction practically parallel to that of imprinting of the imprinting stamp. The stamp limits impact of defects in the substrate printed with the lithographic pattern 7, or thereon, and defects in the stamp or thereon, and any combinations of such defects by localisation of stamp bend in the major component 5 between imprinting components 2, 3.

EFFECT: design of the flexible stamp for "НВЛ" which can limit impact of defects in the substrate.

31 cl, 7 dwg

FIELD: technological processes.

SUBSTANCE: invention is related to galvanoplastics. Matrix for galvanoplastics of printing screens includes matrix plate, on which metal is deposited for moulding of printing screen. Matrix plate includes the main surface of deposition, on which metal deposited to create the main body of printing screen, at least one pair of edge segments at the opposite borders of the main deposition surface, which include edge segments of deposition, which come out from plane produced by the main deposition surface, on which metal is deposited to create fastening elements of printing screen, and angular sections in appropriate angles of deposition surface. Matrix also includes non-conducting elements in the form of edge elements, which are located at edge sections so that they create length of these edge sections, and non-conducting elements in the form of angular elements, which are located near angle sections so that they protect them and create length of the main deposition surface near these angular sections.

EFFECT: expansion of assortment of produced items.

67 cl, 37 dwg

FIELD: production processes.

SUBSTANCE: proposed method serves to plot images on an object (OBJ) and comprises a flat surface arranged perpendicular to radiation a light sensitive zone (PR). Aforesaid object may move crosswise relative to this radiation. The radiation intended for photo lithography comprises, at least, one line in the far-UV range and consists of N consecutive running pulses, their FUV-radiation surface power being measured after this radiation passed through radiating window. The FUV-radiation pulses are produced by exciting an appropriate target with the help of, at least, two laser beams running out from pulsed laser sources selected from a set. Each laser set radiates, on every switching on, a laser pulse with energy (Q) and preset duration (Δt), the laser sources being focused at the same point on target. The proposed method comprises the following reiterative stages within the limits of one n-th repetition: a) integrating the surface power of FUV-radiation that passed through radiating window in n-1 of the last pulses; b) translational movement of the light sensitive object at the distance equal to 1/N-th fraction of radiating window width (L) along the translation axis; c) subtracting the integral obtained at the stage (a) from the amount of power (Wtot) required for photo lithography; d) determining the amount of power to be generated to produce (Wtot); e) computing the number of laser pulses to be generated to n-th running pulse; f) determining the appropriate number of laser sources intended for switching on and selecting the laser sources in the amount equal to integer of the said number; g) synchronous switching on of laser sources selected at the stage (e) and reiterating stages (a) to (f) for the nest running point.

EFFECT: method efficient in continuous operation, error in determining exposure dose not exceeding 0,1% or smaller.

16 cl, 6 dwg

FIELD: pharmacology.

SUBSTANCE: present invention refers to compounds of formula (I) , to its N-oxides, salts, stereoisomer forms where n is equal 1, 2 or 3; R1 means cyano group; X means bivalent radical NR2 or O; R2 means hydrogen or C1-10alkyl, each Q1 independently stands for direct coupling, -CH2- or -CH2-CH2-; each R4 independently means hydrogen or C1-4alkyl; each R5a, R5b, R5c independently means hydrogen, C1-4alkyl or arylC1-4alkyl; each R5e, R5f independently means hydrogen, C1-4alkyl or arylC1-4alkyl, or R5e and R5f together can form bivalent alkandiyl radical of formula -CH2-CH2- or -CH2-CH2-CH2-; R11 means aryl, arylC1-4alkyl, C1-4alkylcarbonyl, arylcarbonyl, arylC1-4alkylcarbonyl, C1-4alkyloxycarbonyl, arylC1-4alkyloxycarbonyl, R5aR5bN-carbonyl, hydroxyC1-4alkyl, C1-4alkyloxyC1-4alkyl, arylC1-4alkyloxyC1-4alkyl, aryloxyC1-4alkyl, pyridyl; -a1=a2-a3=a4- means a bivalent radical of formula -CH=CH-CH=CH- (c-1); where one or two hydrogen atoms in (c-1) are substituted by radical C1-6alkyl, C1-4alkoxy, halogen, hydroxy group, (R5g)(R5h)N-(C1-4alkandiyl)-O-trifluoromethyl, cyano group, radical -COOR4, (R5a)(R5b)N-sulphonyl, pyrrolidinyl-sulphonyl, piperidinyl sulphonyl, radical N(R5a)(R5b), radical (a-1), (a-7), morpholinyl, (R5g)(R5h)N-(C1-4alkandiyl)-N(R5c)-, C1-6alkylcarbonylamino, C1-6alkyloxycarbonylamino, C1-6alkylsulphonylamino, (R5a)(R5b)N-C1-4alkyl; R20 means hydrogen, spiro (C2-4alkylenedioxy), spiro (diC1-4alkyoxy) or -NR5gR5h; each R5g or R5h independently means either hydrogen, or C1-4alkyl, or R5g and R5h together with nitrogen atom whereto attached form pyrrolidinyl, piperidinyl or morpholinyl; R3 means nitro group, cyano group, amino group, halogen, hydroxy group or C1-4alkoxy; aryl means phenyl optionally substituted with one or more substitutes chosen from the group consisting of C1-6alkyl, C1-4alkoxy, halogen, hydroxy, amino and trifluoromethyl. Besides it relates to the pharmaceutical composition with antiviral activity, and method for making said compounds.

