Covering substance with high resistance to scratching and resistant to atmospheric impact

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, and at least one compound (B), containing isocyanate groups, and one or several components of covering substance have between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (I), where R'=hydrogen, alkyl or cycloalkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene or cycloalkylene residue with from 1 to 20 carbon atoms; R"= alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (II), where Z=-NH-, -NR-, -O-; R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above; and polyol (A) contains at least one poly(meth)acrylate polyol. Also claimed are multi-step method of applying coating with application of said covering substance, method application and versions of coating application.

EFFECT: possibility of simple obtaining of transparent varnish coatings with high resistance to crack formation under atmospheric impact and perfect resistance to scratching, which do not cause any ecological problems.

15 cl, 2 tbl, 4 ex

 

The present invention relates to thermally curable highly resistant to scratching the covering means on the basis of aprotic solvents containing polyols and polyisocyanates with structural units of the various alkoxysilane functionality.

In WO-A-01/98393 described 2K-top products containing polyol as a film-forming component, and as a component transverse relationship with the polyisocyanate, which is partially functionalized with alkoxysilane groups. These cover means is used as a primer and is optimized for adhesion to metal substrates, especially aluminum substrates. These top funds within OEM serial coating or repair of the coating can be applied to the compositions of the main lacquer clear lacquer. In terms of resistance to scratching and weathering coating means according to WO 01/98393 not optimized.

In EP-A-0994117 described moisture curing mixture containing polyol as one component and a polyisocyanate component, which may in part be subjected to interaction with monoalkanolamines came into the reaction it is preferable to obtain aspartate. Coverage of these compounds, although having a certain hardness, however, with respect to resistance to atmospheric the stress and in particular with regard to their resistance to scratching for OEM applications are suitable only conditionally.

US-A-2006/0217472 describes the covering means, which may contain hydroxyquinoline acrylate, low-molecular-weight polyol as one component, a polyisocyanate, and amidofunctional alkoxysilyl component, preferably bichlkashvlly. Such cover means is used as a clear varnish in the compositions of the main lacquer clear lacquer and provide a scratch resistant coating. However, such cover means are suitable for storage only very conditionally, and the resulting coatings have a low resistance to weathering, particularly with respect to UV radiation in a cycle of wet-dry.

In WO 2006/042585 describes transparent varnishes suitable for OEM serial coating, which as the main film-forming component containing polyisocyanates, isocyanate groups which are mostly more than 90 mol.% interact with bezalkogolnymi. Transparent varnish of this kind have excellent resistance to scratching with high chemical resistance and resistance to weathering. The truth is still need for further improvement in resistance to atmospheric influences, in particular against crack formation by UV radiation in a cycle of wet-dry, while maintaining a high level stoichastic scratch.

EP-A-1273640 describes 2K-top tool, consisting of a polyol as one component and a component transverse relationship consisting of aliphatic and/or cycloaliphatic polyisocyanates, and 0.1 to 95 mol.% initially available free isocyanate groups are interacting with bezalkogoljnogo. These top funds can be used for OEM serial varnishing and have good resistance to scratching while resistance to environmental influences. However, these top tools are particularly prone to subsequent crosslinking, since the interaction with thermal curing after the application is insufficient. This is a particularly adverse effect on resistance to weathering.

Problem and solution

The present invention was to provide cover means, in particular for coating a transparent varnish with OEM-serial lakirovanie and repair lakirovanie that provide extremely resistant to weathering the grid, and the undesirable formation of hydrolytically unstable and atmosferostojki groups strongly suppressed in order to guarantee a high acid resistance. Along with these top tools should provide coatings which are resistant to scratching and, in particular, maintain a high degree of gloss after exposure tarpanam. In addition, coating and varnish covering, especially a transparent lacquer coating must also be obtained with a layer thickness of >40 μm without the occurrence of cracks due to internal stresses. This is an important prerequisite for the application of coatings and lacquer coatings, particularly coatings transparent varnish, in the technologically and esthetically particularly demanding field of serial finishing paint cars (OEM). In particular, should be made available to the transparent lacquer coating with a high resistance, especially to the formation of cracks at atmospheric UV radiation in a cycle of wet-dry in combination with excellent resistance to scratching.

Moreover, new top funds must be received in a simple way and very well played and during the coating does not cause environmental problems.

The solution of the problem

In light of the above formulation of the problem have been found coating agent containing at least one containing the hydroxyl group of the compound (A)and at least one containing isocyanate groups of the compound (B), characterized in that one or more components of the coating tool as an additional functional components contain between

the 2.5 and 97.5 mol%, in terms of the totality of the structure of the business units (I) and (II), at least one structural unit (I) of the formula

and

R' = hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa,

X,X' = linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,

R" = alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa,

n=0 to 2,

m=0 to 2,

m+n=2, and

x,y=0 to 2,

and 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit (II) of the formula

and

Z=-NH-, -NR-, -O - c

R = hydrogen, alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl,

R' = hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa,

X = linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,

R" = alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa,

x=0 to 2.

Preferably the cover means, in which one or more components of the coating tool as an additional functional components have between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.% and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (I) and (II)at least one structural unit of formula (I) and between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.% and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (I) and (II)at least one structural unit of formula (II).

Whereas the prior art it was surprising and not obvious to a person skilled in the art that the tasks that lay at the basis of the present invention could be solved by using coating means according to the invention.

Components according to the invention can be produced particularly easily and with very good reproducibility, and when the varnish does not cause significant Toxicological and environmental problems.

Cover means according to the invention provide a new coating and varnish coatings, especially transparent lacquer coatings which are highly resistant to scratching and in contrast to common longevity highly crosslinked stand the m to scratching systems are acid-fast. Further, it is possible to obtain coatings according to the invention and varnish covering, especially a transparent lacquer coating, with a thickness of >40 μm without the occurrence of cracks due to internal stresses. And therefore, according to the invention the coating and lacquer coating, in particular a transparent lacquer coating, can be used in the technologically and esthetically particularly demanding field of coating hire repetitive manufacturing (OEM). They are particularly high resistance at an automatic car wash and resistance to scratching. In particular, high resistance to scratch coatings is given after the final curing of the coating, so that the coating can easily apply directly after final curing. In addition, an excellent resistance of the coatings according to the invention against crack formation by UV rays and changes in the wet-dry in SAM-test (according to DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2 Nov 00) in combination with high resistance to scratching.

Description of the invention

Containing the hydroxyl group of the compound (A)

As containing the hydroxyl group of the compound (A) used mainly low molecular weight polyols, as well as oligo - and/or polymeric polyols.

As low molecular weight polyols using the, for example, diols, such as preferably ethylene glycol, neopentylglycol, 1,2-propandiol,2,2,-dimethyl-1,3-propandiol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol,2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and 1,2-cyclohexanedimethanol, and also polyols, such as preferably trimethylated, trimethylolpropane, trimethylhexane, 1,2,4-butanetriol, pentaerythritol and dipentaerythritol.

Preferably, such low molecular weight polyols admixed in minor fractions of oligo - and/or polymer polianovich component (A).

Preferred oligo - and/or polymeric polyols (A) are srednesemennyh molecular weight Mw>500 daltons, as measured by GPC (helpanimals chromatography), preferably between 800 and 100,000 daltons, in particular between 1000 and 50,000 daltons. Particularly preferred polyether polyols poliuretanoviy, polisiloksanovoy and especially polyacrylonitrile and/or polymethacrylates, as well as their copolymers, hereinafter called polyacrylonitrile. The polyols preferably have IT-a number from 30 to 400 mg KOH/g, in particular between 100 and 300 KOH/g transition Temperature in the glassy state polyols, measured by DSC (differential thermal analysis), are preferably between -150 and 100°C., particularly preferably between -120°C and 80°C. Suitable polyether polyols are, for example, described in EP-A-0994117 and EP-A-1273640. Poliuretanoviy mainly produced by the interaction polyetherpolyols fluoropolymers with a suitable di - or polyisocyanates and are described, for example, in EP-A-1273640. Suitable polisiloksanovye are for example described in WO-A-01/09260, and given there polisiloksanovoy preferably can be used in combination with other polyols, in particular having a higher junction temperature in the glassy state.

