WO2017161607A1 - Waterborne radiation curing urethane acrylate composition, preparation method therefor and coating - Google Patents

Abstract

A waterborne radiation curing polyurethane acrylate composition comprises, by weight, 20-80 parts of polyurethane acrylate oligomer A and 20-80 parts of water dispersible polyurethane polymer B. The waterborne radiation curing polyurethane acrylate composition is high in stability and has pH value of 7.5-9 and viscosity of 10-500 cps; when the composition is stored at temperature below 25 DEG C for 20 days, the pH value is lowered by less than 10% with respect to the initial value, and the viscosity is changed by less than 10%with respect to the initial value; when the composition is stored at temperature below 50 DEG Cfor 20 days, the pH value is lowered by less than 20% with respect to the initial value, and the viscosity is changed by less than 50% with respect to the initial value.

Description

Aqueous radiation curable urethane acrylate composition, preparation method and coating Technical field

The invention belongs to the field of coatings, in particular to an aqueous radiation-curable urethane acrylate composition and a preparation method thereof and an aqueous coating material containing the same.

Background technique

The most important component of photocurable waterborne coatings is water-dispersible urethane acrylate oligomers. In order to improve the various mechanical properties and resistance of coatings, some polyfunctional acrylate compounds are usually added to the oligomer or polyfunctional. The hydroxy acrylic acid reacts with the isocyanate group. In the preparation of the aqueous radiation curable urethane acrylate composition for emulsification dispersion, an alkali neutralizing agent is added to neutralize the hydrophilic compound in the urethane acrylate. The photocurable water-based paint prepared in this manner is generally alkaline, and the acrylate group in the resin, especially the polyfunctional free acrylate, is easily hydrolyzed in an alkaline environment during long-term storage and transportation at a high temperature, and the acrylic acid content in the resin system. The increase is greatly increased, the pH is continuously lowered, the pH value is lowered, the degree of ionization of the hydrophilic compound is lowered, the thickness of the double electric layer on the surface of the emulsion particles is reduced, the stability of the emulsion is lowered, and the surface of the emulsion particles is caused by the change of the pH value. The hydrophilicity of the water changes.

In order to facilitate the construction, different thickeners are added to the coating formulation to adjust the viscosity of the coating. Commonly used thickeners are polyurethane associative thickeners, alkali-swelling associative thickeners, and these thickeners are affected by the pH of the coating. The influence is large. As the pH value decreases, the thickening efficiency of the alkali-swelling thickener decreases, the viscosity of the coating decreases, the thickening efficiency of the associative thickener increases, and the viscosity increases greatly, which seriously affects the construction of the coating.

Patent CN101622290A discloses a low-gloss coating radiation-curable aqueous composition, which achieves low gloss of the coating mainly by increasing the particle size (greater than 500 nm) of the particles in the coating, but the particle size is too large, which leads to coating The stability is reduced.

Patent CN101563370A discloses a method for maintaining the viscosity stability of an aqueous radiation-curable coating, which uses a monofunctional tertiary amine neutralizing agent having a pKa of not more than 8 to neutralize the hydrophilic group to control the pH of the coating at 7.5-8.7, and the viscosity of the coating. Stability is up to 1 month. The neutralizing agent used in this patent is weak in alkalinity, and the stability of the coating resin is poor. When preparing the formulated coating, It is prone to instability such as sedimentation.

No. 6,284,836 B1 discloses a low-gloss coating composition in which a matting agent particle such as diatomaceous earth is added to obtain a low gloss effect, but the amount added is more than 6 wt% of the solid content of the coating composition, due to the large amount of addition, The coating is too brittle, the matting agent in the coating is easy to deposit, and the coating resistance is lowered.

Summary of the invention

Accordingly, it is a first object of the present invention to provide an aqueous radiation curable urethane acrylate composition for use in the preparation of a coating which improves the stability of the coating while achieving low gloss of the coating. , in particular, to improve the stability of the coating in higher temperature environments;

A second object of the present invention is to provide a process for the preparation of the above composition;

A third object of the present invention is to provide an aqueous coating which has low gloss and high stability.