EFFECT: there are prepared and described new compounds with antiviral activity.

9 cl, 15 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a dynamic nuclear polarisation method of a compound which contains one or more carboxyl groups, distinguished by that, the radical of formula (I) , where M is one equivalent cation of an alkali metal; and R1, which are identical or different, each represents a C1-C6-alkyl group with a straight or branched chain or a -(CH2)n-X-R2 group, where n equals 1, 2 or 3; X is O; and R2 is a C1-C4alkyl group with a straight or branched chain, which are used a paramagnetic agent in the said dynamic nuclear polarisation process. The invention also relates to new radicals, to their use as paramagnetic agents.

EFFECT: obtaining new radicals of formula (I), which are used as paramagnetic agents in dynamic nuclear polarisation processes.

17 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a liquid composition which contains hyperpolarised 13C-pyruvate, involving: a) formation of a liquid mixture containing a radical of formula (I) , where M is hydrogen or one equivalent cation; and R1, which are identical or different, each represents hydroxylated and/or alkoxolated C1-C4-hydrocarbon group with a straight or branched chain, 13C-pyroracemic acid and/or 13C-pyruvate, and freezing this mixture; b) increasing polarisation of 13C nuclei of pyroracemic acid and/or pyruvate in this mixture through dynamic nuclear polarisation c) addition of a physiologically transferable buffer, which provides for pH in the range from 7 to 8, and a base to the frozen mixture for its dissolution and for converting 13C-pyroracemic acid to 13C-pyruvate, obtaining a liquid composition or, when at stage (a) only 13C-pyruvate is used, addition of a buffer to the frozen mixture for its dissolution, obtaining a liquid composition; and d) possible removal of the radical and/or its reaction products from the liquid composition. The invention also relates to use of such a composition and to a radical of formula (I).

EFFECT: obtaining a composition for use as MP of a visualising agent.

22 cl, 2 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to new compounds with formula I: , where D is O; E is CH2 or O; n equals 1 or 2, and R1 is chosen from hydrogen, halogen or substituted or unsubstituted 5- or 6-member aromatic or heteroaromatic ring with 0, 1 or 2 nitrogen atoms, 0 or 1 oxygen atom, or is chosen from substituted or unsubstituted 8-, 9- or 10-member condensed heteroaromatic ring system with 0 or 1 nitrogen atom, 0 or 1 oxygen atom, where the said aromatic or heteroaromatic rings or ring systems, when they are substituted, have substitutes which are chosen from -C1-C6alkyl, -C3-C6cycloalkyl, -C1-C6alkoxy, halogen, -CF3, -S(O)mR2, where m equals 0, 1 or 2, -NR2R3, -NR2C(O)R3 or -C(O)NR2R3; R2 and R3 are in each case independently chosen from hydrogen, -C1-C4alkyl, -C3-C6cycloalkyl, aryl; or its stereoisomers, enantiomers or pharmaceutically acceptable salts; under the condition that the given compound is not 2-(1-aza-bicyclo[2.2.2]oct-3-yl)-2,3-dihydroisoindol-1-one. The invention also relates to compounds with formulae II or III, to a pharmaceutical composition, as well as to use of compounds in paragraph 1.