According to the invention very particularly preferred polyacrylonitrile typically are copolymers and mostly srednesemennyh molecular weight Mw between 1000 and 20,000 daltons, in particular between 1500 and 10,000 daltons, each time measured by means of gel chromatography (GPC) versus polystyrene standards. The temperature of transition to the glassy state of the copolymers is generally between -100 and 100°C., in particular between -50 and 80°C (measured by DSC measurements). Polyacrylonitrile are preferably IT is in the range from 60 to 250 mg KOH/g, in particular between 70 and 200 KOH/g and an acid number of between 0 and 30 mg KOH/g

Hydroxyl number (OH-number) specifies the number of mg of potassium hydroxide equivalent to the amount of acetic acid which,when acetylation is associated 1 g of substance. When determining the sample is boiled with acetic anhydride-pyridine, and the resulting acid is titrated with potassium hydroxide solution (DIN 53240-2).

When this acid number indicates the number of mg of potassium hydroxide, which is consumed to neutralize 1 g of the corresponding compounds of the component (b) (DIN EN ISO 2114).

As containing the hydroxyl group of the monomer unit is preferably used hydroxyethylacrylate and/or hydroxyethylmethacrylate, such as especially 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2 - hydroxypropylmethacrylate, 2-hydroxypropylmethacrylate, 3-hydroxypropylamino, 3-hydroxypropylmethacrylate, 3-hydroxyethylacrylate, 3-hydroxyethylmethacrylate and in particular 4-hydroxyethylacrylate and/or 4-hydroxyethylmethacrylate.

As the other monomer unit for polyacrylonitriles preferably used alkyl methacrylates and/or alkyl methacrylates, such as predominantly acrylate, ethyl methacrylate, propylacetate, propylbetaine, isopropylacetate, isopropylacetate, butyl acrylate, butylmethacrylate, isobutylacetate, isobutylacetate, tert-butyl acrylate, tert-butylmethacrylate, amylacetate, amylmetacresol, hexidecimal, vexillarius, hexyl acrylate, ethylhexylacrylate, 3,3,5-trimethylhexanoyl, 3,3,5-trimethylhexamethylene, stearyl is relat, sterilisability, laurelcrest or laurenmarie, cycloalkylcarbonyl and/or cycloalkylation, such as cyclopentylamine, cyclopentylmethyl, isobutylacetate, isobornylacrylat or especially cyclohexylacetate and/or cyclohexylmethyl.

As the other monomer unit for polyacrylonitriles can be used vinylaromatic hydrocarbons, such as vinyltoluene, alpha methylsterol or in particular styrene, amides or NITRILES of acrylic or methacrylic acid, a complex of vinyl esters or simple vinyl ethers, as well as in small quantities, in particular acrylic or methacrylic acid.

In another form of the invention containing the hydroxyl group of the compound along with a hydroxyl group has a structural unit of the formula (I) and/or formula (II).

Structural units of the formula (I) may be introduced into the compound (A) by incorporating the Monomeric units with similar units or by reacting polyols, which have other functional groups, with a compound of formula (Ia)

moreover, the substituents have the above significance. To interact polyol with a compound (Ia) polyol, respectively, has other functional groups that react vtorichnoi amino group of compound (Ia), in particular acid or epoxy group. According to the invention preferred compounds (Ia) are bis(2-ethyltrimethoxysilane)amine, bis(3-propyltrimethoxysilane)amine, bis(4-butyldimethylsilyl)amine, bis(2-ethyltriethoxysilane)amine, bis(3-propyltriethoxysilane)amine and/or bis(4-butyldimethylsilyl)amine. Very particularly preferred bis(3-propyltrimethoxysilane)amine. This aminosilane available, for example, under the brand name DYNASILAN ® company DEGUSSA, respectively Silquest ® by OSI.

Monomeric units containing the structural elements (I)primarily represents the interaction products of acrylic and/or methacrylic acid or containing epoxy groups alkylacrylate and/or alkyl methacrylates with the above compounds (Ia).

Structural units of the formula (II) may be introduced into the compound (A) by incorporating the Monomeric units with similar units or by reacting polyols, which have other functional groups, with a compound of formula (IIa)

moreover, the substituents have the above significance. To interact polyol with a compound (Ia) polyol, respectively, has other functional groups that react with the functional group-ZH compounds (IIa), such as in osobennostiiakh, epoxy or ester groups. According to the invention preferred compounds (IIa) are omega-aminoalkyl - or omega-hydroxycorticosterone, such as a predominantly 2-AMINOETHYLPIPERAZINE, 2-aminoethylthiomethyl, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyraldehyde, 4-aminoethylthiomethyl, 2-hydroxyethylaminomethyl, 2-hydroxyethylrutoside, 3-hydroxypropylmethacrylate, 3-hydroxypropylmethacrylate, 4-hydroxymethylimidazole, 4-hydroxymethylimidazole. Particularly preferred compounds (IIa) are N-(2-(trimethoxysilyl) ethyl)bonds alkylamines, N-(3-(trimethoxysilyl)propyl)bonds alkylamines, N-(4-(trimethoxysilyl)butyl)bonds alkylamines, N-(2-(triethoxysilyl)ethyl)bonds alkylamines, N-(3-(triethoxysilyl)propyl)bonds alkylamines and/or N-(4-(triethoxysilyl)butyl)alkylamines followed. Quite especially preferred is N-(3-(trimethoxysilyl)propyl)butylamine. This aminosilane available, for example, under the brand name DYNASILAN ® company DEGUSSA, respectively Silquest ® by OSI.

Monomer units which contain structural elements (II)primarily represents the interaction products of acrylic and/or methacrylic acid or containing epoxy groups alkylacrylate and/or alkyl methacrylates, and in the case of hydroc is all alkoxysilyl compounds are products of the interaction of alkylacrylate and/or alkyl methacrylates, especially with the above hydroxy - and/or amidofunctional alkoxysilane compounds (IIa).

Containing isocyanate groups of the compound (In)

Serve as the primary substance preferably used according to the invention containing isocyanate groups of the compounds (B) di - and/or polyisocyanates preferably represent a known substituted or unsubstituted aromatic, aliphatic, cycloaliphatic and/or heterocyclic polyisocyanates. Examples of preferred polyisocyanates are 2,4-colorvision, 2,6-colorvision, difenilmetana-4,4'-diisocyanate, difenilmetana-2,4'-diisocyanate, p-delete the entry, biphenyldiol, 3,3'-dimethyl-4,4'-diphenyldiisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, isophoronediisocyanate, atlantaatlanta, 1,12-dodecanesulfonate, CYCLOBUTANE-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, methylcyclohexylamine, exagerately-2,4-diisocyanate, exagerately-2,6-diisocyanate, hexahydrofuro-1,3-diisocyanate, hexahydrofuro-1,4-diisocyanate, perheravintolan-2,4'-diisocyanate, 4,4'-methylendysiclogecsyldiizosyonat (e.g., Desmodur ® W firm BayerAG), tetramethyldisilazane (for example, TMXDI ® company American Cyanamid) imesi the above polyisocyanates. Next, the preferred polyisocyanates are the biuret dimers and isocyanurate trimers of the above diisocyanates. Particularly preferred polyisocyanates PI are hexamethylene-1,6-diisocyanate, isophoronediisocyanate and 4,4'-methylendysiclogecsyldiizosyonat, biuret dimers and/or isocyanurate trimers.