The technical solution of the present invention is as follows:

An aqueous radiation curable urethane acrylate composition comprising urethane acrylate oligomer A in a weight fraction of 20-80 and water-dispersible polyurethane polymer B in a weight fraction of 20-80;

Wherein, the urethane acrylate oligomer A comprises the following raw materials:

Polyisocyanate A1, the polyisocyanate A1 parts by weight of 25-75, preferably 41-55;

Acrylate and/or methacrylate compound A2, said acrylate and/or methacrylate compound A2 comprising at least one active hydrogen reactive with said polyisocyanate A1 and at least one acrylate and/or The acrylate group, the acrylate and / or methacrylate compound A2 parts by weight of 25-75, preferably 41-55;

Small molecule polyol A3, the small molecule polyol A3 has a molecular weight of 60-400, a hydroxyl functionality of 2-4, and a weight fraction of 0-6, preferably 2-4;

The water-dispersible polyurethane polymer B comprises the following raw materials:

Diisocyanate B1, the diisocyanate B1 parts by weight of 20-60, preferably 30-50;

An alkyl acid hydrophilic compound B2, the alkyl acid hydrophilic compound B2 containing at least one An active hydrogen reactive with isocyanate B1 and at least one hydrophilic acidic group, the alkyl acid hydrophilic compound B2 in parts by weight of 3-15, preferably 5-10;

Small molecule polyol B3, the small molecule polyol B3 has a molecular weight of 60-400, a hydroxyl functionality of 2-4, and a weight fraction of 0-10, preferably 2-5;

a polymer polyol B4, the polymer polyol B4 being a polyester diol and/or a polyether diol having a weight average molecular weight of 400-4000, in parts by weight of 25-70, preferably 35-50;

An acrylate and/or methacrylate compound B5 comprising at least one active hydrogen reactive with the diisocyanate B1 and at least one acrylate group and/or a methacrylate group, the acrylate and / or methacrylate compound B5 parts by weight of 0-30, preferably 5-15;

The neutralizing agent B6, the molar ratio of the neutralizing agent B6 to the hydrophilic acidic group contained in the alkyl acid hydrophilic compound B2 is (0.5-1.0): 1.0, preferably (0.7-0.8): 1 ;

The diamine chain extender B7, the diamine chain extender B7, has a weight fraction of from 1 to 7, preferably from 3-5.

Preferably, the polyisocyanate A1 is selected from one or more of an aliphatic, alicyclic, and araliphatic diisocyanate having NCO functionality ≥ 2 and derivatives thereof; Dioxadione, isocyanurate, uretdione, carbamate, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, ureide and carbon a diisocyanate derivative of one or more of a diimine;

Preferably, the polyisocyanate A1 is selected from polyisocyanates having a functionality of ≥ 3, more preferably adducts of TDI with trimethylolpropane, HDI biurets, HDI trimers, IPDI trimers, TDI trimerization One or more of the bodies, further preferably an HDI trimer.

Examples of suitable polyisocyanates A1 are: 1,4-butane diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-trimethyl- 1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, bis(4,4'-isocyanatocyclohexyl) methane and/or its isomer , methyl isocyanate-1,8-octane diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI) and/or 2, 6-toluene diisocyanate (TDI), 1,3-bis(2-isocyanatopropan-2-yl)benzene (TMXDI) and 1,4-bis(2-isocyanatoprop-2-yl) Benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), 1,5-naphthalene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl Methane diisocyanate Acid ester, triphenylmethane-4,4',4"-triisocyanate; the polyisocyanate A1 may also have two or more -NCO groups based on the above-mentioned diisocyanate and have uretdione, isocyanide Derivatives of urate, carbamate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures.

Preferably, the diisocyanate B1 is selected from one or more of aliphatic, alicyclic, aromatic and araliphatic diisocyanates, preferably 1,6-hexamethylene diisocyanate (abbreviated as HDI), dicyclohexyl Methane diisocyanate (abbreviated as H ₁₂ MDI), isophorone diisocyanate (abbreviated as IPDI), toluene diisocyanate (abbreviated as TDI), and tetramethylxylene diisocyanate (abbreviated as TMXDI) or A variety, more preferably H ₁₂ MDI.