EFFECT: obtaining new biologically active compounds with activity towards alpha 7 nicotinic acetylcholine receptors (α7 nAChRs).

8 cl, 72 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to the new compounds of formula I in the form of the salt or zwitter-ion, wherein R1 and R3 are independently phenyl, C3-C8 cycloalkyl or thienyl group, R2 is haloid or hydroxyl group; R4 is C1-C8 alkyl substituted with -NR5-CO-R6 or -CO-NR9R10; R5 is hydrogen ; R6 is C1-C8alkyl or C1-C8 alkoxy, each of them is optionally substituted with 5- or 6-membered heterocyclic group containing at least one ring heteroatom selected from nitrogen, oxygen and sulphur, or R6 is 5-10-membered heterocyclic group containing at least one ring heteroatom selected from nitrogen, oxygen and sulphur; R9 is hydrogen or C1-C8alkyl; R10 is C1-C8alkyl, optionally substituted with cyano group, C1-C8 alkoxy group or with 5- or 6-membered heterocyclic group containing at least one ring heteroatom selected from nitrogen, oxygen and sulphur, or R10 is 5-9-membered heterocyclic group containing at least one ring heteroatom selected from nitrogen, oxygen and sulphur. The invention refers also to the pharmaceutic composition, to the application of compound of any of claims 1-5 as well as to the preparation method of compound of formula I of claim 1.

EFFECT: preparation of the new biologically active compounds taking the effect of muscarin receptor M3.

9 cl, 247 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to derivatives of 1,4-diazabicyclo[3,2,1]octanecarboxamide with general formula (1) , in which X is a nitrogen atom, P and W each independently represent a nitrogen atom or a group with general formula C-R3, Q and R each independently represent a group with general formula C-R3, R1 is a hydrogen atom, R3 is a hydrogen atom or halogen or C1-C6-alkyl, C1-C6-alkoxy, O-Ms. The invention also relates to a medicinal preparation and pharmaceutical composition based on these compounds for treating or preventing disorders, related to malfunction of nicotinic receptors.

EFFECT: obtaining new compounds and a pharmaceutical composition based on the said compounds, which can be used for treating cognition failure and attention failure, or for treating motor, neurological or alerting symptoms related to dependency on different addictive substances.

5 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention is related to the compound of general formula 1 or its tautomer or pharmaceutically acceptable salt, where W selected from N and CR4; X is selected from CH(R8), O, S, N(R8), C(=O), C(=O)O, C(=O)N(R8), OC(=O), N(R8)C(=O), C(R8)-CH and C(=R8); G1 - bicyclic or tricyclic condensed derivative of azepin, selected from general formulas 2-9 , or derivative of aniline of common formula 10 , where A1, A4, A7 and A10 are independently selected from CH2, C=O, O and NR10; A2, A3, A9, A11, A13, A14, A15, A19 and A20 are independently selected from CH and N; or A5 stands for covalent connection, and A6 represents S; or A5 stands for N=CH, and A6 represents covalent connection; A8 , A12 , A18 and A21 are independently selected from CH=CH, NH, NCH3 and S; A16 and A17 both represent CH2, or one from A16 and A17 represents CH2, and the one another is selected from C=O, CH(OH), CF2, O, SOc and NR10; Y is selected from CH=CH or S; R1 and R2 are independently selected from H, F, Cl, Br, alkyl, CF3 and group O-alkyl; R3 is selected from H and alkyl; R4-R7 are independently selected from H, F, Cl, Br, alkyl, CF3, OH and group O-alkyl; R8 is selected from H, (CH2)bR9 and (C=O)(CH2)bR9; R9 is selected from H, alkyl, possibly substituted aryl, possibly substituted heteroaryl, OH, groups O-alkyl, OC(=O)alkyl, NH2, NHalkyl, N(alkyl)2, CHO, CO2H, CO2alkyl, CONH2, CONHalkyl, CON(alkyl)2 and CN; R10 is selected from H, alkyl, group COalkyl and (CH2)dOH; R11 is selected from alkyl, (CH2)dAr, (CH2)dOH, (CH2)dNH2, group (CH2)aCOOalkyl, (CH2)dCOOH and (CH2)dOAr; R12 and R13 are independently selected from H, alkyl, F, CI, Br, CH(OCH3)2, CHF2, CF3, groups COOalkyl, CONHalkyl, (CH2)dNHCH2Ar, CON(alkyl)2, CHO, COOH, (CH2)dOH, (CH2)dNH2, N(alkyl)2, CONH(CH2)dAr and Ar; Ar is selected from possibly substituted heterocycles or possibly substituted phenyl; a is selected from 1, 2 and 3; b is selected from 1, 2, 3 and 4; c is selected from 0, 1 and 2; and d is selected from 0, 1, 2 and 3. Besides, the invention is related to pharmaceutical compound and to method for activation of vasopressin receptors of type 2.