In another form of the invention presents the polyisocyanates, the polyisocyanate-prepolymers with urethane structural units, which are obtained by interaction of polyols with a stoichiometric excess of the above polyisocyanates. Such a polyisocyanate prepolymers are described for example in US-A-4598131.

According to the invention very particularly preferred structural units (I) and (II) functionalityand containing isocyanate groups of the compound (In) receive particularly preferably by reacting the above di - and/or polyisocyanates with the above compounds (Ia) and (IIA), that is subjected to interaction between 2.5 and 90 mol.%, preferably from 5 to 85 mol.%, particularly preferably from 7.5 to 80 mol.%, isocyanate groups in the polyisocyanate main substance with at least one compound (Ia) and

between 2.5 and 90 mol.%, preferably from 5 to 85 mol.%, particularly preferably from 7.5 to 80 mol.%, isocyanate groups in the polyisocyanate is the main substance with at least one compound (IIa).

The total share of interacting with the compounds (Ia) and (IIa) isocyanate groups is in the polyisocyanate compound (C) between 5 and 95 mol.%, preferably between 10 and 90 mol.%, especially preferably between 15 and 85 mol.% isocyanate groups in the polyisocyanate primary substance.

Particularly preferred compounds (Ia) are bis(2-ethyltrimethoxysilane)amine, bis(3-propyltrimethoxysilane)amine, bis(4-butyldimethylsilyl)amine, bis(2-ethyltriethoxysilane)amine, bis(3-propyltriethoxysilane)amine and/or bis(4-butyldimethylsilyl)amine. Very particularly preferred bis(3-propyltrimethoxysilane)amine. This aminosilane available, for example, under the brand name DYNASILAN ® company DEGUSSA, respectively Silquest ® by OSI.

Preferred compounds (IIa) are 2-AMINOETHYLPIPERAZINE, 2-aminoethylthiomethyl, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyraldehyde,, 4-aminoethylthiomethyl, 2-hydroxyethylaminomethyl, 2-hydroxyethylrutoside, 3-hydroxypropylmethacrylate, 3-hydroxypropylmethacrylate, 4-hydroxymethylimidazole, 4-hydroxymethylimidazole. Particularly preferred compounds (IIa) are N-(2-(trimethoxysilyl)ethyl)bonds alkylamines, N-(3-(trimethoxysilyl)propyl)bonds alkylamines, N-(4-(trimethoxysilyl)butyl)bonds alkylamines, N-(2-(retaxation)ethyl)bonds alkylamines, N-(3-(triethoxysilyl)propyl)bonds alkylamines and/or N-(4-(triethoxysilyl)butyl)alkylamines followed. Very particularly preferred M-(3-(trimethoxysilyl)propyl)butylamine. This aminosilane available, for example, under the brand name DYNASILAN ® company DEGUSSA, respectively Silquest ® by OSI.

Very particularly preferred containing isocyanate groups with compounds (B) are the products of interactions between hexamethylene-1,6-diisocyanate and/or isophorondiisocyanate and/or their isocyanurate trimers with bis(3-propyltrimethoxysilane)amine and N-(3-(trimethoxysilyl)propyl)butylamine.

Interaction containing isocyanate groups of the compounds (V) with compounds (Ia) and (IIa) occurs mainly in the atmosphere of inert gas at temperatures as high as 100°C., most preferably 60°C.

Free isocyanate group-containing isocyanate groups of the compounds may also be used in blocked form. It is preferable in the case when the coating means according to the invention is used as one-component systems. In principle, for blocking can be used each used for blocking polyisocyanates blocking means with a low enough deblokiruyuschee temperature. Such locking means are well known to the person skilled in the art. Suppose the equipment use the blocking means, such as described in EP-A-0626888 and EP-A-0692007.

The combination of components a and b, as well as other components of the integumentary tools

Weight fraction used containing hydroxyl group of compounds And, in terms of weight fraction containing isocyanate groups of the compounds depends on the hydroxy equivalent weight polyol and from the equivalent weight of free isocyanate groups MDI Century

For the invention it is important that the coating media according to the invention contains from 2.5 to 97.5 mol.%, in terms of the amount of the structural units I and II, structural units I and 2.5 to 97.5 mol.%, in terms of the amount of the structural units I and II, structural units II.

Cover means according to the invention contain preferably between 2.5 and 97.5 wt.%, especially preferably between 5 and 95 wt.%, very particularly preferably between 10 and 90 wt.%, in particular between 20 and 80 wt.%, in terms of the content of nonvolatile substances in the coating vehicle containing hydroxyl group of the compounds (a) and preferably between 2.5 and 97.5 wt.%, especially preferably between 5 and 95 wt.%, very particularly preferably between 10 and 90 wt.%, in particular between 20 and 80 wt.%, in terms of the content of nonvolatile substances in the coating vehicle containing isocyanate groups of the compounds (B).

In terms of the amount of extremely neobhodimaja crosslinking in the coating media according to the invention the functional groups, formed from parts of hydroxyl and isocyanate groups, as well as parts of the structural elements (I) and (II), structural elements (I) and (II) are preferably containing from 2.5 to 97.5 mol.%, especially preferably between 5 and 95 mol.% and very particularly preferably between 10 and 90 mol.%.

In order to further ensure the stability of the coatings according to the invention against the formation of cracks when UV radiation and cycle wet-dry in SAM-test (in accordance with DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2 Nov 00) in combination with high resistance to scratching directly after thermal curing, high gloss and high gloss retention after weathering, in addition, it is preferable content of the structural units (I)and/or (II), and/or (III) to choose the most so high that the top funds according to the invention contain less than 6.5 wt.% Si structural units (I)and/or (II), and/or (III), particularly a maximum of 6.0 wt.% Si structural units (I)and/or (II), and/or (III), each time calculated on the solids content of a coating means. The content of the silane wt.% Si calculated from the quantities of compounds with the structural unit (I), respectively, compounds (IIa), (IIIa).

In another form of the invention, the structural elements (I) and/or (II) can optionally be part of one or more different from components (a) and (b) other components (C), and apply the above criteria. For example, as component (C) may apply oligomers or polymers with alkoxysilane groups, such as, for example, described in patents and patent applications US-A-4499150, US-A-4499151 or EP-A-0571073 poly(meth)acrylates as carriers of structural elements (II), or specified in WO-A-2006/042585 compounds as carriers of structural elements (I). As a rule, use the following components (C) with a share of up to 40 wt.%, preferably up to 30 wt.%, particularly preferably up to 25 wt.%, in terms of non-volatile components of a coating means.

The weight proportion of the polyol and MDI In predominantly chosen so that the molar euqivalent the ratio of unreacted isocyanate groups isocyanatomethyl compounds (B) to hydroxyl groups containing hydroxyl group of compound (A) is between 0.9:1 and 1:1,1, preferably between from 0.95:1 and 1.05:1, particularly preferably between to 0.98:1 to 1.02:1.

If we are talking about one-component coating tools, then select containing isocyanate groups of the compound (In)free isocyanate groups are blocked described above, the blocking means.

In a preferred according to the invention 2-component (2K) coating means shortly before application of a coating means mixed world is mainly lacquer component, which contains involving the hydroxyl group of the compound (A), as well as others described in further components, with other lacquer component, including containing isocyanate groups of the compound (C) and optionally other components is described further in, and, as a rule, lacquer component containing compound (A)contains a catalyst, and solvent.