Preferably, in the alkyl acid hydrophilic compound B2, the active hydrogen reactive with the diisocyanate B1 is selected from a hydroxyl group and/or an amino group, and the hydrophilic acidic group is selected from a carboxyl group and/or a sulfone. Acid base

The alkyl acid hydrophilic compound B2 is preferably a monohydroxycarboxylic acid, a dihydroxycarboxylic acid, a monoaminocarboxylic acid, a diaminocarboxylic acid, a monohydroxysulfonic acid, a dihydroxysulfonic acid, a monoaminosulfonic acid or a diaminosulfonic acid. One or more; further preferably dimethylolpropionic acid, dimethylolbutanoic acid, hydroxypivalic acid, N-(2-aminoethyl)-β-alanine, 2-(2-amino group Ethylamino)ethanesulfonic acid, ethylenediaminepropylsulfonic acid, ethylenediaminebutylsulfonic acid, 1,2-propylenediamine-β-ethanesulfonic acid, 1,3-propanediamine-β-ethanesulfonate One or more of acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine and 3,5-diaminobenzoic acid, more preferably dimethylol Propionic acid and/or dimethylolbutanoic acid.

The carboxyl group or the sulfonic acid functional group in the alkyl acid hydrophilic compound B2 is neutralized by a neutralizing agent to become a hydrophilic carboxylate or a sulfonate ion, thereby imparting water dispersibility to the polyurethane polymer B, and making the polyurethane polymer B It acts as an emulsifier in the emulsification and dispersion process. The electric double layer structure formed by the carboxylate or sulfonate ion on the surface of the emulsion particles causes the urethane acrylate oligomer A to be encapsulated in the middle of the emulsion particles to form a stable dispersion.

Preferably, the small molecule polyols A3 and B3 may comprise an aliphatic, alicyclic or aromatic group; the small molecule polyols A3 and B3 are polyols having a carbon number of ≤20.

Preferably, the small molecule polyols A3 and B3 are independently selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,4-butanediol. (abbreviated as BDO), 1,3-butanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentane Glycol (abbreviated as NPG), hydroquinone dihydroxyethyl ether, bisphenol A (short for 2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-di(4-) Abbreviation for hydroxycyclohexyl)propane), trimethylolpropane, glycerol, pentaerythritol, α-hydroxybutyl-ε-hydroxycaproate, ω-hydroxyhexyl-γ-hydroxybutyrate, adipic acid One or more of (β-hydroxyethyl) ester and bis(β-hydroxyethyl) terephthalate; preferably a binary and/or trihydric alcohol such as 1,2-propanediol, 1,3 -propylene glycol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, glycerol, trimethylolpropane and 1,4 One or more of cyclohexanedimethanol; further preferably neopentyl glycol (abbreviated as NPG).

Preferably, in the polymer polyol B4, the polyether diol is one or more selected from the group consisting of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether diol, preferably polyhexamethylene adipate Alcohol ester diol, polyadipate neopentyl glycol hexanediol ester diol, polybutylene adipate diol, polyadipate diethylene glycol diol, polyhexan Acid neopentyl glycol ester diol, polycarbonate diol, polyhexylene phthalate diol, polypentylene glycol phthalate diol, polycaprolactone binary One or more of an alcohol and a hydroxyl-containing polyacrylate diol;

Preferably, the polymer polyol B4 is selected from one of a polytetrahydrofuran ether glycol having a weight average molecular weight of 1000-2000 and a polypentylene glycol diol glycol having a weight average molecular weight of 1000-2000 or a plurality of; further preferably, the polymer polyol B4 is a combination of a polytetrahydrofuran ether glycol and a polyadipyl glycol adipate diol in a weight ratio of 1:4 to 4:1. The mixture is preferably 1:1 by weight.

