Photoactivating aqueous-base covering composition

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

 

The present invention relates to photoactivated coverts of the composition is water-based, including (meth)acryloylmorpholine polyurethane dispersion and UV initiator.

Photoactivated coverts composition of the type specified above is known from (among other sources) EP-A-0952170. The system disclosed here is based on a dual curing, and therefore includes, in addition to the dispersion of the (meth)acryloylmorpholine polyurethane, free isocyanate groups, which can further react with one or more active hydrogen atoms in the water opaque composition. Although high-quality layers of coatings can be obtained using known coverts composition water-based properties of aqueous polyurethane dispersions used in famous songs are still an issue that requires improvement, particularly in regard to the appearance of the layers that contain the specified dispersion when applied to substrates with uneven surfaces.

Photo-activated polyurethane resin as such for use in clear coatings were already known from DE-C-19635447. This document describes the use of polyurethane and/or polyester(meth)acrylate resin with diacrylate monomers as reactive diluents. Though it is specified that these compositions are suitable for use in to the Nasiriyah solvent-based and water-based in the examples were used only composition based solvents, which were overidealize pulses of ultraviolet radiation of high power. In EP-A-0965621 disclosed photoactivated covering composition, which includes (meth)acryloylmorpholine polyurethane and photoinitiator, such as phenylglyoxylate acid or their esters or salts or derivatives thereof, optionally with other photoinitiators. Although clearly mentioned about the possible use of declared coverts compositions in water-based systems, in the examples used only systems solvent-based.

In the present invention proposed coverts composition water-based characteristics do not deteriorate when applied to substrates with uneven surfaces and which do not need to be cured of pulses of ultraviolet radiation of high power, but which can otvetit UV radiation, such as UV-a radiation. In addition, it was found that the resin used in opaque compositions, water-based present invention, cannot be used as such in the covering composition, solvent-based, especially if covering the composition-based solvent is used as a clear coating on top of the basic coverage. The resulting coating of opaque composition nastojasih the invention has excellent properties, such as resistance to water and solvents, hardness, scratch resistance, appearance, dry and wet adhesion and flexibility.

The present invention relates to opaque compositions are water-based, including:

a) a dispersion of a (meth)acryloylmorpholine polyurethane, in which (meth)acryloylmorpholine polyurethane contains from 5 to 18 wt%. alkalinising groups, whereas the (meth)calolina functionality is a value in the range from 2 to 40, and

b) UV-initiator.

Preferred acceleratedly group in the (meth)acryloylmorpholine polyurethane are ethyleneoxide groups, but you can also use propylenoxide group or mixture ethylenoxide and propylenoxide groups. For example, acceleratedly group can be a C1-C4alkoxyamine of polyalkylene glycols of the following structure:

where R1 represents a hydrocarbon radical containing from 1 to 4, preferably 1 or 2 carbon atoms; R2 represents a methyl group; x takes values from 0 to 40, preferably from 0 to 20, most preferably from 0 to 10; y takes values from 0 to 50, x+y take values from 2 to 50, preferably from 2 to 25. Examples are detoxifier of glycols or polypropyleneglycol with srednekislovsky molecular the m weight of from 100 to 3000, preferably from 200 to 1500, and most preferably from 350 to 1000.

So, very good results were achieved by using a (meth)acryloyl-functional polyurethane containing from 8 to 18 wt%. alkalinising groups.

(Meth)calolina functionality of the polyurethane is in the range from 2 to 40, preferably from 2.5 to 20, more preferably from 3 to 10.

Acid number (meth)acryloylmorpholine polyurethane is preferably up to 15 mg KOH/g solids, more preferably up to 10.

Excellent results are usually achieved when using a (meth)acryloylmorpholine polyurethane, if srednetsenovoj molecular weight (meth)acryloylmorpholine polyurethane is in the range from 1000 to 20,000, while the best results were obtained for the (meth)acryloylmorpholine polyurethane with srednekislovsky molecular weight in the range from 1200 to 8000.

A distinctive feature of opaque compositions are water-based present invention is their good appearance when used as a transparent coating when applied over (metal) primary coverage. It is shown that the good appearance as the optimal density of crosslinks and shrinkage of the obtained films is completely sufficient is passed, if the equivalent weight of the (meth)acryloylmorpholine polyurethane is in the range from 200 to 4000 g/EQ. In the calculation of the solid is preferably from 350 to 1000.

Dispersion of a polyurethane containing (meth)acryloyl group, can be obtained using conventional methods of synthesis of polyurethane by reacting polyisocyanates and hydroxyalkyl(meth)acrylates and optionally chain extension.

Suitable chain extenders include diols, polyols, developed, politely, diamines and polyamine. Preferred (meth)acryloylmorpholine polyurethane, which is obtained by the interaction of:

a) at least one organic MDI,

b) optionally at least one organic compound containing at least two isocyanatobenzene group, with srednekislovsky molecular weight in the range from 400 to 6000,

c) at least one isocyanatobenzene and/or isocyanatobenzene compounds containing non-ionic dispersing groups,

d) at least one isocyanatobenzene (meth)acryloylmorpholine connection

e) optionally, at least one active hydrogen-containing chain extension, and

f) optionally, at least one active hydrogen-containing compound and the by group.

The organic polyisocyanate (a), which is used in obtaining (meth)acryloylmorpholine polyurethane polymer may be aliphatic, cycloaliphatic or aromatic di-, tri - or tetraisostearate, which can be ethyleneamines or not, such as 1,2-propylenediene, trimethylindolenine, tetramethyldisilane, 2,3-butylenediamine, hexamethylenediisocyanate, octamethyltrisiloxane, 2,2,4-trimethylhexamethylenediamine, dodecyltrimethoxysilane, ω,ω'-dipropylenetriamine, 1,3-cyclopentadiene, 1,2-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isophorondiisocyanate, 2-methyl-1,3-diisocyanatohexane, transdenominational, dicyclohexylmethane-4,4'-diisocyanate (Desmodur® W), colorvision, 1,3-bis(isocyanatomethyl)benzene, xradiation, α,α,α',α'-tetramethylethylenediamine (TMXDI®), 1,5-dimethyl-2,4-bis(2-isocyanatomethyl)benzene, 1,5-dimethyl-2,4-bis(2-isocyanatomethyl)benzene, 1,3,5-triethyl-2,4-bis(isocyanatomethyl)benzene, 4,4'-diisocyanatobutane, 3,3'-dichloro-4,4'-diisocyanatobutane, 3,3'-diphenyl-4,4'-diisocyanatobutane, 3,3'-dimethoxy-4,4'-diisocyanatobutane, 4,4'-diisocyanatobutane, 3,3'-dimethyl-4,4'-diisocyanatobutane, diisocyanatomethyl, the adduct of 2 molecules of a diisocyanate, such as hexamethylenediisocyanate or isophorone socyanate, and a diol such as ethylene glycol, the adduct of 3 molecules of hexamethylenediisocyanate and 1 molecule of water (available under the trademark Desmodur N of Bayer), the adduct of 1 molecule of trimethylolpropane and 3 molecules colordistance (available under the trademark Desmodur L of Bayer), the adduct of 1 molecule of trimethylolpropane and 3 molecules of isophorondiisocyanate connections such as 1,3,5-triisocyanate and 2,4,6-triisocyanate, and the adduct of 1 molecule of pentaerythritol and 4 molecules colordistance. It is preferable to use aliphatic or cycloaliphatic di - or triisocyanate containing from 6 to 36 carbon atoms. The most preferred dicyclohexylmethane-4,4'-diisocyanate and hexamethylenediisocyanate.

You can use a mixture of polyisocyanates and polyisocyanates which have been modified by the introduction of urethane, allophanate, urea, burtnyk, carbodiimide, uretonimine or which remains.

Organic compounds (b)containing at least two isocyanatobenzene group and having srednetsenovoj molecular weight in the range of from 400 to 6000, which can be used to obtain (meth)acryloylmorpholine polyurethane, is preferably an organic polymer polyols with hydroxyl groups at the end. Organic polyols, in particular diols include trioli and mixtures thereof, but you can use the polyols of higher functionality, such as minor components in a mixture with dialami. The polyols can be selected from the group of polyesters, complex polyetherimides, polyesters, policyeview, polycarbonates, Polyacetals, polyolefins and polysiloxanes. Preferred polyols with molecular weights in the range from 700 to 3000.

The polyether polyols which can be used include the reaction products of polyols with hydroxyl terminal groups, such as ethylene glycol, propylene glycol, diethylene glycol, neopentylglycol, 1,4-butanediol, 1,6-hexanediol, furandione, dimethylcyclohexane, glycerin, trimethylolpropane or pentaerythritol, or mixtures thereof with polycarboxylic acids, especially dicarboxylic acids or their derivatives, forming esters, for example, succinic, glutaric and adipic acids or their dimethyl complex esters, phthalic anhydride, hexahydrophthalic anhydride or exporter.

You can also use polyesters obtained by polymerization of lactones, such as caprolactone, together with the polyol. It is preferable to obtain a complex of the polyester of 1,6-hexandiol and hexahydrophthalic anhydride.

Polyetherimide polyesters can be obtained by including in polyesterification is a mixture of aminoalcohols, such as ethanolamine.

Suitable polyether polyols and polyethers include glycol polyalkylene for which accelerated may be selected from ethylenoxide and/or propylenoxide links.