As catalysts for crosslinking alkoxysilyl units, and also for the reaction between hydroxyl groups of the compound (a) and the free isocyanate groups of the compound (In) can be used known compounds. Examples are Lewis acid (compound with a lack of electrons), such as, for example, tin naphthenate, tin benzoate, octoate tin, tin butyrate, dibutylthiourea tin, dibutylthiourea tin, dibutylated tin, octout lead, and catalysts such as described in WO-A-2006/042585. As catalysts for crosslinking alkoxysilyl units prefer preferably the amine addition products of phosphoric acid or sulfonic acids (for example, types of Nacure King Industries).

As the catalyst is particularly preferable to use phosphorus-containing, in particular phosphorus - and nitrogen-containing catalysts. This can also be used a mixture of two or more different ka is alization.

Examples of suitable phosphorus-containing catalysts are substituted complex diesters of phosphonic acids and complex diesters diphosphonic acids, mainly from the group consisting of acyclic phosphonic diesters of acids, cyclic diesters of phosphonic acid, acyclic diphosphonic diesters of acids and cyclic diphosphonic diesters of acid. Such catalysts are described, for example, in German patent application DE-A-102005045228.

However, it is particularly preferable to use substituted complex monetary phosphoric acid and complex diesters of phosphoric acid, mainly from the group consisting of acyclic complex of diesters of phosphoric acid and cyclic complex of diesters of phosphoric acid, particularly preferably addition products amine complex monoamino and diesters of phosphoric acid. In particular, use appropriate aminoketone esters of phosphoric acid and here preferably aminocarbonyl ethylhexylamine esters of phosphoric acid and aminocarbonyl phenyl esters of phosphoric acid, very particularly preferably aminocarbonyl bis(2-ethylhexyl)new esters of phosphoric acid.

The catalysts used mainly in the percentage from 0.01 to 20 wt.%, particularly preferably in the percentage of the t 0.1 to 10 wt.%, in terms of non-volatile components of a coating tool according to the invention. Minor activity of the catalyst can be partially offset by a commensurate higher quantities of feed material.

As solvents for the coating means according to the invention particularly suitable those in top tool are chemically inert in relation to compounds (a) and (b) and also during the curing of the coating means not react with (a) and (B). Examples of such solvents are aliphatic and/or aromatic hydrocarbons, such as toluene, xylene, solvent-naphtha, Solvesso 100 or Hydrosol ® (ARAL), ketones, such as acetone, methyl ethyl ketone or methylmercaptan, esters such as ethyl acetate, butyl acetate, pentalateral or teleconversation, ethers, or mixtures of the above solvents. Preferably aprotic solvents or solvent mixtures have a water content of at most 1 wt.%, particularly preferably a maximum of 0.5 wt.%, in terms of solvent.

Along with the compounds (A), (b) and (C) can be used with other binders (D), which primarily react with hydroxyl groups of the compound (A), and/or with the free isocyanate groups of the compound (C), and/or with Alcock usilinnymi groups of compounds (A), (B) and/or (C), and can form a net structure.

For example, as component (D) used aminoplastic resin and/or apoximately. Suitable are conventional and known aminoplastic resin, methylol and/or methoxymethyl groups can be partially defunctionalization using urethane or allophanate groups. Crosslinking agents of this type are described in patent descriptions US-A-4710542 and ER-IN-0245700, as well as in article C. Singh and employees "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, volume 13, p. from 193 to 207.

As a rule, use the following components (D) with a share of up to 40 wt.%, preferably up to 30 wt.%, particularly preferably up to 25 wt.%, in terms of non-volatile components of a coating means.

Over this coating tool according to the invention may contain at least one customary and known lacquer additive in effective amounts, i.e. in amounts mostly to 30 wt.%, particularly preferably up to 25 wt.% and in particular up to 20 wt.%, every time in terms of non-volatile components of a coating means.

Examples of suitable lacquer additives are:

especially UV absorbers;

in particular, the light stabilizers such as HALS-compounds, benzotriazole or oxalanilide;

- acceptors of free radicals;

- supplements improved the non slip;

inhibitors of polymerization;

- antispyware;

- reactive diluents, as they, in General, are known from the prior art, which preferably are inert in respect of the-Si(OR)3 groups.

- wetting agents such as siloxanes, fluorine compounds, monoether carboxylic acids, phosphoric esters, polyacrylic acids and their copolymers, or polyurethanes;

- adhesion promoters, such as tricyclopentadiene;

- to contribute to spreading;

- film-forming AIDS, such as derivatives of cellulose;

- fillers such as, for example, nanoparticles based on silicon dioxide, aluminum oxide or zirconium oxide; an additional reference is made to Römpp Lexikon Lacke und Druckfarben", Georg Thieme Verlag, Stuttgart, 1998, c.250 to 252;

- additives that control the rheology, such as is known from the patent descriptions WO 94/22968, EP-A-0276501, EP-A-0249201 or WO 97/12945; crosslinked polymeric microparticles, as they are disclosed, for example, in EP-A-0008127; inorganic layered silicates, such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium-fluorine-lithium layered silicates of the type montmorillonite; silicic acid, such as aerosol; or synthetic polymers with ionic and/or associative existing groups, such as polyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic to the slot, polyvinylpyrrolidone, styrene-maleic anhydrite copolymers or ethylene-maleic anhydrite copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;

and/or fire retardant means.

In another form of the invention, the coating tool according to the invention may also contain other pigments and/or fillers and serve to produce pigmented top layer. Used to do this, pigments and/or fillers known to the person skilled in the technical field.

As obtained from the coating means according to the invention the coating according to the invention also exclusively linked to already otverzhdennye electrophoretic lacquer coating, lakirovanie filler, the base lakirovanie or the usual and well-known transparent lakirovanie, along with the use in the automotive serial varnishing (OEM) they are remarkably suitable for repair lacquering or modular, resistant to scratching, finish already painted automobile bodies.

The application of the coating means according to the invention may be carried out by all of the usual application methods, such as, for example, sputtering, relevane, promazyvanie, color filling, dipping, soaking, dripping or rolling. Pokrywa the range of the substrate per se can be fixed, moreover, the equipment or installation for applying moves. Meanwhile, the coated substrate, in particular a roll, may also move, and equipment for applying relative to the substrate is stationary or is moving properly.

Mostly used methods of spray application, such as, for example, air spray, airless spray, high-speed rotation, electrostatic spray coating (ESTA), optionally coupled with hot spray application such as, for example, spraying hot air.

Curing the applied coating means according to the invention may be carried out after a certain period of rest. The rest period is used, for example, for spreading and for degassing lacquer layers or for the evaporation of volatile components such as solvent. The rest period may be reinforced and/or reduced by the application of elevated temperatures and/or low humidity, because in this case there is no damage or changes lacquer layers, such as premature complete crosslinking.

Thermal curing of the coating means has no methodological features, and occurs according to standard and well known methods such as heating in a drying oven with circulation of ozdoba or irradiation with IR lamps. In this case thermal curing may also occur gradually. Another preferred method of curing is the curing in the near infrared spectrum (NIR radiation). Preferably thermal curing occurs at a temperature of from 30 to 200°C., particularly preferably 40 to 190°C. and in particular 50 to 180°C. over a period of time from 1 minute to 10 hours, particularly preferably 2 min to 5 h and in particular from 3 min to 3 h, and when repair coating applied temperature, which preferably are between 30 and 90°C, can also be used for a longer time to cure.

Cover means according to the invention provide a new cured coatings, particularly coatings that are particularly transparent lacquer coating, fittings, especially optical fittings, and svobodnaia films that are resistant to scratching and particularly resistant to chemicals and weather. In particular, it is possible to obtain coatings according to the invention and varnish covering, especially a transparent lacquer coating, with a thickness of >40 μm without the occurrence of cracks due to internal stresses.