Preferably, the acrylate and/or methacrylate compounds A2 and B5 both contain 1-2 hydroxyl groups and 1-10 acrylate groups and/or methacrylate groups;

Preferably, the acrylate and/or methacrylate compounds A2 and B5 are obtained by reacting acrylic acid and/or methacrylic acid with a binary, ternary, polyhydric or epoxy compound and containing 1-2 hydroxyl groups and a product of from 1 to 10 acrylate groups and/or methacrylate groups;

Preferably, the A2 and B5 are each independently selected from the group consisting of hydroxyethyl acrylate (abbreviated as HEA), hydroxyethyl methacrylate (abbreviated as HEMA), hydroxypropyl acrylate (abbreviated as HPA), glycidyl tert-carbonate. Acrylate, 1,3-butylene glycol acrylate, 1,3-butylene glycol methacrylate, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl acrylate Glycol ester, neopentyl glycol methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol A glycidyl diacrylate, bisphenol A dimethyl Glycidyl acrylate, ethylene oxide modified bisphenol A glycidyl diacrylate, ethylene oxide modified bisphenol A glycidyl dimethacrylate, trimethylolethane diacrylate, three Hydroxymethylethane dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol triacrylate, two One or more of pentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, and hydroxyl group-containing polyester acrylate oligomer Preferred; one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, glycidyl acrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate, and dipentaerythritol pentaacrylate One or more; pentaerythritol triacrylate is further preferred.

Preferably, the A2 and B5 are each independently selected from the group consisting of hydroxyethyl acrylate (abbreviated as HEA), hydroxyethyl methacrylate (abbreviated as HEMA), hydroxypropyl acrylate (abbreviated as HPA), glycidyl tert-carbonate. One or more of acrylate, pentaerythritol triacrylate (abbreviated as PETA), trimethylolpropane diacrylate, and dipentaerythritol pentaacrylate.

Preferably, the -NCO group in the diisocyanate B1 and the alkyl acid hydrophilic compound B2, the optional small molecule polyol B3, the polymer polyol B4 and optionally the acrylate and/or methyl group The molar ratio of the total amount of active hydrogen which can react with the diisocyanate B1 in the acrylate compound B5 is (1.1 - 1.8): 1, preferably (1.2 - 1.5): 1.

Preferably, the neutralizing agent B6 is selected from the group consisting of organic tertiary amines or inorganic bases, including trimethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N- Phenyldiethanolamine, diethylethanolamine, N-methylmorpholine, pyridine, triethylamine (abbreviated as TEA), N,N-dimethylethanolamine (abbreviated as DMEA), the inorganic bases including alkali metals The hydroxide, the alkali metal hydroxide comprises sodium hydroxide, potassium hydroxide; the neutralizer B6 is preferably triethylamine (abbreviated as TEA).

Preferably, the diamine chain extender B7 is selected from the group consisting of aliphatic and/or alicyclic diamines having from 2 to 10 carbon atoms, preferably ethylenediamine (abbreviated as EDA), propylenediamine, butadiamine One or more of 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, hexamethylenediamine and isophoronediamine (abbreviated as IPDA), further preferably different Buddha Ketone diamine (abbreviated as IPDA).

A method of preparing the above composition comprising the steps of:

(1) reacting the polyisocyanate A1, the acrylate and/or methacrylate compound A2 and the optional small molecule polyol A3, and after complete reaction, obtaining an acrylate and/or methacrylate-terminated urethane acrylate Oligomer A;

(2) reacting a diisocyanate B1, an alkyl acid hydrophilic compound B2, an optional small molecule polyol B3, a polymer polyol B4, and an optional acrylate and/or methacrylate compound B5, after complete reaction Obtaining an NCO-terminated water-dispersed polyurethane prepolymer;

(3) mixing the urethane acrylate oligomer A obtained in the step (1) and the water-dispersed polyurethane prepolymer obtained in the step (2), and neutralizing the obtained mixture with a neutralizing agent B6, and dispersing with water. After the addition of the diamine chain extender B7, the chain extension is carried out to obtain an aqueous dispersion of a mixture of the urethane acrylate oligomer A and the water-dispersible polyurethane polymer B, that is, an aqueous dispersion of the composition is obtained.

Preferably, the step of subjecting the obtained aqueous dispersion of the composition to vacuum evaporation to remove the solvent is further included; preferably, the temperature of the vacuum evaporation is from 30 to 60 ° C, preferably from 40 to 50 ° C.

Preferably, the molar ratio of the diamine chain extender B7 to the terminal NCO group of the water-dispersible polyurethane prepolymer obtained in the step (2) is from 0.3 to 1.0:1, preferably from 0.85 to 0.95:1.