Politicality that can be used include products obtained by condensing one of thiodiglycol either one, or with other glycols, dicarboxylic acids, formaldehyde, aminoalcohols or aminocarbonyl acids.

Polycarbonatediol include products obtained by the interaction of diols, such as 1,3-propandiol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol or tetraethylene glycol, with dellcorporate, for example diphenylcarbonate or with phosgene.

Suitable polyolefin polyols include Homo - and copolymers of butadiene with terminal hydroxyl.

In order to ensure that the (meth)acryloylmorpholine polyurethane was satisfacgermany in the water, you should include at least one isocyanatobenzene and/or isocyanatobenzene compound containing non-ionic group (s), as a reagent in obtaining (meth)acryloylmorpholine polyurethane.

Suitable non-ionic dispersing groups are disclosed above mono C1-C4alkoxybenzenes. Preferably, the button (meth)acryloylmorpholine polyurethane contains from 8 to 18 wt%. alkalinising groups. Suitable C1-C4polyalkylbenzene compounds contain at least one hydroxyl group. Examples include glycols methoxypolyethyleneglycol, 1-3-diols of methoxypolyethyleneglycol, such as Tegomer® D-3123 (PO/EO=15/85; Mn=1180), Tegomer® D-3409 (PO/EO=0/100; Mn=2240) and Tegomer® D-3403 (PO/EO=0/100; Mn=1180), which is available from Goldschmidt AG, Germany. Optimum results are achieved with the use of (meth)acryloylmorpholine polyurethane, in which polyalkylbenzene links are the links of polyethylene oxide.

Mono C1-C4alkoxybenzenes can be used as they are or they can be included in the adduct. For example, you can use adduct polycarboxylic acid, polyol and one of the above C1-C4aloxiprin. Examples of polycarboxylic acids include dicarboxylic acids or their derivatives, which form esters, for example succinic, glutaric and adipic acids or their dimethyl esters, phthalic anhydride, hexahydrophthalic anhydride or terephthalate or mixtures thereof. Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, neopentylglycol, 1,4-butanediol, 1,6-hexanediol, furandione, dimethylcyclohexane, glycerol, di(trimethylolpropane), trimethylolpropane or pentaerythritol or mixtures thereof. Suppose the equipment adduct hexahydrophthalic anhydride, di(trimethylolpropane) and glycol methoxypolyethyleneglycol above.

As isocyanatobenzene (meth)acryloylmorpholine compounds (d) can be used hydroxyalkyl- (meth)acrylates, such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxyhexyl(meth)acrylate, and propilenglikole(meth)acrylate.

Excellent results are usually achieved using additional products difunctional or polyfunctional epoxy compounds and methacrylic acid. As examples of suitable difunctional or polyfunctional epoxy compounds, which as such can be solid or liquid, you can specify diglycidyl or polyglycidyl ethers of (cyclo)aliphatic or aromatic hydroxyl compounds, such as ethylene glycol, glycerin, cyclohexanediol, and mononuclear or polynuclear difunctional or polyfunctional phenols and bisphenol, such as bisphenol-a and bisphenol-F, epoxydecane aliphatic and/or cycloaliphatic alkenes, such as dipentene dioxide, Dicyclopentadiene dioxide and dioxide vinylcyclohexane. So, fairly good results were obtained using difunctional epoxides selected from the group of hydrogenated bisphenol diglycidylether ether, 1,4-what tenderlipsyulia ether, 1,6-sexunderagesmalltalk ether and neopentylglycol ether. You can also use a mixture of these additional products and above hydroxyalkyl(meth)acrylates.

As the active hydrogen-containing extension (extension cords) circuit can be used compounds containing groups which are reactive in relation to isocyanate groups. The chain extension can serve as water but also organic polyol, polyamine or polythiol.

Preferably, the organic polyols include compounds with srednekislovsky molecular weight less than 400. They include diols and trioli and their mixtures, but you can use the polyols of higher functionality. Examples of such low molecular weight polyols include ethylene glycol, diethylene glycol, tetraethylene glycol, bis(hydroxyethyl)terephthalate, cyclohexanedimethanol, furandione, glycerin, trimethylolpropane and the reaction products of such polyols with propylene oxide and/or ethylene oxide with a molecular weight of up to 400.

It is not necessary that at least one active hydrogen-containing compound containing ionic groups (f)can be included as a reagent in obtaining (meth)acryloylmorpholine polyurethane. Examples include dimethylolpropionic acid, sulfosuccinates, postnatal, monohydro the C acid (hydroxycarbamoyl acid), hydroxysulfonic acid, hydroxyphosphonic acid and any salts of these acids. Preferred sulfosuccinates obtained from Cardura® E10, maleic acid and tonita sodium.

It is more preferable to obtain a (meth)acryloylmorpholine polyurethanes resulting from the interaction of:

a) at least one organic MDI,

c) at least one isocyanatobenzene and/or isocyanatobenzene compounds containing non-ionic dispersing groups,

d) at least one isocyanatobenzene (meth)acryloylmorpholine connection, and

e) at least one chain extension containing active hydrogen

or as a result of interaction

a) at least one organic MDI,

c) at least one isocyanatobenzene and/or isocyanatobenzene compounds containing non-ionic dispersing groups,

d) at least one isocyanatobenzene (meth)acryloylmorpholine connection, and

f) at least one containing an active hydrogen compounds containing ionic groups,

or as a result of interaction

a) at least one organic MDI,

b) optionally at least one organic connect the tion, containing at least two isocyanatobenzene group with srednekislovsky molecular weight in the range of from 400 to 6000,

c) at least one isocyanatobenzene and/or isocyanatobenzene compounds containing nonionic dispersing group, and

d) at least one isocyanatobenzene (meth)acryloylmorpholine connection.

(Meth)acryloylmorpholine polyurethane, suitable for covering composition water-based present invention can be obtained in the usual way, interacting stoichiometric amount or an excess of organic MDI (a) with other reagents (c) and (d) and, optionally, (b), (e)and (f) in practically anhydrous conditions at a temperature in the range of from about 30°C to 130°C to complete the reaction between isocyanate groups and isocyanatobenzene groups. The reagents are usually used in such a ratio that corresponds to a ratio of isocyanate groups to isocyanatobenzene (usually hydroxyl) groups of from about 1:1 to about 6:1, preferably about 1:1. If you are using an excess of organic MDI (a), the prepolymer with isocyanate end get on the first stage. In the second stage you can add a compound containing, on graynamore, one isocyanatobenzene group, such as a chain extension (e). Elongation of the chain can be performed at high, low or at room temperature. Typically, the temperature ranges from about 5°C to 95°C or, more preferably, from about 10°C to about 45°C.

Preferably, opaque composition of the present invention include one or more of the reactive diluents. Compounds suitable as reactive diluents, usually Ethylenediamine connections. As representative examples of such compounds can be specified compounds disclosed in the previously mentioned EP-A-0965621. The reactive diluent preferably has a molecular weight of from about 80 to about 800, more preferably from about 100 to about 400. Compounds that meet this requirement relative to the molecular weight, suitable to reduce the viscosity of opaque composition. It is preferable to use reactive diluents in an amount of 5 to 50 wt%. calculated on solid resin, more preferably 10-40 wt%.

Examples of monofunctional reactive diluents include esters of acrylic and methacrylic acid such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acryl is t, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, neopentyl(meth)acrylate, isopentyl(meth)acrylate, n-hexyl(meth)acrylate, isohexyl(meth)acrylate, n-heptyl(meth)acrylate, isoheptyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, isononyl(meth)acrylate, decyl(meth)acrylate, Isodecyl(meth)acrylate, undecyl(meth)acrylate, Isodecyl(meth)acrylate, dodecyl(meth)acrylate, soddell(meth)acrylate, tridecyl(meth)acrylate, isotridecyl(meth)acrylate, tetradecyl(meth)acrylate, azotetrazole(meth)acrylate and mixtures thereof. In addition, the above-mentioned esters of acrylic and methacrylic acid may contain radiationresistant bonds in the alcohol radicals. Additional monofunctional susceptible to radiation compounds that can be used as reactive diluents include diallylmalonate, diallylphthalate, vinyl acetate and N-vinyl-2-pyrrolidone, especially the last connection.