Therefore, the coating means according to the invention especially suitable as a decorative, protective and/or come is the relevant effect, highly resistant to scratching coatings and coating of vehicle bodies (especially vehicles with an engine, such as motorcycles, buses, trucks or cars), or their parts; internal and external areas of the buildings; furniture, Windows and doors; mouldings made of synthetic materials, in particular CDs and Windows; industrial small parts, coils, containers, and packaging; products white; films; optical, electrical and mechanical components, as well as hollow glass products and consumer goods.

In particular, the coating means according to the invention and of the lacquer coating, in particular a transparent varnish used in the technologically and esthetically particularly demanding field of coating hire repetitive manufacturing (OEM), and also repair coating. Especially preferably the coating means according to the invention is used in multi-step method of applying coatings, in particular in the way in which optionally pre-coated substrate is first applied pigment master lacquer layer and then layer with the coating agent according to the invention.

Can be used as water-based base lacquers, and the basic lacquers based on organic solvents. Suitable BA is easen varnishes are for example, described in EP-A-0692007 and there in the documents column 3, lines 50 and beyond. Preferably the applied base lacquer is first dried, that is, from the core of the lacquer film during the evaporation phase is removed, at least one organic solvent, water respectively. Drying occurs mainly at temperatures from room temperature to 80°C. After drying of the applied coating agent according to the invention. Then burn double-layer coating is preferably under the conditions used in the varnishing of vehicles series production at temperatures from 30 to 200°C., particularly preferably 40 to 190°C. and in particular 50 to 180°C. over a period of time from 1 minute to 10 hours, particularly preferably 2 min to 5 h and in particular from 3 min to 3 h, and when repair coating applied temperatures are preferably between 30 and 90°C, can also be used for a longer time to cure.

The layers obtained by means of a coating tool according to the invention is primarily distinguished by its especially high resistance to chemicals and weathering, as well as very good resistance at an automatic car wash and resistance to scratching, especially thanks to the exceptional combination stoikos and to scratching and weathering against UV radiation in the wet-dry cycle.

In another preferred form of the invention, the coating tool according to the invention is used as a light, transparent lacquer for coating a polymeric substrate, especially a transparent polymer substrates. In this case, the covering means comprise UV absorbers, based on the number and type are also designed for effective UV protection polymer substrates. In this context, the covering means differ due to the exceptional combination of resistance to scratching and weathering against UV radiation in a cycle of wet-dry. Covered in a similar manner polymeric substrates are mainly used to replace the glass components in the automotive industry, and polymer substrates preferably comprise polymethylmethacrylate or polycarbonate.

Examples

The receiving component In accordance with the invention

Example of getting VB1 - receiving partially silanizing MDI (HDI with 100 mol.% IIa: the degree of interaction between the C=30 mol.%) (comparative example)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, covering nitrogen and paramasivan is to 21.8 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (IIa) (Dynasilan ® 1189 company Degussa) is added so not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 70 mol.%.

The solution is partially silanizing MDI has a solids content in 47,1 wt.%.

Example obtain B1 - receiving partially silanizing MDI (HDI 70 mol.% IIa and 30 mol.% Ia: the degree of interaction between the C=30 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and to 69.7 parts by weight of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring, a mixture of 14.8 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan ® 1189 company Degussa) (IIa) and 9.2 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (Ia) (Dynasilan ® 1124 company Degussa) are added in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically designed 70 mol.%. The solution is partially silanizing MDI has a solids content in 53,9 wt.%.

Example obtain B2 - receiving partially silanizing floor the isocyanate (HDI with 30 mol.% IIa and 70 mol.% Ia: the degree of interaction between the C=30 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and to 69.7 parts by weight of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring, a mixture of 6.4 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan ® 1189 company Degussa) (IIa) and 21.5 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (Ia) (Dynasilan ® 1124 company Degussa) are added in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically designed 70 mol.%. The solution is partially silanizing MDI has a solids content in 55,0 wt.%.

Example of getting VB2 - receiving partially silanizing MDI (HDI with 100 mol.% Ia: the degree of interaction between the C=30 mol.%) (comparative example)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring of 30.7 parts by weight of parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (Ia) (Dynasilan ® 1124 company Degussa) is dobavlaut thus, not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 70 mol.%.

The solution is partially silanizing MDI has a solids content in 63,0 wt.%.

Example of getting VB3 - receiving partially silanizing MDI (HDI with 100 mol.% IIa: the degree of interaction with=70 mol.%) (comparative example)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring of 49.4 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (IIa) (Dynasilan ® 1189 company Degussa) are added in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 30 mol.%.

The solution is partially silanizing MDI has a solids content in of 54.8 wt.%.

An example of obtaining B3 - receiving partially silanizing MDI (HDI 70 mol.% IIa and 30 mol.% Ia: the degree of interaction with=70 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and to 69.7 parts by weight of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring, a mixture of 34.6 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan ® 1189 company Degussa) (IIa) and 21.5 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (Ia) (Dynasilan ® 1124 company Degussa) are added in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 30 mol.%. The solution is partially silanizing MDI has a solids content in 61,9 wt.%.

An example of obtaining B4 - receiving partially silanizing MDI (HDI with 30 mol.% IIa and 70 mol.% Ia: the degree of interaction with=70 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring, a mixture of 14.8 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan ® 1189 company Degussa) (IIa) and 50.2 weight parts of the bis-[3-(trimethoxysilyl)propyl]-amine (Ia) (Dynasilan ® 1124 company Degussa) is added so not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 70 mol.%. The solution is partially silanizing MDI has a solids content in 58,2 wt.%.

Getting polyacrylonitrile And

In the steel hull reactor, equipped with a Monomeric flow, initiating flow, thermometer, heating the liquid fuel and reflux condenser, heated 29,08 weight parts of a standard aromatic solvent mixture (solvent-naphtha ® company DHC Solvent Chemie GmbH) to 140°C. the mixture is Then A1 from 3,39 weight parts of the solvent-naphtha 2.24 parts by weight of tert.-butyl peroxy-2-ethylhexanoate added under stirring with such speed that the addition of a mixture of A1 ends of 6.75 hours Later, 15 minutes after the start of addition of the mixture A1 add a mixture of A2 consisting of equal to 4.97 weight parts of styrene, 16,91 parts by weight of tert.-of butyl acrylate, 19,89 weight parts of 2-hydroxypropylmethacrylate, 7,45 weight parts of n-butyl methacrylate, and of 0.58 parts by weight of acrylic acid with such speed that the addition of a mixture of A2 is completed within 6 hours After addition of the mixture A1, the reaction mixture is kept for another 2 h to 140°C and then cooled to below 100°C. Then the reaction mixture is more diluted with the mixture of A3 3,70 weight parts of 1-methoxypropylacetate-2, 3,06 weight parts of butylchloroformate and 6,36 weight parts of butyl acetate 98/100. The resulting solution polyacrylonitrile And has a solids content in 52,4% (1 h, 130°C, drying oven with air circulation), the viscosity of 3.6 dPas (ICI-viscometer with cone and plate, 23°C), hydroxyl number 155 mg KOH/g and an acid number of 10-13 mg KOH/g

Composition of a coating means according to the invention and comparative examples

Cover means according to the invention and comparative examples are as follows.

Component 1 containing component a (polyol) and standard additives and catalyst and solvent, shortly before applying the merge component 2 containing the component (a modified polyisocyanate), and stir until then, until a homogeneous mixture is formed. Application is done pneumatically at 2.5 bar in three passes. The coating for 5 minutes and subjected to evaporation at room temperature and then at 140°C for 22 minutes fired.

Table 1 lists all of the cover means relative shares of the components.