Preferably, a catalyst is optionally added in the step (1) and the step (2), and the catalyst is preferably used for a urethanated phosphonium salt (III) catalyst, further preferably ruthenium bromide, ruthenium chloride, phosphoric acid铋, barium acetate, barium neodymium citrate, barium octoate, barium salicylate, barium ethylhexanoate, barium naphthenate or barium citrate, further preferably barium ethylhexanoate; the amount of the catalyst is 0.01-0.5 Wt%, in the step (1), the amount is based on the weight of the polyisocyanate A1, which is used in the step (2) based on the weight of the diisocyanate B1.

The method of preparing a composition of the present invention can also be carried out as follows:

The polyisocyanate A1, the acrylate and/or methacrylate compound A2 and the optional small molecule polyol A3 are reacted, and after complete reaction, an acrylate and/or methacrylate terminated urethane acrylate oligomer is obtained. A; continuing to add thereto a diisocyanate B1, an alkyl acid hydrophilic compound B2, an optional small molecule polyol B3, a polymer polyol B4, and optionally an acrylate and/or methacrylate compound B5, completely reacted Thereafter, neutralizing agent B6 is added thereto, and then water is dispersed, and then diamine chain extender B7 is added, followed by chain extension to obtain water dispersion of a mixture of urethane acrylate oligomer A and water-dispersed polyurethane polymer B. The aqueous dispersion of the composition is obtained.

Preferably, the step of subjecting the obtained aqueous dispersion of the composition to vacuum evaporation to remove the solvent is further included; preferably, the temperature of the vacuum evaporation is from 30 to 60 ° C, preferably from 40 to 50 ° C.

Preferably, during the preparation, a catalyst is added while adding the polyisocyanate A1, the acrylate and/or the methacrylate compound A2 and the optional small molecule polyol A3, and the catalyst is preferably used for urethanization. The cerium salt (III) catalyst is further preferably cerium bromide, cerium chloride, cerium phosphate, cerium acetate, cerium neodecanoate, cerium octoate, cerium salicylate, cerium ethyl hexanoate, cerium naphthenate or citric acid. Further, hydrazine ethylhexanoate is further preferred; the catalyst is used in an amount of from 0.01 to 0.5% by weight based on the weight of the polyisocyanate A1.

Preferably, during the preparation, a diisocyanate B1, an alkyl acid hydrophilic compound B2, an optional small molecule polyol B3, a polymer polyol B4 and optionally an acrylate and/or methacrylate compound B5 are added. At the same time, a catalyst is added, and the catalyst is preferably used for a urethanated phosphonium salt (III) catalyst, and further preferably ruthenium bromide, ruthenium chloride, ruthenium phosphate, ruthenium acetate, ruthenium neodecanoate, bismuth octoate, water Barium sulphate, barium ethylhexanoate, barium naphthenate or barium citrate, further preferably barium ethylhexanoate; the catalyst is used in an amount of from 0.01 to 0.5% by weight, based on the weight of the diisocyanate B1.

In the above two preparation methods, preferably, the reaction temperature of the reaction of A1, A2 and A3 is 60-90 ° C, preferably 70-80 ° C;

Preferably, the reaction temperature of the reaction of B1, B2, B3, B4 and B5 is 60-90 ° C, preferably 70-80 ° C;

Preferably, the reaction temperature of the acrylate and / or methacrylate-terminated urethane acrylate oligomer A with B1, B2, B3, B4 and B5 is 60-90 ° C, preferably 70-80 ° C;

Preferably, the neutralization reaction temperature is 30-60 ° C, preferably 35-45 ° C;

Preferably, the chain extension reaction temperature is 30-50 ° C, preferably 35-40 ° C;

Preferably, a volatile organic solvent such as acetone, methyl ethyl ketone or the like is preferably added to the reaction system, preferably acetone.

The addition of an organic solvent can lower the viscosity of the reaction system.

Preferably, a polymerization inhibitor is further added during the preparation, and the polymerization inhibitor is selected from the group consisting of a phenolic polymerization inhibitor and an anthraquinone polymerization inhibitor, and further preferably hydroquinone, p-benzoquinone, methylhydroquinone, and para Oxyphenol, 2-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, more preferably p-methoxyphenol, the polymerization inhibitor is used in an amount based on the urethane acrylate combination The total weight of the material is from 0.01 to 0.2% by weight, preferably from 0.02 to 0.05% by weight.