The most preferred reactive diluents for transparent coatings of the present invention are those in which there is more than one susceptible to radiation due. Such compounds usually are esters of acrylic or methacrylic acid and polynuclear alcohol. Other suitable reactive diluents are the camping urethane acrylates, the melamine acrylates, adducts epoxyacrylate acid and reactive diluents containing polyethylene oxide. Examples of the above difunctional diluents are etilenglikolevye, propilenglikolstearat and dimethacrylate. Similarly, diolaiuti and dimethacrylate butane, pentane, hexane, heptane, etc. up to (and including) diols, containing thirty-six carbon atoms, can be used in transparent coatings of the present invention as reactive diluents. Of particular interest are 1,4-potentialities, 1,6-hexanediamine, diethylene glycol diacrylate, trimethylolpropane and pentaerythritoltetranitrate. Thus, the best results were achieved with the use of reactive diluents selected from the group 3-methoxypropyl-, benzyl-, octyl-, 2-hydroxyethylnitrosamine, (meth)acrylate ester butanediol, hexanediol and trimethylolpropane, diacrylate ester potentialapplications ether, triacrylate of ethoxylated trimethylolpropane and the reaction product α,α,α',α'-tetramethylethylenediamine (TMXDI®) and 4-hydroxyethylacrylate and/or the product of esterification of 1 mole of 2-and 2 hydroxyethylacrylate of moles of caprolactone and/or methoxypolyethyleneglycol with molecular weight between 300 is 1000. As examples of UV initiators that can be used in transparent coatings of the present invention, it is possible to specify benzoic ether (Esacure® ex Fratelli Lamberti), acetal of benzyldimethylamine (Irgacure® 651 ex Ciba), 1-hydroxycyclohexane (Irgacure® 184 ex Ciba), 2-hydroxy-2-methyl-1-phenylpropane-1-on (Darocur® 1173 ex Ciba), 1-(4-isopropylphenol)-2-hydroxy-2-methylpropan-1-he (Darocur® 1116 ex Ciba), diethoxyacetophenone (DEAP® ex decision Upjohn), methylthionine (Quantacur® ex Shell), oxide, 2,4,6-trimethylbenzenesulfonyl (Lucirin TPO® ex BASF), and the bisphosphine oxides, such as CGI® 819 and CGI® 403 ex Ciba. The number of used UV-initiator is in the range from 0.001 to 10 wt%. in the calculation of the solid product, preferably from 1 to 8 wt%, more preferably from 2 to 6 wt%.

Covering compositions of the present invention otverzhdajutsja under the action of radiation after application and, optionally, after evaporation of the solvent. They are particularly suitable for curing under the action of UV radiation. You can also use a combination IR/UV radiation. As radiation sources can be used those which are conventional for UV, such as mercury lamps, high and medium pressure.

In order to avoid any risk, including the use of UV-radiation of very short wavelengths (UV-B and/or UV-C radiation), preference (especially for COI is whether in workshops, where re-polished cars) fluorescent lamps, the radiation which provides less damaging UV And radiation. The amount of energy required for curing of the reactive components, of course, will depend on the intensity of the light, the angle at which the exposure, the distance from the radiation source and the thickness of the applied coating, and the presence or absence of a catalyst, initiating free radicals. For a given composition the best way to determine the required number and duration of exposure is an experimental determination of the number of groups susceptible to radiation and uncured after exposure to the radiation source.

In those circumstances, where, apparently, it is desirable to increase the speed of curing in areas that are not sufficiently covered UV rays, covering the composition is water-based may include compounds containing one or more of the groups containing active hydrogen which can react with refinancing groups contained in the dispersion (meth)acryloylmorpholine polyurethane.

Suitable containing active hydrogen groups are activated CH group, i.e. methylene and/or monosubstituted methylene group α-position to two carbonyl groups, such the AK malanta and/or acetoacetate group. Examples of compounds containing malonate groups, and oligomeric and polymeric compounds containing malonate group, are disclosed in U.S. patent US-A-2759913 and US-A-4602061 respectively. The preferred compounds are oligomeric and/or polymeric compounds containing malonate groups, such as polyurethanes, polyesters, polyacrylates, epoxy resins, polyamides, and polyvinyl resins, which contain malonate group in the main chain or group, which is suspended from the main chain, or both together.

Polyurethanes containing malonate group, can be obtained, for example, interacting MDI containing a hydroxyl group complex ether polyol and malonic acid, or as a result of esterification or transesterification hydroxyquinoline polyurethane c malonic acid or diallylmalonate.

Polyesters containing malonate group, can be obtained, for example, by polycondensation of malonic acid, allylmalonic acid (for example, ethylmalonic acid), mono - or dialkylamino esters such malonic acid and/or reaction products of malonic of ester and alkyl(meth)acrylate, optionally with other di - or polycarboxylic acids with di - and/or more than di-functional hydroxyl-containing joint is mi, and optionally a monofunctional hydroxy and/or carboxyl compounds.

Epoxy esters containing malonate group, can be obtained, for example, as a result of esterification of epoxy resin c malonic acid or mono(complex)ester of malonic acid or transesterification c diallylmalonate, optionally, with other carboxylic acids and their derivatives.

Polyamides containing malonate group, can be obtained, for example, in the same way as polyesters, and in this case, at least part of hydroxycodone replace one or polyvalent primary and/or secondary amine.

As examples of compounds containing acetoacetate group, you can specify acetoacetate esters disclosed in U.S. patent US-A-2759913 (see especially column 8, lines 53-54), diacetoacetate compounds disclosed in U.S. patent US-A-4217396 (see especially column 2, line 65 to column 3, line 27), and oligomeric and polymeric compounds containing acetoacetate group disclosed in U.S. patent US-A-4408018 (see especially column 1, line 51 to column 2, line 6). Preferred oligomeric and/or polymeric compounds containing acetoacetate group.

Suitable oligomeric and polymeric compounds containing acetoacetate group, can be obtained, for example, from polisport and/or hydroxyquinolines polyester, complex polyester, polyacrylate, vinyl or epoxy oligomers and polymers in the reaction with diketene or transesterification using allylacetate. Such compounds can also be obtained by copolymerization acetoacetotoluidide acrylic monomer with other vinyl and/or acrylontrile monomers.

For use in the present invention the most preferred among the compounds containing acetoacetate groups are containing acetoacetate group oligomers and polymers containing at least 2 acetoacetate group. In addition, particularly preferably compounds containing acetoacetate group, srednetsenovoj molecular weight was in the range of from about 234 to about 30,000 and an acid number was about 2 or less.

Compounds containing as malonate and acetoacetate group in the same molecule, can also be used to obtain, for example, in the reaction of Michael montfortianus complex polyester and acetoacetotoluidide acrylic compounds (for example, acetoacetanilide). In addition, you can use a physical mixture of compounds containing malonate and acetoacetate group. In addition, allylacetate can be used as reactive dilute the her.

Optionally, compounds containing activated CH groups can be used in the form of enamines, such as those disclosed in the patent EP-A-0420133.

The reaction between compounds containing activated CH group, and refinancing compounds are in the presence of a base. It is preferable to use the base in which the conjugated acid has a pKa of at least 12, such as tetrabutylammonium hydroxide, epoxy adduct of tertiary amines, amine type amidine, examples of which include tetramethylguanidine and 1,8-diaza-[5,4,0]-bicycloheptane, and the catalysts disclosed in the patent EP-A-0596461. So, the best results were obtained using 1,8-diaza-[5,4,0]-bicycloheptane.

In accordance with the present invention, suitable catalysts may be grounds with electric charge, provided that their conjugate acid has a pKa > 10, preferably > 12. As representative examples of the bases can be specified metal-containing base. Examples of suitable bases include metal oxides, such as methanolic sodium; metal hydroxides, such as sodium phenolate; metal-containing hydrocarbon compounds such as n-utility; metal hydrides such as sodium hydride; amides of metals, such as potassium amide; and metal carbonates, such as carbon and the tons of potash.

Instead of compounds containing activated CH group, the composition may include polyamine, such as polyaminoamide with amine number of 60-1000 that react with (meth)acrylate groups present in the (meth)acryloylmorpholine polyurethane resin, such as those disclosed in the patent EP-A-0262720. You can also use the oligomeric sterically difficult polyamine, such as those disclosed in the patent EP-A-0678105. Tifunctional compounds such as pentaerythritoltetranitrate, which is reacted with (meth)acrylate groups present in the (meth)acryloylmorpholine polyurethane resin, can be used to improve curing the surface and increase resistance to scratches in the obtained coatings.

Preferred coverts compositions that include compounds containing groups with active hydrogen atoms, such as hydroxyl, thiol and/or amidofunctional groups that are reactive with respect to the desired isocyanate groups, and isocyanatobenzene group can be included in the (meth)acryloylmorpholine polyurethane resin. For use in covering compositions, water-based present invention preferred compounds containing hydroxyltoluene group.

From organic polyisocyanates to be used in covering compositions, water-based dual-cured, preferred hydrophobic polyisocyanates comprising polyfunctional, preferably free polyisocyanates, with an average NCO functionality of from 2.5 to 5, which can be (cyclo)aliphatic, analiticheskie or aromatic in nature. The polyisocyanates can include Burenie, urethane, uretdione and which is derived. Examples of polyisocyanates are 1,6-hexadienal, isophorondiisocyanate or bis(isocentrically)methane and the above derivatives. Typically, these products are liquid at room temperature and commercially available in a wide variety. Preferred cyclic trimers (isocyanurates) 1,6-exanguination and isophorondiisocyanate. Typically, these compounds contain small quantities of its higher homologues. Hydrophobic polyisocyanates optionally can be partially replaced by hydrophilic polyisocyanates. The polyisocyanate, (meth)acryloylmorpholine polyurethane resin and, optionally, other isocyanatobenzene functional compound or resin should be mixed so that the ratio of NCO: isocyanatobenzene group was in the range of from 0.25 to 4:1, preferably 0.5 to 3:1, more preferably 0.75 to 2.5 to 1, and most preferably 1-2:1.

The polyisocyanate can be added to the dispersion of the (meth)acryloyloxy the national polyurethane in any convenient way.

Typically, however, the mixing can be difficult. Sometimes it may be convenient to dilute the polyisocyanate with an organic solvent such as ethyl acetate or 1-methoxy-2-propyl to reduce viscosity. In addition, opaque compositions containing free isocyanate groups, may be included reactive diluents, such as water-soluble mono or (preferably) polynuclear alcohols, examples of which include ethylene glycol, propylene glycol, isomeric butandiol, of polyethylene oxide glycols or glycol of polypropyleneoxide, trimethylolpropane, pentaerythritol and glycerin.