EFFECT: compounds according to invention represent agonists of receptor of vasopressin V2, which stipulates for their application (another object of invention) for preparation of medicine for treatment of condition selected from polyuria, including polyuria, which is due to central diabetes insipidus, nocturnal enuresis of nocturnal polyurea, for control of enuresis, to postpone bladder emptying and for treatment of disorders related to bleeds.

21 cl, 228 ex

FIELD: chemistry.

SUBSTANCE: present invention refers to substituted 8-heteroarylzantines of general formula where R represents hydrogen, (C1-C5)alkyl or halogen(C1-C8)alkyl; R1 is chosen from (C3-C6)cycloalkyl or (C3-C6)cycloalkyl(C1-C4)alkyl-; R2 is chosen from (C1-C8)alkyl, (C3-C8)alkenyl, (C3-C8)alkinyl, (C3-C8)cycloalkyl, (C3-C8)cycloalkyl(C1-C8)alkyl- or (C6-C10)aryl(C1-C8)alkyl-; X represents 3-pyridyl substituted in 6th position with Z; Z represents -NR4R5 or (C4-C10)heterocycle where heterocycle is optionally substituted with 1, 2, 3 or 4 substitutes independently chosen from (C1-C8)alkyl; each Z1 independently represents halogen or -NR7R8; R5 is chosen from -C(O)R6, -CO2R6 or -C(O)NHR7; R4 is chosen from hydrogen, (C1-C8)alkyl, (C3-C8)cycloalkyl, (C3-C8)cycloalkyl(C1-C8)alkyl-, (C3-C10)heterocycle(C1-C8)alkyl-, (C6-C10)aryl, (C6-C10)aryl(C1-C8)alkyl-, (C5-C10)heteroaryl, (C5-C10)heteroaryl(C1-C8)alkyl-, -((CH2)2-4)Y)q-(CH2)2-4-X1, -C(O)R6, -CO2R6 or -C(O)NR7R8; or R4 and R5 together with atoms whereto attached form saturated mono-or bicyclic ring with 5, 6, 7 or 8 ring atoms and optionally containing 1 or 2 heteroatoms chosen of non-peroxide oxy (-0-) and amine -N(R9)- in the ring where the ring is optionally substituted by 1, 2, 3 or 4 substitutes independently chosen from -C(O)Ra and -C(O)NRbRc; X1 represents -OR6; and Y represents oxy (-O-); where alkyl, alkenyl, cycloalkyl, alkinyl, aryl, heterocyclic or hetero aryl groups from R1, R2, R3, R4 and R5 groups are optionally substituted by one or more substitutes independently chosen from (C1-C8)alkyl, -ORa, (C6-C10)aryl, hydroxy(C1-C8)alkyl and RbRcN(C1-C8)alkyl; where R6 represents (C1-C8)alkyl or (C4-C10)heteroaryl; where heteroaryl is optionally substituted by 1, 2, 3 or 4 substitutes independently chosen from halogen, -ORa and halogen(C1-C8)alkyl; where R7, R8 and R9 independently represent (C1-C8)alkyl, RaO(C1-C8)alkyl, (C6-C10)aryl or (C4-C10)heteroaryl; where heteroaryl or aryl are optionally substituted by 1, 2, 3 or 4 substitutes independently chosen from halogen and -ORa; Ra represents hydrogen or (C1-C6)alkyl; each Rb and Rc independently represents hydrogen or (C6-C10)aryl; and where n is equal to 0, 1 or 2; and q is equal to 1; or its pharmaceutically acceptable salt. In addition, the invention concerns pharmaceutical composition based on compound of formula I.