The addition of a polymerization inhibitor reduces the self-polymerization of the acrylate compound at the reaction temperature.

Preferably, the composition has a particle size of from 60 to 300 nm, preferably from 80 to 180 nm. The pH is 7.5-9 and the viscosity is 10-500 cps, preferably 10-200 cps.

An aqueous coating comprising the following parts by weight:

The composition is the above composition or the composition obtained according to the above production method.

The leveling agent can be any leveling agent known to those skilled in the art, such as BYK-348 from BYK Chemicals.

The antifoaming agent may be any defoaming agent known to those skilled in the art, such as BYK-028 from BYK Chemical Co., Ltd.

The thickener is selected from the group consisting of polyurethane associative thickeners and/or alkali-swellable associative thickeners, preferably polyurethane associative thickeners, such as VesmodyTM U604 from Wanhua Chemical Group Co., Ltd., based on the amount Construction viscosity requirements are adjusted.

The matting agent includes, but is not limited to, silica, diatomaceous earth, talc, etc., such as Evonik Industries Group's Ts-100, and the amount of the matting agent can be adjusted based on the gloss requirements of the coating.

The photoinitiator may be any photoinitiator known to those skilled in the art, including but not limited to photocleavage type, dehydrogenation type free radical initiators, such as acetophenone, alpha, alpha-dimethoxy- --phenylacetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, aroylphosphine oxide, bisbenzoylphenylphosphine oxide benzophenone, benzophenone Ingredient ethyl ether, benzoin isopropyl ether, hydroxyisobutyl benzophenone, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, etc., preferably parts by weight A mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone in a ratio of 1:1. The photoinitiator includes, but is not limited to, BASF's Irgcure 500.

The beneficial effects of the invention are:

(1) Commonly used water-based radiation-curable urethane acrylate resins and coatings are generally alkaline due to their synthetic process characteristics, and the molecular weight of the resin is small. Under alkaline conditions, small molecule acrylate compounds are easily hydrolyzed, resulting in sustained pH. Decreased, and the change of pH causes the hydrophilicity of the aqueous resin particles to change. Under the action of the thickener, the viscosity also changes greatly, which affects the construction of the coating, and even after the long-term storage, the coating gels and is scrapped. In addition, the commonly used aqueous radiation-curable urethane acrylate resin synthesis process results in a smaller molecular weight, the matting effect is poor after the addition of the matting agent, the gloss of the coating after construction is high, and the matting agent is unevenly arranged, and the appearance effect is also Poor; the composition of the present invention introduces an acrylate radiation curing group through the A component to ensure the content of the radiation curing group of the resin to ensure better performance of the coating, such as higher hardness and better chemical resistance. The B component is obtained by a post-chain extension process to obtain a large molecular weight substance, while passing through a raw material formulation such as an aqueous group content and neutralization thereof. Control Optimization of pH of the resin is controlled, so that the degree of hydrolysis of the acrylate compound is greatly reduced, and because the presence of large molecular weight species, the matting agent added may be arranged uniformly in the coating layer, the glossiness is also greatly reduced;

(2) The aqueous radiation-curable urethane acrylate composition of the present invention has a pH of 7.5-9, a viscosity of 10-500 cps, and is stored at 25 ° C for 20 days, and the pH value is less than 10% lower than the initial value, and the viscosity is The value changes by less than 10% from the initial value, and stored at 50 ° C for 20 days, the pH value is less than 20% lower than the initial value, the viscosity value is less than 50% than the initial value, and the stability is improved in a higher temperature environment;

(3) The coating obtained from the above composition is stored at 25 ° C for 20 days, the viscosity value and the pH value are changed by less than 10% from the initial value, and stored at 50 ° C for 20 days, the pH value is reduced by less than 20% from the initial value. The viscosity value changes less than 50% from the initial value;

(4) After the radiation curing of the coating of the invention, the coating has good matting performance, high extinction efficiency, 60° glossiness after curing is less than 40, low gloss, delicate appearance and beautiful appearance, and can be widely applied to wood furniture, floor and cabinet. And other fields.