In the presence of free MDI typically use the catalyst on the basis of Sn. The duration of storage of free polyisocyanate composition at room temperature is usually from 4 to 12 hours depending on the catalysts and their quantities.

A suitable method of coating a substrate comprises applying the described coverts composition of water based on the substrate, removing carrier phase water-based forced or free and by curing the surface of the obtained film by ultraviolet light, and curing unexposed layers completely at room temperature or when heated.

Coverts composition can further include other ingred the coefficients, additives or auxiliary agents, such as other polymers or dispersion of polymers, pigments, dyes, emulsifiers (surface active agents), means for dispersing pigments, leveling agents, agents that prevent the formation of depressions, protivovspenivayushchie agents, agents that prevent the formation of stains, heat stabilizers, UV absorbers, antioxidants and fillers.

Suitable types of other polymer dispersions include emulsions of acrylic polymers and aqueous dispersions of polyurethanes.

Covering compositions of the present invention can be applied to any substrate. The substrate may be, for example, metal, plastic, such as PVC, wood, glass, ceramics or any other covering layer. This is another opaque layer may consist of opaque compositions of the present invention, or it may be another opaque composition. Covering compositions of the present invention demonstrate special applicability as transparent coatings, basic coatings, pigmented top coats, primers and fillers. Opaque compositions can be applied by conventional means, such as spray gun, brush or roller, preferably sputtering. The curing temperature is preferably from 0 to 80°C and more preferably from 20 to 60°C. Comp is the stand of the present invention is particularly suitable for coating metal substrates, such as in the case of the applied re-polishing, in particular, in industries associated with the application of polished surfaces, in particular in body shops for repair of cars and vehicles, and an outer coating of large vehicles, such as cars, trucks, buses and airplanes.

It is preferable to use opaque compositions of the present invention as a transparent coating. For transparent coatings need to be highly transparent and they must stick to the main layer of the coating. In addition, it is necessary that the transparent coating did not change the aesthetic aspect of the primary coating, penetrating into it, i.e. discoloring the main floor due to its dissolution transparent coating composition or as a result of yellowing clear coating under the influence of the external environment. Transparent coatings based on opaque compositions of the present invention does not have such disadvantages.

In that case, if opaque composition is a transparent coating, the base coating can be normal main floor, well-known experts in this field. Examples are basic coatings, solvent-based, for example Autobase® ex Akzo Nobel Coatings BV, and basic coating, water based, for example Autowave® ex Akzo Nobel Coatings BV. The AOC is e, basic coatings can contain pigments (coloured pigments, metal and/or mother-of-pearl), waxes, solvents, additives, providing fluidity, neutralizing agents and protivovspenivayushchie agents. You can also use the main cover with a large content of the solid part. Transparent opaque compositions are applied to the surface of the primary coating and then utverjdayut. Sometimes you can enter the intermediate stage of curing.

In another preferred embodiment, opaque composition of the present invention can be applied as a transparent coating on the flexible material for flooring. The preferred method of application in this case will be drawing with the help of rollers.

Hereinafter the present invention will be illustrated with reference to the following examples. Of course, these examples are presented only for a better understanding of the invention and in no way should be considered as limiting the scope of invention.

EXAMPLES of Methods

The corresponding average particle size in the dispersion is determined using dynamic light scattering, and dispersion is diluted to a content of solid particles about 0.1 wt%.

The solids content is determined in accordance with ASTM method No.1644-59 when heated to 140°C for 30 minutes.

Srednevekovoi molecular weight Mw and Rednikova molecular weight Mn determined, using helpanimals chromatography using polystyrene as a standard.

The hardness of Perozo obtained plating layers determine after 1-7 days of aging in accordance with standard French industrial method NF T30-016, and the results are expressed in seconds.

Resistance to methyl ethyl ketone (MEK) and water was determined after 1 and 7 days of aging and exposure within 1 minute (MEK) or for 1 hour (for water). In tests on the stability of 0 means the dissolution, 3 means weak damage, and 5 means excellent results.

Appearance is assessed visually. Good appearance means: the surface is smooth with strong luster. Bad appearance means: the surface is dull, weak Shine.

Resistance against scratches determine, pushing and scratching the floor with a nail. (-) means: the floor is very easily damaged; (+) means: for damage to the coating must strong pressure.

Evaluation of adhesion is carried out using the test cross section. To test the adhesion of the wet samples are left in the water for 5 days, then dried for 1 hour. Scores range from 0 to 5, and 5 is the best rating.

Obtaining dispersion acryloylmorpholine polyurethane containing polietilenoksidnoy group

a) Obtaining a complex poly is Fira, containing groups of the polyethylene oxide

The 3-liter 2-necked flask equipped with stirrer with adjustable speed, thermocouples in combination with a regulator, distillation column, reflux condenser, nitrogen bubbler and a jacket for heating, the mixture was charged, consisting of 332 g hexahydrophthalic anhydride and 1,614 g nanometrology ether of polyethylene glycol with an average molecular weight of 750. The mixture is heated to 170°C for 30 minutes, cooled to 140°C and add 269 g of di(trimethylolpropane), and then 132 g of xylene and 3.3 g of 85% aqueous phosphoric acid. The mixture is heated to 235°C and water are removed by azeotropic distillation until then, until the acid number of the reaction mixture does not fall below 5 mg KOH/g Then the mixture is cooled to 180°C and the xylene is distilled off under reduced pressure. Received polyetherdiol cures at room temperature and has an acid value of 3.9 mg KOH/g and a hydroxyl number of 59 mg KOH/g

b) Obtaining acryloylmorpholine diol

A 2-liter 2-necked flask equipped with stirrer with adjustable speed, thermocouple inlet dry air through the top, dip tube and jacket for heating load 573 g of hydrogenated bisphenol-diglycidylether ether (Eponex® 1510 ex Shell)and 17.5 g of acrylic acid and 0.56 g of 2,6-decret-butyl-p-cresol. The mixture is heated to 95°C, barbotine dry Vozduh for about 3 hours added dropwise a mixture of 157,7 g of acrylic acid, 0.56 g of 2,6-ditretbutyl-p-cresol and 0.75 g of chromium-2-ethylhexanoate. The temperature of the reaction mixture support between 95 and 100°C. Stirring at this temperature is continued until until the acid number of the reaction mixture does not fall below 5 mg KOH/g Obtained adduct is cooled and diluted with 97 g of dry 2-butanone.

c) obtaining a dispersion acryloylmorpholine polyurethane containing polietilenoksidnoy group

The 3-liter 2-necked flask equipped with stirrer with adjustable speed, thermocouples in combination with a regulator, a refrigerator, a bubbler for dry air and a jacket for heating, the mixture was charged, consisting of 273,2 g acryloylmorpholine diol Ab), 146,7 g complex polyester (Aa), of 12.26 g of trimethylolpropane, of 99.1 g of 2-hydroxyethylacrylate, 260,8 g Desmodur® W (polyisocyanate from Bayer), 1.50 g of 2,6-decret-butyl-p-cresol and 250 g of 2-butanone. The mixture is heated to 45°C and stirred to homogeneity, barbotine dry air. Then after one hour of stirring 0,94 g octanoate tin(II). The reaction mixture is stirred for approximately 6 hours at 80°C up until the isocyanate content is less than 0.1 %weight. Then add 3 ml of ethanol (100%) and stirring is continued for about 30 minutes. The reaction mixture is cooled to 45°C. After dilution of the reaction mixture of 154 g of 2-butanone speed AC is shivani increase and add 1,125 g of water at a rate of 12 ml/min After you add all the water, the head of the column and a vacuum pump connected to the flask and the pressure is gradually reduced until, until away the entire 2-butanone. Get a white emulsion with the following characteristics: solids content portion 44%, an equivalent weight of 535 per solid portion, Mn 2686, Mw 11153, pH 5.5, to a particle size of 120 nm.

Obtaining dispersion acryloylmorpholine polyurethane, comprising the ammonium and carboxylate groups of the polyethylene oxide B

The 3-liter 2-necked flask equipped with stirrer with adjustable speed, thermocouples in combination with a regulator, a refrigerator, a bubbler for dry air and a jacket for heating, the mixture was charged, consisting of 264,3 g Desmodur® W, 300 g of dry 2-butanone and 0.87 g of octanoate tin(II). The mixture is heated to 70°C, barbotine dry air. Then pre-mixed homogeneous mixture at 45°C, consisting of 273,6 g acryloylmorpholine diol Ab), of 52.8 g of a complex of the polyester (Aa), 16.7 g dimethylolpropionic acid, to 108.5 g of 2-hydroxyethylacrylate, 1.40 g of 2,6-decret-butyl-p-cresol and 270 g of 2-butanone added dropwise so as to maintain the exothermic reaction at 80°C. the Reaction is continued with stirring for about 6 hours at 80°C. After one hour stirring an additional portion of 0.87 g of octanoate tin(II). The reaction is ionic mixture is stirred for approximately 6 hours at 80° C up until the isocyanate content is less than 0.1 %weight. Then add 3 ml of ethanol (100%) and stirring is continued for about 30 minutes. The reaction mixture is cooled to 45°C. Then 95% of the acid groups of the reaction mixture is neutralized with N,N-dimethylethanolamine. The mixing speed increase and add 1,125 g of water at a rate of 12 ml/min After add all the water, the head of the column and a vacuum pump connected to the flask and the pressure is gradually reduced until, until away the entire 2-butanone. Get a white emulsion with the following characteristics: solids content part of the 47%, the equivalent weight 560 per solid portion, Mn 2286, Mw 6476, pH 8,8, the particle size of 120 nm.