Table 1
Composition of a coating means according to the invention and comparative examples
Component In accordance with exampleVB1B1B2VB2VB3B3B4
weight part polyacrylonitrile And according to the example45,045,045,045,045,045,045,0
the weight of the component52,0to 47.248,343,7144,9133,0153,0
weight part of catalyst1(Nacure 4167, King Industries) non-volatile fraction of 25%2,12,22,32,46,97,27,8
weight parts BYK 301 (a means of facilitating spreading, wook Chemie)0,2 0,20,20,20,20,20,2
weight parts of Tinuvin 384.2 (Ciba)0,90,90,90,90,90,90,9
weight parts of Tinuvin 292 (Ciba)0,80,80,80,80,80,80,8
weight parts of the solvent-naphtha (DHC Solvent Chemie GmbH)20,020,020,020,020,020,020,0
the equivalent ratio of free isocyanate groups in the component to hydroxyl groups in polyacrylonitrile And1,00:1,001,00:1,001,00:1,001,00:1,00 1,00:1,001,00:1,001,00:1,00
1) a catalyst based on aminocarbinol partial ester of phosphoric acid

The resistance to scratching of the surfaces of the obtained coatings was tested using tests on abrasion (Crockmeter) (following EN ISO 105-X12 with 10 double moves and 9N applied force when using 9 micron polishing paper (3M 281Q wetordry™production™) with subsequent determination of residual gloss at 20° standard gloss meter), and the test raskovka (Hammertest) (10 100 double passages with steel wool (RAKSO®00 (thin)and applied weighing 1 kg, carried out with the assistance of a hammer. Then again determined residual gloss at 20° standard gloss meter) resistance to weathering was investigated using SEM-test (according to DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2Nov00). The results are shown in table 2.

Table 2
Properties of layers of transparent varnish obtained by using coating means according to the invention
Top tool component according To exampleVB1 B1B2VB2VB3B3B4
Test abrasion (residual gloss in %)41535863758895
Test raskovka 10 DH (residual gloss in %)38496064798893
Test raskovka 100 DH (residual gloss in %)011828658192
HIMSELF 180 test (h) prior to the occurrence of cracks5500525050004500525050004000

Table 2 indicates the smooth tool according to the invention with components B1, B2, B3 and B4 as compared with the coating means containing isocyanurate product joining In on the basis of interaction with HDI-isocyanurate, hereinafter abbreviated as HDI, and exclusively component Ia (comparative example VB2) IIA respectively (Comparative examples VB1 and VB3).

When the degree of interaction of the isocyanate groups of HDI 30 mol.% VB1 (containing the structural unit (II) compared to VB2 (containing structural units (I) shows clearly a longer period of time in SAM test prior to the initiation of cracks. Accordingly, when the degree of interaction of the isocyanate groups of HDI 70 mol.% example VB3 (containing only structural units (II) compared to B4 (containing 70 mol.% structural units (I) shows clearly a longer period of time in SAM test prior to the initiation of cracks. Other than resistance, is the case with scratch resistance: the extent of interaction of the isocyanate groups of HDI 30 mol.% VB1 (containing the structural unit (II) compared to VB2 (containing structural units (I) shows clearly weaker scratch resistance in various tests tarpanam. Accordingly, when the degree of interaction of the isocyanate groups of HDI 70 mol.% example VB3 (containing only structural units (II) compared to B4 (containing 70 mol.% structural units (I) shows clearly the weaker of the mouth of icewall to scratch in various tests tarpanam. As the relative share of structure I is responsible for the scratch resistance and the share structure II for weather resistance, thorough mixing of both siloxane Ia, IIa respectively, can be fine-tuned between the time of atmospheric exposure and resistance to scratching. For example, here VB1 and VB2 must be contrasted compared to B1 and B2 in the group with 30 mol.% the degree of interaction of the isocyanate functions. VB1 reaches high values in weather resistance, but the resistance to scratching is mediocre. VB2 is good resistance to scratching, but is weaker when weather resistance. Both examples B1 and B2 compared to VB1 have better resistance to scratching and compared with VB2 best periods of atmospheric exposure. Similar applies to VB3 compared to B3 and B4 in the group with 70 mol.% the degree of interaction of isocyanate here, however, as resistance to scratching, and resistance to weathering due to the high relative proportion of siloxane functions are under an even stronger impact. Also it is clear that with a high degree of interaction isocyanate functions relative share structure II has significantly stronger effect on the weather resistance than the structure I for resistance to scratching, which can be easily set p and the comparison of the values of B3 B4 u. In General, the value of the resistance to scratching is correlated with the interaction of the isocyanate groups with compounds I and II, and to obtain very high resistance to scratching also requires increased interaction isocyanate groups.

In addition, matters that the resulting coatings have good resistance to scratching directly after curing for 20 minutes at 140°C and, therefore, directly after thermal curing without problems are easy to use.

1. The covering means on the basis of the aprotic solvent containing at least one containing the hydroxyl group of the compound (A)and at least one containing isocyanate groups of the compound (B), characterized in that
(i) one or more components of the coating tool as an additional functional components are between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (I)

and
R'=hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with RA=alkyl, cycloalkyl, aryl or aralkyl,
X,X'=linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,
R"=alkyl, the cycle is alkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with RA=alkyl, cycloalkyl, aryl or aralkyl,
n=0 to 2
m=0 to 2, m+n=2, and x,y=0 to 2, and
between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (II)

moreover, Z=-NH-, -NR-, -O - C
R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
R'=hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
X=linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,
R"=alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with RA=alkyl, cycloalkyl, aryl or aralkyl,
x=0 to 2 and
(ii) the polyol (A) contains at least one poly(meth)acrylation.

2. Coating tool according to claim 1, characterized in that one or more components of the coating tool as an additional functional components have between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially predpochtitelno between 20 and 80 mol.%, and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (I) and (II)at least one structural unit of formula (I) and between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.%, and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (I) and (II)at least one structural unit of formula (II).

3. Coating tool according to claim 1, characterized in that the structural elements (I) and (II) are present in proportions ranging from 2.5 to 97.5 mol.%, in terms of the amount of badly needed to stitch in top tool functional groups, formed from parts of hydroxyl and isocyanate groups, as well as parts of the structural elements (I) and (II).

4. Coating tool according to claim 1, characterized in that the polyisocyanate (A) has structural units (I) and (II).

5. Coating tool according to claim 4, characterized in that the polyisocyanate (B)
between 2.5 and 90 mol.% isocyanate groups in the polyisocyanate main substance is subjected to interaction to obtain the structural units (I) and
between 2.5 and 90 mol.% isocyanate groups in the polyisocyanate main substance is subjected to interaction to obtain the structural units (II)
and the total share of which came in the reaction of the isocyanate groups in the polyisocyanate main substance to obtain structural the units (I) and (II) is between 5 and 95 mol.%.

6. Coating tool according to claim 1, characterized in that the polyisocyanate base material selected from the group 1,6-hexamethylenediisocyanate, isophoronediisocyanate, and 4,4'-methylendysiclogecsyldiizosyonat, biuret dimers of the above polyisocyanates and/or isocyanurate trimmers above polyisocyanates.

7. Coating tool according to claim 1, characterized in that as the catalyst for curing the coating means used is between 0.1 and 20 wt.%, in terms of non-volatile components of a coating means, aminocarbonyl phosphoric acid.

8. Multistage method of coating, characterized in that optionally pre-coated substrate is applied pigmented layer of base paint and then a layer of the covering means on the basis of the aprotic solvent containing at least one containing
the hydroxyl group of the compound (A)and at least one containing isocyanate groups of the compound (B), characterized in,
that one or more components of the coating tool as an additional functional components are between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (I)

and
R'=hydrogen, alkyl or cycloalkyl, priceplenna chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with RA=alkyl, cycloalkyl, aryl or aralkyl,
X,X'=linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,
R"=alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with RA=alkyl, cycloalkyl, aryl or aralkyl,
n=0 to 2, m=0 to 2
m+n=2, and x,y=0 to 2 and
between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (II)

moreover, Z=-NH-, -NR-, -O - C
R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
R'=hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
X=linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,
R"=alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with RA=alkyl, cycloalkyl, aryl or aralkyl,
x=0 to 2.