The word "optional" as used in this application has the meaning of "contains" or "does not contain".

detailed description

The technical solutions of the present invention and the effects thereof will be further described below through specific embodiments. The following examples are merely illustrative of the invention and are not intended to limit the scope of the invention. Simple modifications of the invention are possible within the scope of the invention as claimed.

In the following examples and comparative examples, the sources of the main raw materials are as follows:

H ₁₂ MDI, HDI, IPDI, HDI trimer, IPDA, Wanhua Chemical Group Co., Ltd., industrial products;

HDI biuret, Asahi Kasei, industrial products;

IPDI trimer, Evonik, industrial products;

PNA1000 (weight average molecular weight 1000), PNA2000 (weight average molecular weight 2000), polyadipate neopentyl glycol diol, Qingdao Yutian, industrial products;

PBA1000 (weight average molecular weight 1000), polybutylene adipate diol, Huada Chemical, industrial products;

PTMEG1000 (weight average molecular weight 1000), polytetrahydrofuran ether glycol, Shanxi three-dimensional, industrial products;

Hydroxyethyl methacrylate (HEMA), Shanghai Huayi, industrial products;

Hydroxyethyl acrylate (HEA), Shanghai Huayi, industrial products;

Pentaerythritol triacrylate (PETA), Yantai Houde, industrial products;

Dimethylolpropionic acid (DMPA), Perstorp, Sweden, industrial product.

testing method:

The viscosity test tool is a Brookfield Rotational Viscometer S61 rotor with a viscosity unit of cps.

Tolerance test standard: Tested in accordance with HG/T 38280.

Test - NCO group method: test by potentiometric titration, take the sample containing -NCO group, add chlorobenzene solvent to dissolve, add quantitative di-n-butylamine and react with residual -NCO group in the sample, and then use quantitative quenching The remaining di-n-butylamine was neutralized by titration of the hydrochloric acid solution, and the end point of the titration reaction was determined by a potential method to determine the amount of the diluted hydrochloric acid, and the content of the residual-NCO group was calculated by the amount of di-n-butylamine and the amount of the titrated hydrochloric acid.

Example 1

In a 2000 ml four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermocouple, 90 g of HDI trimer (A1), 90 g of PETA (A2), 20 g of HEA (A2) and 5 g of NPG (A3), and 0.2 g were added. The ruthenium ethylhexanoate catalyst and 0.15 g of the polymerization inhibitor p-methoxyphenol were reacted at 80 ° C for 2 hours, and after the content of the -NCO group was 0.05 wt%, the reaction was completed, and 160 g of H ₁₂ MDI was further added thereto. B1), 100g PNA1000 (B4), 30g DMPA (B2), 10g NPG (B3) and 30g PETA (B5), while adding 50g of acetone to reduce the reaction viscosity, after reacting at 80 ° C for 2 hours, start sampling test reaction system -NCO group content, until the -NCO group content is 2.2wt% to stop the reaction, adding 200g of acetone to cool down to the temperature of the reaction system reaches 40 ° C, 17.5g of triethylamine (B6) is added to the reaction system, stirring and neutralization After 5 minutes, 840 g of water was added to carry out dispersion emulsification to obtain a milky white emulsion, and 24 g of IPDA (B7) was added to the emulsion to continue stirring for 5 minutes, and the emulsion was removed by a rotary evaporator to obtain a 1# emulsion having a solid content of 40% by weight. The emulsion had a particle size of 110 nm. 1# Emulsion is an aqueous dispersion of the composition prepared in this example.

Example 2

In a 1000 ml four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermocouple, 120 g of IPDI trimer (A1) and 350 g of PETA (A2), and 0.4 g of ruthenium octylate metal catalyst and 0.15 g of a polymerization inhibitor were added. The oxyphenol was reacted at 80 ° C for 2 hours, and after the content of the -NCO group was 0.05 wt%, the reaction was completed to obtain a urethane acrylate oligomer A for use. Another 46 g of HDI (B1), 50 g of PBA 1000 (B4), 100 g of PNA2000 (B4), 16.8 g of DMPA (B2), and 30 g of acetone were reacted at 80 ° C for 2 hours, and sampling was started to test the -NCO group in the reaction system. The content was stopped until the content of the -NCO group was 1.7 wt%, and the residual urethane acrylate oligomer A was uniformly mixed, and 200 g of acetone was added to cool down to a temperature of 40 ° C, and 12.6 g of triethylamine was added. (B6) was added to the reaction system, and after stirring for 5 minutes, 1050 g of water was further added to carry out dispersion emulsification to obtain a milky white emulsion, and 4.5 g of IPDA (B7) was added to the emulsion, stirring was continued for 5 minutes, and the emulsion was removed by a rotary evaporator. A 2# emulsion having a solid content of 40% by weight was obtained, and the test emulsion had a particle diameter of 180 nm. 2# Emulsion is an aqueous dispersion of the composition prepared in this example.