Obtaining dispersion acryloylmorpholine polyurethane containing sulfopropyl and groups of polyethylene oxide With

a) Obtaining sulfosuccinimidyl

A 5-liter chetyrehosnuju round bottom flask, equipped with a fridge, a thermocouple, stirrer and input for nitrogen, add 1249,5 g of Cardura E10 ex Shell Chemicals. The temperature was raised to 140°C and then portions over 1 hour add 290,3 g of maleic acid. After that, the reaction mixture is heated with stirring at 150°C. Once the value of the acid number decreases to below 2 mg KOH/g, the reaction temperature was lowered to 95°C. Then add 475 g of water, 10 g of Dowanol-PM ex Dow Chemicals and 228,0 g dithionite sodium and stirring is continued for 1 hour at 60° C and one hour at 95°C. Then water and Dowanol distilled off from the reaction mixture under reduced pressure and the last traces removed by azeotropic distillation with 300 g of o-xylene. Then the reaction mixture is cooled to room temperature, add 600 g of dry 2-butanone and the precipitate is filtered from the product.

b) obtaining a dispersion acryloylmorpholine polyurethane containing sulfopropyl and groups of polyethylene oxide.

A 2-liter chetyrehosnuju round bottom flask, equipped with a fridge, a thermocouple, stirrer and input for dry air, reaching the reaction mixture was loaded to 144.7 g of Desmodur® W, 0,43 g octanoate tin (II) and 70 g of dry 2-butanone. This solution is heated and at 70 °C for one hour add the mixture 166,0 g acryloylmorpholine diol Ab), 39,1 g complex polyester Aa), 62,7 g sulfosuccinate diol Ca), and 63.3 g of 2-hydroxyethylacrylate, 0.8 g of ionol and 70 g of dry 2-butanone. After that add another 0,43 g octanoate tin(II) and the reaction mixture is heated under stirring at 80°C up until the isocyanate content becomes less than 0.1 %weight. Then the remaining isocyanate extinguish ethanol.

250 g of this solution add to 266 g of water for 1.5 hours at 50°C under vigorous stirring. Stirring is continued for 1.5 hours at 50°C, and then 2-butanone removed from the dispersion PE is Agency under reduced pressure. Get a dispersion with the following characteristics: solids content part 44,4%, equivalent weight 506 in the calculation of the solid portion, Mn 1781, Mw 5231, pH of 6.9, the particle size of 229 nm.

Obtaining dispersion acryloylmorpholine polyurethane containing sulfopropyl and groups of polyethylene oxide D

A 2-liter chetyrehosnuju round bottom flask, equipped with a fridge, a thermocouple, stirrer and input for dry air, reaching the reaction mixture was loaded 120,9 g Desmodur® W, 0.28 g of octanoate tin(II) and 60 g of dry 2-butanone. This solution is heated and at 70°C for 1 hour add the mixture of humidity 131.6 g acryloylmorpholine diol Ab), 44.4 g of a complex of the polyester (Aa), 39,8 g sulfosuccinate diol Ca), 53,5 g of 2-hydroxyethylacrylate, 0.5 g of BHT and 60 g of dry 2-butanone. After that, add 0.20 g of octanoate tin(II) and the reaction mixture is heated under stirring at 80°C up until the isocyanate content becomes less than 0.1 %weight. Then the remaining isocyanate extinguish ethanol. 410 g of this product add to 395 g of water for 1.5 hours at 50°C under vigorous stirring. Stirring is continued for 1.5 hours at 50°C, and then 2-butanone removed from the dispersion by distillation under reduced pressure. Get a dispersion with the following characteristics: solids content part 43.2%, the equivalent weight of 458 per the firmness of the blowing part, Mn 1934, Mw 6687, the particle size of 207 nm.

Obtaining dispersion acryloylmorpholine polyurethane containing sulfopropyl and groups of polyethylene oxide E

A 2-liter chetyrehosnuju round bottom flask, equipped with a fridge, a thermocouple, stirrer and input for dry air, reaching the reaction mixture was loads of 116.8 g of Desmodur® W, 0.27 g of octanoate tin(II) and 60 g of dry 2-butanone. This solution is heated and at 70°C for 1 hour add the mixture 144,4 g acryloylmorpholine diol Ab), 62,7 g complex polyester Aa), 9.7 g of sulfosuccinate diol Ca)and 50.3 g of 2-hydroxyethylacrylate, 0.85 grams of ionol and 60 g of dry 2-butanone. After that add another 0,41 g octanoate tin(II) and the reaction mixture is heated under stirring at 80°C up until the isocyanate content becomes less than 0.1 %weight. Then the remaining isocyanate extinguish ethanol.

235 g of this product add to 244 g of water for 1.5 hours at 50°C under vigorous stirring. Stirring is continued for 1.5 hours at 50°C, and then 2-butanone removed from the dispersion by distillation under reduced pressure. Get a dispersion with the following characteristics: solids content part of 49.4%, an equivalent weight of 449 per solid portion, Mn 2071, Mw 7663 and particle size 837 nm.

Obtaining dispersion acryloylmorpholine polyurethane containing groups of poly is telenokia F

In a 1-liter chetyrehosnuju round bottom flask, equipped with a fridge, a thermometer, a stirrer, input for dry air, reaching the reaction mixture, and the oil bath for heating load of 94.6 g of 1,6-hexamethylenediisocyanate, of 167.2 g acryloylmorpholine diol Ab), 100,5 g complex polyester Aa)and 6.9 g of trimethylolpropane, of 55.9 g of 2-hydroxyethylacrylate, 0.45 g of 2,6-decret-butyl-p-cresol and 150 g of dry 2-butanone. The reaction mixture is heated to 45°C and then add 0.25 g of octanoate tin(II). After that, the reaction mixture is heated further to 70°C and then added 0.20 g of octanoate tin(II). The reaction mixture is heated under stirring at 80°C up until the isocyanate content becomes less than 0.1 %weight. The remaining isocyanate extinguish ethanol. 50 g of 2-butanone added to 400 g of thus obtained solution of the polyurethane. At 45°C add 450 g of water for 2 hours under vigorous stirring. Stirring is continued for 1 hour. Then 2-butanone removed from the dispersion using a rotary evaporator. Get a dispersion with the following characteristics: solids content part of 41.6%, equivalent weight 431 in the calculation of the solid portion, Mn 2414, Mw 20884, particle size 2385 nm.

Obtaining dispersion acryloylmorpholine polyurethane containing groups of the polyethylene oxide G

a) obtaining the diol complex is on polyester

A 2-liter 2-necked flask equipped with stirrer with adjustable speed, thermocouple, in combination with the regulator, distillation column with a nozzle, an inlet for nitrogen and a jacket for heating, download 874,4 g of 1,6-hexandiol, 59,7 g hexahydrophthalic anhydride and 0.42 g of the oxide dibutylamine. The reaction mixture is heated with stirring in a stream of nitrogen up to 250°C. This temperature is maintained for 4 hours and evaporated 75 g of water. The reaction mixture is cooled to 105°C. the Rest formed in the reaction water is distilled off under reduced pressure. The obtained diol complex polyester has an acid number of 3.2 mg KOH/g, hydroxyl number 172 mg KOH/g, 990 Mn and Mw 1600.

b) obtaining a dispersion acryloylmorpholine polyurethane containing groups of the polyethylene oxide G.

In a 1-liter chetyrehosnuju round bottom flask, equipped with a fridge, a thermometer, a stirrer, input for dry air, reaching the reaction mixture, and the oil bath for heating, download 110,0 g Desmodur® W, is 120.7 g acryloylmorpholine diol Ab), 105,0 g complex polyester Aa), 76,3 g diol complex polyester Ga), of 22.2 g of 2-hydroxyethylacrylate, 0.8 g of 2,6-ditretbutyl-p-cresol and 175 g of dry 2-butanone. The reaction mixture is heated to 45°C and then add 0.25 g of octanoate tin(II). After that, the reaction mixture is heated further to 70°C and then we use the t 0.25 g octanoate tin(II). The reaction mixture is heated under stirring at 80°C up until the isocyanate content becomes not smaller than 0.15 wt%. The remaining isocyanate extinguish ethanol. 100 g of 2-butanone added to 400 g of thus obtained solution of the polyurethane. At 45°C add 450 g of water for 2 hours under vigorous stirring. Stirring is continued for 1 hour. Then 2-butanone removed from the dispersion using a rotary evaporator. Get a dispersion with the following characteristics: solids content part 44,8%, equivalent weight 763 per solid portion, Mn 4251, Mw 34288 and the particle size of 128 nm.

Properties obtained above (meth)acryloylmorpholine polyurethane resins are presented in table 1.

Table 1
Resin%weight. EOAcid number (mg KOH/g)MnEw (g/EQ)Functionality
A14,5026865355,6
B5,61022865604,1
C6,18,081781506the 3.8
D8,16,071934 4584,3
Ethe 11.61,5220714494,5
F14,7,Not defined24144315,6
G14,8Not defined42517635,8

Examples 1-5

Get the following opaque composition.