EFFECT: new substituted 8-heteroarylxantines are selective antagonists of A2B adenosine receptors.

38 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to new photochromic monomers and new polymers based on such monomers, intended for use in making two-photon photochromic recording media for three dimensional optical memory and photoswitches of optical signals. Description is given of monomers

Q=; ; ;

Alk=CH3-C10H21 X=Cl, Br, I, F, NH2, CH2OH, CH2Cl, CH2Br, CHO, CO2H and X=CH2, O, S, NAlk; Y=O, S, NAlk; n=0-6; Q=; ; ; ; ;

Alk=CH3-C10H21, methods of obtaining them, photochromic polymers based on them, method of obtaining photochromic monomers and their application. The proposed materials exhibit thermal irreversibility of photochromic transformations and properties, making it possible to use photochromic polymers in two-photon random access optical memory.

EFFECT: obtaining materials with thermal irreversibility of photochromic transformations and properties, making it possible to use photochromic polymers in two-photon random access optical memory.

15 cl, 46 dwg, 31 ex

FIELD: chemistry.

SUBSTANCE: invention concerns compounds of formula (I) and their pharmaceutically acceptable salts as β-lactamase inhibitors, method of their production, pharmaceutical composition based on them, and methods of treatment involving the claimed compounds. In the general formula (I) one of A and B is hydrogen, while the other is optionally substituted condensed bicyclic heteroaryl group; if aromatic ring part of bicyclic heteroaryl group is imidazole, non-aromatic ring part does not include S atom adjacent to head carbon atom of bridge group; X is S; R5 is H, C1-C6-alkyl or C5-C6-cycloalkyl; or its pharmaceutically acceptable salt where bicyclic heteroaryl group is (1-A) , where one of Z1, Z2 and Z3 is independently S, while the others are CR2 or S, if one of Z1-Z3 is carbon and is linked to the rest of molecule; W1, W2 and W3 are independently CR4R4, S, O or N-R1, if it does not form S-S, O-O, or S-O link with saturated ring system; t=1-4; R1 is H, C1-C6-alkyl, C5-C7-cycloalkyl, -C=O-aryl, -C=O(C1-C6)-alkyl, -C=O(C5-C6)-cycloalkyl, aryl-C1-C6-alkyl, optionally substituted C1-C6-alkoxy; heteroalkyl- C1-C6-alkyl or C=O(heteroaryl), where heteroaryl is 6-member ring containing 1 nitrogen atom, R2 is hydrogen, C1-C6-alkyl, R4 ir H, C1-C6-alkyl.

EFFECT: efficient application in bacterial infection treatment.

29 cl, 3 tbl, 58 ex

FIELD: chemistry.

SUBSTANCE: invention relates to self-organising supramolecular ion-associates of oppositely charged phthalocyanines and their use for oxidising sodium sulphide. A catalyst for oxidising sodium sulphide is described, where the said catalyst is a phthalocyanine derivative and is distinguished by that, it is a supramolecular ion-associate of oppositely charged phthalocyanines with structural formula I, I:(R+)nPcM, where R=-CH2N+(CH3)2CH2CH2OHCl- (choln- PcM), n=2÷8, M=Co, Fe; (pymn-PcM), n=2÷8, M=Co, Fe; (R-)nPcM, where R=-CH2P(=O)(O-Na+)2(phosn-PcM), n=8, M-Co and II, II:(R-)nPcM, where R=R1=R2=-C(O)O-Na+ (carb8-PcM), n=8, M=Co, Fe; R=R1=-C(O)O-Na+, R2=H (carb4-PcM), n=4, M=Co; R= R1=-S(O)2O-Na+ , R2=H (sul4-PcM), n=4, M=Co. Also described is a method of oxidising sodium sulphide with oxygen in the presence of the above described catalyst.

EFFECT: achieved complete substrate conversion corresponding to activity 3.1x103 mol(Na2S)/mol (catalyst) min.

3 cl, 2 tbl, 44 ex

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