9. Multistage method of coating of claim 8, wherein the polyisocyanate (A) has structural units the units (I) and (II).

10. Multistage method of coating according to claim 9, characterized in that the polyisocyanate (B) is between 2.5 and 90 mol.% isocyanate groups in the polyisocyanate main substance is subjected to interaction to obtain the structural units (I) and between 2.5 and 90 mol.% isocyanate groups in the polyisocyanate main substance is subjected to interaction to obtain the structural units (II) and the total share of which came in the reaction of the isocyanate groups in the polyisocyanate main substance to obtain the structural units (I) and (II) is between 5 and 95 mol.%.

11. Multistage method of coating of claim 8, wherein the main lacquer pigmented base layer, put a layer of a coating tool according to one of claims 1 to 7.

12. Multistage method of coating one of PP-11, characterized in that the applied primary pigmented lacquer base lacquer is dried at temperatures from room temperature up to 80°C, and applied to the primary varnish base layer top tool utverjdayut at temperatures from 30 to 200°C over a period of time from 1 minute to 10 hours

13. Application of the method according to one of p-12 for coating cars mass production and for repair lacquering.

14. The application of the covering means on the basis of the aprotic solvent containing at least one is teramae hydroxyl group of the compound (A), and at least one containing isocyanate groups of the compound (B), in which one or more components of the coating tool as an additional functional components are between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (I)

and
R'=hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
X,X ' =linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,
R"=alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
n=0 to 2, m=0 to 2, m+n=2, and x,y=0 to 2, and
between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (II)

moreover, Z=-NH-, -NR-,-O -
R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
R'=hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by means of not related the s groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
X=linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms,
R"=alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra=alkyl, cycloalkyl, aryl or aralkyl,
x=0 to 2
as a transparent lacquer for coating cars mass production and for repair lacquering.

15. The application of the covering means on the basis of the aprotic solvent containing at least one containing the hydroxyl group of the compound (A)and at least one containing isocyanate groups of the compound (B), in which one or more components of the coating tool as an additional functional components have
between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (I)

moreover, R', X, X', R', n, m, m+n, and x, y have the above values, and between 2.5 and 97.5 mol%, in terms of the totality of the structural units (I) and (II)at least one structural unit of formula (II)

where Z, R, R', X, R" and x have the above values, as a light, transparent lacquer for coating polymer is s substrates.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: polyurethane coating is made from a composition which contains refined castor oil, an ester, an antifoaming additive BYK-066 based on fluorine-modified polysiloxanes, aluminium oxide, titanium oxide, aerosil, a water adsorbent, an additive BYK-410 - urea in an organic solvent N-methylpyrrolidone, a curing agent isocyanate SUPRASEK 5025, which is 4,4'-diphenylmethane diisocyanate and additionally as filler - dolomite or zeolite or a mixture of dolomite and zeolite in ratio 3.25:1.

EFFECT: coating has high breaking strength and modulus of elasticity in tension, while providing sufficiently high deformation characteristics, particularly tensile elongation.

2 tbl

FIELD: construction.

SUBSTANCE: method to manufacture a coating includes preparation of a mixture by means of mixing of a filler from rubber crumb and a binder based on polyurethane. Simultaneously and separately from each other mixtures are produced for basic and upper layers, at the same time in the mixture for the basic layer they use a filler from rubber crumb with fraction of 2-12 mm, and in the mixture for the upper layer they use a filler from rubber crumb with fraction of 1-3 mm and a pigment dye. In process of mixture mixing for its upper layer it is compacted, afterwards the mixture for the upper layer is serially discharged into a die mould, then the mixture for the basic layer is discharged, and pressed under pressure with the help of a press, then maintained until full hardening, and the produced coating is discharged from the die mould.

EFFECT: high efficiency of coating manufacturing, higher reliability and durability of a coating, possibility to manufacture a double-layer coating with damping properties.

8 cl

FIELD: chemistry.

SUBSTANCE: formulation composition contains: A) 5-95 wt % at least one radiation-curable resin, B) 5-25 wt % silicic acid, C) 0.1-10 wt % at least one adhesion promoter, D) 5-90 wt % at least one radiation-curable reactive diluent, E) 0.5-5 wt % at least one dispersant. The adhesion promoter is selected form phosphoric acid and/or phosphonic acid and/or products of reaction thereof with functionalised acrylates. The composition can additionally contain photoinitiators, pigments and additives, selected from diffusion promoting agents, delustering agents and degassing agents. The compositions are used as a primer, an intermediate layer, coating varnish and/or clear varnish, as well as for making coatings via a coil coating technique.

EFFECT: coatings have flexibility, thereby providing excellent protection of metal substrates from corrosion.

18 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a self-crosslinking binder for coating compositions containing an aqueously dispersed polymer component A having at least one carbonyl group of the ketone or aldehyde type per molecule, and a component B having at least two hydrazine or hydrazide groups per molecule, and at least one structural unit -NR1-NR2-CHR3-CHR4-NH-R5 (I), where the radicals R1, R2, R3 and R4 are each individually selected from a group consisting of a hydrogen radical and a linear or branched alkyl radical having from 1 to 10 carbon atoms, R3 and R4 may additionally be selected from a group consisting of aryl and alkylaryl radicals having from 6 to 15 carbon atoms, and from oxyalkyl radicals with 1 to 10 carbon atoms, where oxy groups may be inserted into the alkyl chain or at the end of an alkyl chain, and R5 is selected from a group consisting of a hydrogen radical, alkyl radicals which may be linear, branched or cyclic and may have from 1 to 10 carbon atoms, and residues of formula -(CH2)n-CO-O-X, where n is an integer of from 1 to 6, and X is a residue of a polyatomic alcohol or phenol. A method of producing such a binder is also described.

EFFECT: producing a coating binder which is self-crosslinking when drying, having fast drying properties and improved chemical resistance and weather resistance.

17 cl, 5 ex, 5 tbl

FIELD: construction.

SUBSTANCE: invention represents an emulsion, in which oligomers with terminal isocyanate groups are a dispersion medium, and a disperse phase is a solution or a dispersion produced as a result of mixing a lime solution with calcium hydroxide content of 10-70 wt % with glycerine in the amount of 1-250 wt parts per 100 wt parts of calcium hydroxide, besides, the disperse phase content in the composition makes 1-55 wt %.

EFFECT: development of a cheap and easy to apply composition, coatings from which have high adhesion to moist metal or concrete surfaces, have proper adhesion to concrete applied onto them, are hardened with specified speed at temperature from zero and above, inhibit processes of metal corrosion and have low elasticity module.

1 tbl

FIELD: chemistry.

SUBSTANCE: coating has surface tension less than 20 mN/m, wherein the coating material used is hydrolysis-resistance lacquers, and where the hydrolysis-resistant lacquers are selected from a group consisting of polyurethanes, acryl and silicones, where the coating has a random topography with roughness of less than 500 nm, preferably less than 300 nm.

EFFECT: coating prevents deposit of bacteria and improves thermal conduction of the coated material.

19 cl, 4 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aldimines of formula (I)

where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.

EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.

22 cl, 18 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: powder coating is obtained from a composition containing at least one binding material (A) from polyester resin with a hydroxyl functional group and at least one polyurethane resin (B) as a cross-linking agent containing blocked isocyanate groups. At least one binding material from the polyester resin (A) with a hydroxyl functional group and at least one polyurethane resin (B) have melting point of 60-180°C, specifically 60-160°C. The powder composition is deposited on a substrate and cured. The substrate can be metal, plastic, wood, paper or glass.