Coverts composition 1 contains 50.0 g of dispersion acryloylmorpholine polyurethane A (solids content part of 24.3 g), to which is added 7.50 g of water, 2.50 g of butylglycol, 0.25 g BYK 346 (wetting agent containing solid part of 0.12 g) and 1.28 g of Darocur® 1173 (UV initiator from Ciba).

Coverts composition 2 was the same as composition 1, except that the added 7.30 g Craynor 132 (acryloylmorpholine reactive diluent from Cray Valley).

Coverts composition 3 contains 50.0 g of dispersion acryloylmorpholine polyurethane B (solid content part of 20.0 g), to which was added 2.50 g of butylglycol, 0.25 g BYK 333 (wetting agent containing solid portion 98%) and of 0.83 g of Lucirin TPO-L (UV initiator from BASF).

Coverts composition 4 similar composition 3 after adding 6,23 g Craynor 132.

Coverts composition 5 contains 50.0 g of dispersion acryloylmorpholine polyurethane A (solids content part to 25.15 g), which is obavljeno 7.50 g of water, 2.50 g of butylglycol, 0.25 g BYK 333, of 7.55 g Craynor 132 and 1.31 g of Lucirin TPO-L.

Compositions 1-4 applied to tin-plated panel traction beam (thickness 100 μm when wet application). Songs 1-5 is applied by spraying the blue metal surface, the resulting water-based (Autowave®). The dry thickness of the transparent coating is in the range from 65 to 90 μm. The panel is dried to evaporate all the water (at least 90 minutes at room temperature or 30 minutes at 60°). Then the film is irradiated for 10 minutes at room temperature lamps for tanning (TL 09, distance 10 cm).

Properties of the obtained layers of coatings on tin-plated panels (tracks 1-4) or on the coatings obtained water-based (in the case of composition 5 for all characteristics and compositions 1-4 to determine appearance) are presented in table 2.

Table 2
ExampleThe hardness of PerozoResistance to methyl ethyl ketone (MEK)Resistance to waterAppearance and scratch resistanceLayer thickness (μm)
1 day7 days1 day7 days1 day7 days
11672383-43-455The via./+67
21651815555Good/+71
31571703-41)3-41)3-42)3-42)Bad/-80
41331203-41)3-41)3-42)3-42)Bad/-79
5Not ODA.Not ODA.3-43-455Good/+86
1) the top layer of the film dissolved

2) the film becomes turbid after exposure in water for 1 hour

The appearance of layers of coatings obtained from compositions 2 and 5 were the best. This experiment demonstrates the preference coverts compositions comprising (meth)acryloylmorpholine polyurethane containing from 8 to 18 wt%. alkalinising groups. Even more preferably the covering composition, includes a reactive diluent.

Comparative example A

Prepare opaque composition is A solvent-based, containing 50.0 g of a solution acryloylmorpholine polyurethane (as described for dispersion A) meilensteine with Craynor 132 (solid content part of 44.7 g) as a reactive diluent and, in addition, 1,00 g butylglycol, 21,43 g of butyl acetate, 16,07 g of methyl ethyl ketone and 1.88 g Darocur® 1173.

After applying the spray on blue metal surface, the resulting water-based (Autowave®)obtained covering layer is dried and irradiated with the methods described for layers obtained in examples 1-5. Properties of the resulting opaque layer of opaque compositions are solvent-based, as it turns out, have worse characteristics. The covering layer is highly colored.

Examples 6-8

Each of the opaque compositions 6-8 contains 50.0 g of dispersion acryloylmorpholine polyurethane A (solids content part of 24.3 g), to which is added 7.50 g of water, 2.50 g of butylglycol, 0.25 g BYK 346 (wetting agent containing solid part of 0.12 g) and 1.28 g of Darocur® 1173. In addition, the respective compositions include 10 %weight. (based on the dispersion of polyurethane) Sartomer® 214 (1,4-potentialtarget from Sartomer) (track 6), 10%weight. (based on the dispersion of polyurethane) Sartomer® 239 (1,6-hexanediamine kilat from Sartomer) (composition 7) and 30%by weight. (based on the dispersion of polyurethane) Sartomer® 350 (trimethylolpropane from Sartomer) (composition 8).

When applied to tin plate the resulting layers of the coating is dried and irradiated similarly to the method above for layers obtained in examples 1-5. Properties of hardened layers of coatings on tin-plated panels (tracks 2-8) are presented in table 3.

Table 3
ExampleThe hardness of PerozoResistance to methyl ethyl ketone (MEK)Resistance to waterAppearance and scratch resistanceLayer thickness (μm)
1 day7 days1 day7 days1 day7 days
62102093-43-454Good72
72262173-43-454Good75
82352393-43-45 4Good78

Opaque compositions 6, 7 and 8 was applied also on a blue metallic coatings obtained water-based (Autowave®). All three coatings had good appearance.

Examples 9-12

Four dispersion acryloylmorpholine polyurethane containing various amounts alkalinising groups tested in opaque compositions, as indicated in table 4 (amounts are given in grams:

0,46
Table 4
9101112
Dispersion And20,0---
Dispersion E-20,0--
Dispersion D--20,0-
Variance---20,0
Water5,03,03,03,0
Butylglycol1,01,01,01,0
Byk 3460,10,10,10,1
Darocur 11730,470,510,45
Craynor 1322,702,962,592,66,

These compositions are applied on a tin plate and blue metallic coatings obtained water-based (Autowave®). Drying and curing are carried out by the methods of examples 1-5. The results are presented in table 5.

Table 5
TrackLayer thickness (μm)Resistance to methyl ethyl ketone (MEK) (1 day aging)Resistance to water (1 day aging)The hardness of Perozo (s) after 1 day of agingThe appearance on top of the basic coveragescratch resistance
97955185Good+
109045188Good+
11753-45197Good+/-
12773-43-4199Good-

These experiments also show a preference for opaque compositions, VK is uchumi (meth)acryloylmorpholine polyurethanes, containing from 8 to 18 wt%. alkalinising groups and reactive solvent.

Example 13

Get the following compositions listed in table 6 (amounts are given in grams):

Table6
Dispersion And20,0
Water3,0
Butylglycol1,0
BYK 3460,1
3-methoxypropylamine2,92
Darocur 11730,51

This composition is applied on a tin plate and the blue metal surface, the resulting water-based (Autowave®). Drying and curing is carried out according to the method of examples 1-5. The film has the following characteristics, listed in table 7:

Table 7
ExampleThe hardness of PerozoResistance to methyl ethyl ketone (MEK)Resistance to waterAppearance and scratch resistanceLayer thickness (μm)
171717
daydaysdaydaysdaydays
131711754455Good/+74

Example 14 and comparative example

Get the following coverts compositions listed in table 8 (the amount is given in grams):

Borshigel LW44
Table 8
14In
Lux VP 101Dispersion of aliphatic polyurethane (s.c. 40%) ex Alberdingk Boley34,887
Variance52,2-
Esacure KIP 100FPhotoinitiator ex Lamberti1,31,3
Speedcure BEMPhotoinitiator ex Lambson0,40,4
Byk 346Protivovspenivayushchie agent ex Byk Chemie0,30,3
Byk 333A balancing agent ex Byk Chemie0,20,2
Orgasol 2001Polyamide wax ex Elf Atochem1,510,5
Polyurethane thickener0,30,3

Compositions are applied to the PVC flooring roll in the range from 10 to 50 g/m2. The substrates with the coating is dried until then, until all the water evaporates (3 minutes at 120°C). Then the film is irradiated at a speed of the conveyor belt 5 to 10 meters per minute mercury lamp of 80 W/see the results Obtained are presented in table 9.

Table 9
TrackDry adhesionWet adhesion
1455
B30

Other properties such as chemical resistance and flexibility, were at the same level or better than the results of the comparative example.

Example 15 and comparative example C

Get the following coverts compositions listed in table 10 (the amount is given in grams):

Table 10
15C
Lux VP 101Dispersion of aliphatic polyurethane (s.c. 40%)

ex Alberdingk Boley
20,631,7
Variance/td> 32,5-
Primal E-3120Acrylic emulsion (s.c. 40%) ex Rohm & Haas39,661,0
Esacure KIP 100Fphotoinitiator ex Lamberti1,51,5
Speedcure BEMphotoinitiator ex Lambson0,50,5
Dehydran 1293Protivovspenivayushchie agent

ex Cognis
0,60,6
Byk 346Protivovspenivayushchie agent

ex Byk Chemie
0,30,3
Byk 333A balancing agent

ex Byk Chemie
0,20,2
Orgasol 2001Polyamide wax

ex Elf Atochem
the 3.8the 3.8
Acrysol RM-2020Polyurethane thickener

ex Rohm & Haas
0,40,4

Compositions are applied to the polyolefin flooring roller in the range from 10 to 50 g/m2. Drying and curing is carried out according to the method of example 14. The results are presented in table 11.

Table 11
TrackDry adhesionWet adhesion
15 55
C30

Other properties such as chemical resistance and flexibility, were at the same level or better than the results of the comparative example.

Examples 16 and 17

Get the following opaque composition.

Coverts composition 16 contains 50.0 g of dispersion acryloylmorpholine polyurethane F (solid content part of 20.8 g), which is added 7.50 g of water, 2.50 g of butylglycol, 0.25 g BYK 346 and 0.85 grams Darocur® 1173.

Coverts composition 17 contains 50.0 g of dispersion acryloylmorpholine polyurethane G (solid content part of 22.4 g), to which is added 7.50 g of water, 2.50 g of butylglycol, 0.25 g BYK 346, 1.10 g Darocur® 1173 and 6,30 g Craynor 132.

Compositions 16 and 17 applied to tin-plated panel traction beam (thickness 100 μm in wet deposition) and the blue metal coating water-based (Autowave®) sputtering. The panel is dried until then, until all the water evaporates (at least 90 minutes at room temperature or 30 minutes at 60°). Then the film is irradiated for 10 minutes at room temperature lamps for tanning (TL 09, 10 cm distance). Properties of the obtained layers of the coatings are presented in table 12.

Table 12
ExampleVerdot on Personu Resistance to methyl ethyl ketone (MEK)Resistance to waterAppearance and scratch resistanceLayer thickness (μm)
1day7 days1 day7 days1 day7 days
161581705555Good/+65
171371355555Good/+77

These experiments show that coverts compositions of the present invention provide coatings with good properties.

1. Photoactivated opaque composition is water-based, including;

a) a dispersion of a (meth)acryloylmorpholine polyurethane, and (meth)acryloylmorpholine polyurethane comprises from 5 to 18 wt.% alkalinising groups, and (meth)calolina functionality is a value in the range from 2 to 40, and

b) UV-initiator.

2. Covering the composition is water-based according to claim 1, characterized in that the (meth)acryloylmorpholine polyurethane contains from 8 to 18 wt.% alkalinized the x groups.

3. Covering the composition is water-based according to any one of the preceding paragraphs, characterized in that it comprises a reactive diluent.

4. Covering the composition is water-based according to any one of the preceding paragraphs, characterized in that srednetsenovoj molecular weight (meth)acryloylmorpholine polyurethane is in the range from 1200 to 8000.

5. Covering the composition is water-based according to any one of the preceding paragraphs, characterized in that the equivalent weight of the (meth)acryloylmorpholine polyurethane is in the range from 200 to 4000 g/EQ in the calculation of the solid product.

6. Covering the composition is water-based according to any one of the preceding paragraphs, characterized in that the (meth)acryloylmorpholine polyurethane can be obtained by the reaction

a) at least one organic MDI,

b) optionally at least one organic compound containing at least two isocyanatobenzene group and having srednetsenovoj molecular weight in the range of from 400 to 6000,

c) at least one isocyanatobenzene and/or isocyanatobenzene compounds containing non-ionic dispersing groups,

d) at least one isocyanatobenzene (meth)acryloylmorpholine connection

e) optionally at least one chain extension containing active hydrogen, and

f) optionally, at least one compound containing active hydrogen containing ionic groups.

7. Covering the composition is water-based according to any one of the preceding paragraphs, characterized in that the covering composition comprises an organic polyisocyanate and compounds, including isocyanatobenzene groups such as hydroxyl groups.

8. Covering the composition is water-based according to claim 7, characterized in that the connection involving isocyanatobenzene groups, such as hydroxyl group is (meth)acryloylmorpholine polyurethane.

9. Covering the composition is water-based according to any one of claims 7 and 8, characterized in that coverts the composition ratio of free isocyanate groups to izotiotsianovoy groups is 0.25-4:1.

10. Covering the composition is water-based according to any one of the preceding paragraphs, characterized in that the covering composition is a transparent coating is water-based.

11. Method of coating a substrate that includes applying a covering composition for water-based according to any one of the preceding paragraphs on the substrate, removing carrier phase water-based forced or free way and overide the e surface of the obtained film by ultraviolet light.

12. Method of coating a substrate that includes applying a covering composition for water-based according to any one of claims 7 and 9 on the substrate, removing carrier phase water-based forced or free and by curing the surface of the obtained film by ultraviolet light, and curing is not exposed to UV light layers completely at room temperature or when heated.

13. Method of coating a metal substrate primary coverts composition and a transparent covering composition, wherein the transparent cover includes a dispersion of a (meth)acryloylmorpholine polyurethane containing from 8 to 18 wt.% alkalinising groups and UV initiator.

14. The method of applying a flexible floor covering transparent covering composition, characterized in that the transparent covering composition comprises a dispersion of a (meth)acryloylmorpholine polyurethane containing from 5 to 18 wt.% alkalinising groups and UV initiator.

15. The method according to any of PP and 14, characterized in that the transparent covering composition comprises a reactive diluent.



 

Same patents:

The invention relates to compositions based on emulsified resins, curable by ultraviolet radiation, which includes: unmodified oligomers as the basis of composition, which determines the final properties of the cured product; curing agents consisting of polyfunctional monomers; photoinitiator initiating polymerization; additives to make the product special properties

The invention relates to the field of coatings, curing under the action of radiation of low energy in the wavelength range of 400-700 nm and used in such fields as dentistry, electronics, printing

The invention relates to the field of rocket technology and concerns a method for obtaining a modifier, which is the basis for unsaturated polyester compounds

The invention relates to methods for elastomeric materials and may be used in the manufacture of sealants, coatings and molded articles

FIELD: polymer materials.

SUBSTANCE: invention relates to ionomer thermoplastic polyurethane, method for preparation thereof, use of indicated ionomer thermoplastic polyurethane to prepare aqueous dispersions thereof, as well as to a method for preparing aqueous dispersions of ionomer thermoplastic polyurethanes. Ionomer thermoplastic polyurethane is prepared via continuous reaction of (i) 4-50% if diisocyanate; (ii) 35-95% of bifunctional polyatomic alcohol selected from group comprising (a) polycaprolactone with mean molecular mass between 500 and 15000 and general formula I: (I), (b) polyesterdiol with mean molecular mass between 500 and 15000 and general formula II: (II), (c) polyesterdiol selected from polypropylene glycol, polytetramethylene glycol, and polyethylene glycol, (d) polycarbonatediol with mean molecular mass between 500 and 15000 and general formula III: (III), and (e) copolymers obtained from two bifunctional polyatomic alcohol from groups (a), (b), (c), or (d); (iii) 0.2-16% of chain-elongation glycol of general formula IV: (IV); and (iv) 0.2-3% of chain-elongation anionic-type ionomer glycol of general formula V: (V).

EFFECT: enabled preparation of ionomer polyurethane suitable for being stored in solid form for subsequent preparation of aqueous dispersions of thermoplastic polyurethanes appropriate as industrial adhesives and coating materials for flexible and rigid substrates.

34 cl, 2 tbl, 10 ex

The invention relates to rigid polyurethane foams and methods for their preparation using a mixture of polyols

FIELD: polymer materials.

SUBSTANCE: invention relates to ionomer thermoplastic polyurethane, method for preparation thereof, use of indicated ionomer thermoplastic polyurethane to prepare aqueous dispersions thereof, as well as to a method for preparing aqueous dispersions of ionomer thermoplastic polyurethanes. Ionomer thermoplastic polyurethane is prepared via continuous reaction of (i) 4-50% if diisocyanate; (ii) 35-95% of bifunctional polyatomic alcohol selected from group comprising (a) polycaprolactone with mean molecular mass between 500 and 15000 and general formula I: (I), (b) polyesterdiol with mean molecular mass between 500 and 15000 and general formula II: (II), (c) polyesterdiol selected from polypropylene glycol, polytetramethylene glycol, and polyethylene glycol, (d) polycarbonatediol with mean molecular mass between 500 and 15000 and general formula III: (III), and (e) copolymers obtained from two bifunctional polyatomic alcohol from groups (a), (b), (c), or (d); (iii) 0.2-16% of chain-elongation glycol of general formula IV: (IV); and (iv) 0.2-3% of chain-elongation anionic-type ionomer glycol of general formula V: (V).

EFFECT: enabled preparation of ionomer polyurethane suitable for being stored in solid form for subsequent preparation of aqueous dispersions of thermoplastic polyurethanes appropriate as industrial adhesives and coating materials for flexible and rigid substrates.

34 cl, 2 tbl, 10 ex

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyurethane-polyol compositions comprising product of reaction of a polyol and Herbert alcohol, the two containing In average 12 carbon atoms. Preferred polyols are α,β-diols and α,β-diols. Polyurethane-polyol compositions exhibit very low viscosity and are particularly suitable in coating compositions with very low content of volatile organics. Hardened coating obtained from claimed compositions ensure high resistance to cracking and can be applied on various substrates such as metal, plastic, wood, glass, ceramics.

EFFECT: increased strength of coatings on a variety of substrates.

5 cl, 3 tbl

FIELD: composite materials.

SUBSTANCE: in particular, invention relates to employment of polyisocyanates compositions as binders for composites containing lignocellulose fibers such as oriented wood chipboard.

EFFECT: improved performance characteristics regarding detachment of product as compared to conventional polyisocyanates employed for binding lignocellulose material.

11 cl, 7 tbl, 8 ex

FIELD: polymer production.