EFFECT: obtaining coatings with the required processing properties, specifically obtaining thin films and high flexibility combined with excellent mechanical coating properties.

11 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: paint with thermo-, fire-protective properties contains (wt %): binder based on acrylic (co)polymers and/or silicone resins and organosoluble polyurethanes - (20-40), filler in form of a mineral component - (10-30), antipyrene additive - (10-20), modifying additive in form of ceramic and/or glass microspheres with diameter of 20-150 mcm -(10-30) and an organic solvent - the rest. The paint composition additionally contains bentonite powder, intercalated with cobalt Co2+ ions and/or cerium Ce3+ ions in amount of 3-7 wt %.

EFFECT: invention increases stability of the formed protective paint coating to thermal-oxidative reactions, improves environmental safety, fire-resistance of the protective coating and endows said coating with bactericidal properties.

7 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing microporous coatings, wherein a composition is foamed and dried, said composition containing an aqueous, anionically hydrophilised polyurethane dispersion (I) and a cationic coagulant (II), wherein the cationic coagulant (II) is a polymer with number-average molecular weight ranging from 500000 to 50000000 g/mol, which has structural links of general formulae and ,

where R denotes C=O, -COO(CH2)2- or -COO(CH2)3- and X- denotes a halide ion. The invention also describes a microporous coating obtained using said method, a composition for producing microporous coatings and a substrate coated with said microporous coating.

EFFECT: production of microporous coatings using a novel method, having good mechanical properties and a thin microporous structure.

10 cl, 9 ex, 1 tbl

FIELD: inorganic chemistry.

SUBSTANCE: invention refers to polymer chemistry particularly to polyurethanes and foamed polyurethanes processing technologies. Described method of all-purpose metal-complex modifier for polyurethane implies solution of metal halogenide in solvent. This method is characterized by solution of metal halogenide having variable valence of stable oxidation level, for example manganese chloride (II) tetrahydrate, in N,N-dimethylethanolamine and ε-caprolactam at mole ratio of metal halogenide: dimethylethanolamine: ε-caprolactam 1:5:5-20. Modifying agent is added to laprole component. Polyurethanes produced with modifying agent are characterized by improved physical-mechanical properties such as ultimate breaking stress, rigidity at deformation 40% and comfort coefficient.

EFFECT: production of polyurethanes with improved physical-mechanical properties; increased comfort coefficient rigidity and ultimate breaking stress.

1 cl, 6 tbl

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to mixtures consisting of blocked polyisocyanates designated as hardening agents in monocomponent lacquers of hot drying and comprising: (a) blocked polyisocyanate based on 1,6-diisocyanate hexane; (b) blocked polyisocyanate based on cycloaliphatic diisocyanates chosen from group comprising 1-isocyanato-3,3,5-trimethyl-5-ixocyanatomethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, 2,6-bis-isocyanatonorbornane, 2,5-bis-isocyanatonorbornane, 1,4-bis-isocyanatomethylcyclohexane and their mixtures, and (c) 3,5-dimethylpyrazole as a single blocking agent of agent of polyisocyanates named in (a) and (b). Blocked polyisocyanates are taken in the weight ratio (a) : (b) = 1:(1.8-2.2). Using mixtures of blocked polyisocyanates provides preparing clear lacquers with good acid resistance, stability against scratching and thermal yellowing.

EFFECT: improved and valuable properties of agents.

1 cl, 6 ex

The invention relates to the technology of polyurethanes, which can be used as adhesives, paints, construction materials

The invention relates to the chemistry of polymers, namely, anti-static polyurethane, which can be used for the manufacture of anti-static products and coatings, in particular rollers, pulleys and couplings in textile machinery

FIELD: chemistry.

SUBSTANCE: polyacrylic (co)polymer which is curable under the effect of atmospheric moisture and having elastometic properties is a plurality of acrylic prepolymer segments interlinked by urea or urethane links caused by moisture curing. Each of the plurality of prepolymer segments is a homopolymer or a copolymer of methylmethacrylate, C1-C16-alkylacrylate and C1-C16-alkylmethacrylate as the predominant monomer group. The moisture-curing method involves formation of a plurality of segments of an acrylic prepolymer, obtaining isocyanate-functionalised segments of the acrylic prepolymer, storing the isocyanate-functionalised segments in anhydrous state, followed by deposition thereof onto a substrate and moisture-curing to form a polyacrylic polymer.

EFFECT: obtaining polyacrylic (co)polymers cured under the effect of atmospheric moisture and having elastomeric properties, which retain resistance to UV rays, optical transparency, wear and physical properties of conventional thermoplastic acrylic polymers.

14 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: multicomponent aqueous composition contains an aqueous dispersion and a component containing a material having functional groups. The components are mixed with each other before applying the composition onto the substrate. The aqueous dispersion contains a polycarbonate-polyurethane polymer and an acrylic polyol. The aqueous dispersion also contains an organic solvent. The material having functional groups reacts with functional groups of the acrylic polyol and/or polycarbonate-polyurethane polymer. The acrylic polyol has number-average molecular weight from 500 to 4000. The polycarbonate-polyurethane polymer is obtained via a reaction between hydroxy-functional carbonate-containing material and polyisocyanate. The hydroxy-functional carbonate-containing material contains a product of reaction between carbonic acid or derivative thereof and a diol. The diol is hexane-1,6-diol.

EFFECT: composition has low content of volatile substances, as well as high water resistance and hardness.

20 cl, 3 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: 100 - copolymer of butadiene and piperylene with molecular weight 1200-3200 and content of hydroxyl groups 0.8-1.1%, 20-polymethylene polyphenyl isocyanate with content of isocyanate groups 29-31%, 70-100 - rubber crumbs, and 25-20 - high-molecular polyethylene with molecular weight 30000-800000.

EFFECT: high dynamic and physical-mechanical properties of the composition based on the filled foamed polyurethane.

1 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a coating composition containing a) polyacrylate polyol obtained via polymerisation of unsaturated olefin monomers, where at least 40 wt % of the monomers include straight or branched alk(en)yl or alk(en)ylene groups, having at least 4 carbon atoms; b) polyether polyol obtained via esterification of component links having functional groups which form an ester, where at least 30 wt % of component links include straight or branched alk(en)yl or alk(en)ylene groups with at least 4 carbon atoms per functional group, which forms an ester, where he polyether polyol has hydroxyl number higher than 280 mg KOH/g and hydroxyl functionality of at least 2, and c) isocyanate-functionalised cross-linking agent. The invention also relates to a set of parts for preparing the coating composition and a method of applying the coating composition. The coating composition can be used as a top coating layer in multilayer paint coats, in finishing or reworking automobiles or large vehicles.

EFFECT: coating has high hardness, scratch resistance, lustre, longevity and wear resistance, chemical resistance and UV radiation resistance.

15 cl, 6 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to coating composition, applied, for instance, as transparent coatings, base coatings, pigmented coating layers, used, prime coatings, etc. Composition contains polyisocyanate, polyol, metal-based catalyst for carrying out reaction of addition reaction between isocyanate groups and hydroxyl groups, thiol-functioning compound and carboxylic acid, carbonyl group of carboxylic acid being in connection with π-electronic system.

EFFECT: creation of novel coating composition, demonstrating presence of favourable property balance, namely, low level of volatile organic solvent content with operation viscosity, high rate of hardening and long viability, which results in obtaining coatings, which demonstrate good outlook characteristics, in particular, low liability to formation of pinholes, and good hardness.

14 cl, 2 tbl

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