SUBSTANCE: invention relates to process of producing elastomeric polyurethane material having Shore hardness up to 5 (DIN 53505), density 500 kg/m3 or higher (DIN 53420), compressive load (40%) deflection 600 kPa or less (DIN 53577), and elasticity 25% or less (ISO 8307). Process is accomplished by interaction of (i) polymethylene-polyphenylene-polyisocyanate with average isocyanate functionality 2.4 or more; (ii) polyol with average equivalent mass at least 500 and average nominal hydroxyl functionality 2-4; (iii) polyoxyalkylenemonool with nominal hydroxyl functionality 1 and average equivalent mass at least 500; and (iv) optional additives and auxiliary substances known per se in amount less than 5%. Reaction is carried out at index 90-110 and equivalent amount of polymer (iii) lies within a range of 25-80% based on accessible NCO equivalents. Elastomeric polyurethane material accordingly obtained is a soft gel-like material showing some degree of tackiness. Advantageously, this material is obtained using as little additives and auxiliary substances as possible, which results in reduced content of washed out products and residual reactive group in elastomeric polyurethane material. The latter can be employed in vehicle interior objects such as elbow-rests and instrumentation panels, in bicycle sittings, and in mouse tappets.

EFFECT: improved consumer's quality of elastomers.

1 tbl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing stable aqueous dispersions of polycarbodiimide for using as a cross-linking agent and no containing organic solvents. Method is realized by carrying out interaction of polyisocyanate in the presence of 0.5-3% of catalyst in reaction for formation of carbodiimide to form polycarbodiimide intermediate substance at 120-1800C for aliphatic polyisocyanate and at 80-1200C for aromatic polyisocyanate up to preparing 5-10% of NCO wherein polyisocyanate is represented by toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or their mixture, diphenyl-4,4'-diisocyanate, 1,4-phenylenediisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, 1,6-hexyldiisocyanate, 1,4-cyclohexyldiisocyanate, norbornyldiisocyanate or their mixture. Then method involves carrying out break and/or elongation of polycarbodiimide chain of intermediate substance by addition of equivalent compound comprising hydrophilic group and one or more amino- and/or hydroxyl functional groups during formation of polycarbodiimide intermediate substance or after formation of polycarbodiimide at temperature 70-1000C for aliphatic polycarbodiimide intermediate substance and at temperature 40-700C for aromatic polycarbodiimide intermediate substance. Then reaction in mixture is carried out up to disappearance of isocyanate functional group wherein a hydrophilic group-containing compound is represented by polyethoxymono- or diol, polyethoxy/polypropoxymono- or diol, polyethoxymono- or diamine, polyethoxy/polypropoxymono- or diamine, diol or diamine with polyalkoxy-containing by-side chain, hydroxy- or aminoalkylsulfonate, or dialkylaminoalkyl alcohol or -amine, or their mixture. Prepared compound is dispersed in water at temperature 40-1000C at pH 11-14 by addition of a base and/or buffer to water used for dispersing, and/or to prepared aqueous dispersion wherein a base is represented by alkaline metal hydroxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or trialkylamine, or trialkylamine containing hydroxy-groups, and wherein buffer is represented by usually used buffer with effective pH value 11-14. Polycarbodiimide dispersions prepared by above described method are stable for at least some weeks at temperature 500C. Also, invention describes a covering mixture comprising polycarbodiimide dispersions and solidified material prepared by applying abovementioned covering mixture on substrate and evaporation of water.

EFFECT: improved preparing method of dispersions.

3 cl, 2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: invention concerns expandable polyamide composition consisting basically of: (A) compound with at least one isocyanate group, possible blocked one, (B) polyamide, and (C) compound with at least one acid group, preferrably carboxyl one. The invention also concerns production of polyamide foam from the said composition and the foam produced in this process. The said process allows obtaining foam directly from the said composition, i.e. without addition of any extra compounds, as well as foaming reaction control. Moreover, according to the invention, this foam has regular cell distribution conforming to the closed type and can be applied in various fields, e.g. in thermal or sound insulation and saddlery.

EFFECT: obtainment of foams of various types and properties.

30 cl, 1 tbl, 7 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns multicomponent local foam system for obtaining foam polyurethanes for local construction purposes, consisting of polyisocyanate (component A), and polyene containing water (component B), stored in separate containers, and epoxy resin based on bisphenol A and bisphenol F, and/or siloxane forpolymer with average mol weight from 200 g/mol to 10000 g/mol with reactive end alcoxy groups (component C), generic catalyst for polyurethane generation reaction and/or generic binding agent for siloxane forpolymer (component D) in spatially divided form, and optional filler, one or more colourants or pigments and generic additives. When mixed, the components of foam system form interpenetrating polymer mesh structure out of foamed polyurethane and at least one other polymer, with excellent adhesion to adjoining wall material, thus reducing water penetration or forming mechanically stable cork in case of fire to render resistance to fire. Claimed foam system is foaming and solidifying in severe conditions on construction site, e.g. at temperatures from 0°C to 40°C, and non-homogeneously filling of volume.

EFFECT: sealing of fractures and/or through orifices in building walls and/or floors.

23 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention concerns two-pack composition for ground reinforcement by compression in mining and construction engineering. Composition includes forpolymer component based on methylenediphenyldiisocyanate and multiatom alcohol component with several functional groups, mixing and compression of which ensures fast polymerisation, reaction temperature of 130°C, foaming below five times increase of initial volume, mechanical tension of 1 MPa by ageing for 30 minutes to 5 hours after gluing, and devoid of significant fissuring caused by internal tension during polymerisation. Limited reaction capability is achieved by volumetric mixing of components at 1:1 ratio of methylenediphenyldiisocyanate forpolymer with N=C=O number from 18 to 24, preferably 22, to multiatom alcohol with several functional groups maintaining N=C=O number from 1.1 to 1.4, and ensures good adhesion to carrier. One of the composition components includes foam suppressant consisting of non-ion surfactants and non-saponifying substances.

EFFECT: obtaining composition with enhanced fireproof properties, limited foaming at contact with unlimited water quantity, ensuring reduced danger of forming fractures and heating related to possible air leakage, and good mechanical properties.

15 cl

FIELD: technological processes, chemistry.

SUBSTANCE: invention is related to method for production of polyurethane foam with application of secondary waste of polyethylene terephtalate, and may be used for production of hard polyurethane foams. Polyurethane foam is produced by interaction of polyisocyanate with polyol component containing secondary waste of polyethylene terephtalate dissolved in triethanolamine or in mixture of mono-, di-, trichloracetic acids, in amount of not more than 67 wt % from total weight of polyol component. At that interaction is carried out at the ratio of polyol component : polyisocyanate as 1:1 - 1:2. Prepared polyurethane foams have good consumer properties, such as compression strength, oil-, heat resistance and reduced inflammability.

EFFECT: recycling of polymer wastes in the form of containers and package from polyethylene terephtalate, considerable reduction of polyurethane foam cost with simultaneous solution of environmental problems due to recycling of secondary polyethylene terephtalate.

16 ex

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

FIELD: glue compositions.

SUBSTANCE: invention relates to UV-strengthening glue compositions used for gluing polymethylmethacrylate with metal. Proposed composition comprises oligourethane-acrylate representing product of interaction of oligobutadienediol of molecular mass 2000-3000 Da, aliphatic or aromatic diisocyanate and hydr(o)oxyalkylmethacrylate taken in the molar ratio = 1:2:2, reactive monomer-diluting agent representing a mixture of mono- and polyfunctional methacrylate, polymeric filling agent - polyethylene of high density with particles size below 50 mcm, photoinitiating agent, antioxidant of phenolic type and adhesion promoter - a mixture of chlorinated polyvinyl chloride with chlorine content 62-64 wt.-% and oxalic acid, and the composition comprises additionally thixotropic agent - aerosil with specific surface 175-380 m2/g and ester plasticizing agent. Invention provides the development of UV-strengthening glue composition showing the thixotropy coefficient K = 2-3, shrinkage 4%, not above, break off strength both in the parent state and after heat effect, moisture and temperature drop 1.5 MPa, not less, and stability in storage above one year. The composition can be used as adhesive in electronic devices, such as optical reading head, thin-film transistor - mesomorphic display and organic electroluminescent unit.

EFFECT: valuable properties of composition.

5 cl, 2 tbl, 5 dwg, 8 ex

FIELD: glue compositions.

SUBSTANCE: invention relates to UV-strengthening glue compositions used for gluing substrates metal-silicate glass in electronic devices, such as optical reading head, thin-film transistor - semiconducting mesomorphic display, organic luminescent unit. The composition comprises oligourethaneacrylate - a mixture of oligourethaneacrylates of two type: the first is prepared by interaction of oligooxyalkylenepolyol of molecular mass 1000-5000 Da, diisocyanate of aliphatic or aromatic structure and alkylene glycol monomethacrylate, and the second based on oligobutadienediol of molecular mass 2000-3000 Da, diisocyanate of aliphatic or aromatic structure and alkylene glycol monomethacrylate in the mass ratio of the first to the second = (1.0-4.0):1, reactive monomer as a diluting agent, silicate filling agent, organic tert.-butylperbenzoate, thixotropic agent - aerosil and photoinitiating agent, and, additionally, it comprises oxalic acid as adhesion promoter, silane dressing agent and antioxidant of phenolic type. Invention provides the development of UV-strengthening glue composition possessing thixotropy, high strengthening rate, high adhesion strength being especially at effect of heat and moisture, temperature drop, low shrinkage and stability in storage.

EFFECT: improved and valuable properties of composition.

7 cl, 2 tbl, 5 dwg, 8 ex

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