Example 3

In a 2000 ml four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermocouple, 97.2 g of HDI biuret (A1), 52.5 g of HEMA (A2), and 7.6 g of BDO (A3), and 0.13 g of ruthenium acid catalyst were added. And 0.1 g of the polymerization inhibitor p-methoxyphenol, reacted at 80 ° C for 2 hours, After the test-NCO group content was 0.05% by weight, the reaction was completed, and 195 g of IPDI (B1), 190 g of PNA1000 (B4), 26.5 g of DMPA (B2), and 175 g of PETA (B5) were continuously added thereto, and at the same time, in order to lower the reaction viscosity, 50g of acetone, after reacting at 80 ° C for 2 hours, began sampling to test the content of -NCO groups in the reaction system until the content of -NCO groups was 2.9 wt% to stop the reaction, adding 200 g of acetone to cool down until the temperature of the reaction system reached At 40 ° C, 14 g of triethylamine (B6) was added to the reaction system, and after stirring for 5 minutes, 1080 g of water was added to carry out dispersion emulsification to obtain a milky white emulsion, and 8.3 g of ethylenediamine (EDA) (B7) was added to the emulsion to continue. After stirring for 15 minutes, the emulsion was removed from the acetone by a rotary evaporator to obtain a 3# emulsion having a solid content of 40% by weight, and the test emulsion had a particle diameter of 150 nm. 3# Emulsion is an aqueous dispersion of the composition prepared in this example.

Example 4

In a 2000 ml four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermocouple, 90 g of HDI trimer (A1), 90 g of PETA (A2), 20 g of HEA (A2), and 5 g of NPG (A3), and 0.2 g were added. The ruthenium ethylhexanoate catalyst and 0.15 g of the polymerization inhibitor p-methoxyphenol were reacted at 80 ° C for 2 hours, and after the content of the -NCO group was 0.05 wt%, the reaction was completed, and 102.5 g of HDI (B1) was continuously added thereto. ), 40g PNA1000 (B4), 40g PTMEG1000 (B4), 33.2g DMPA (B2) and 26g 1,4-cyclohexanedimethanol (CHDM) (B3), while adding 50g of acetone to reduce the reaction viscosity, at 80 ° C After the next reaction for 2 hours, the content of the -NCO group in the reaction system was started to be sampled until the content of the -NCO group was 1.8 wt%, the reaction was stopped, and 200 g of acetone was added to cool down until the temperature of the reaction system reached 40 ° C, which was 12.5 g. Ethylamine (TEA) (B6) was added to the reaction system, and after stirring for 5 minutes, 690 g of water was added to carry out dispersion emulsification to obtain a milky white emulsion, and 14 g of IPDA (B7) was added to the emulsion to continue stirring for 5 minutes, and the emulsion was subjected to rotary evaporation. The acetone was removed to obtain a 4# emulsion having a solid content of 40% by weight, and the particle size of the test emulsion was 110 nm. 4# Emulsion is an aqueous dispersion of the composition prepared in this example.

Comparative example 1

In a 2000 ml four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermocouple, 100 g of H ₁₂ MDI (B1), 150 g of PNA 1000 (B4), 10 g of DMPA (B2), 3.1 g of NPG (B3), and 30 g of diluted acetone were added. And 0.15 g of ruthenium hexanoate catalyst, sampled at 80 ° C for 1 hour, and sampled until the content of -NCO group was 3.6 wt%, and then added 120 g of PETA (B5), 0.3 g of ruthenium hexanoate catalyst and 0.15 g. The polymerization inhibitor p-methoxyphenol, after reacting at 80 ° C for 3 hours, began sampling to test the content of -NCO groups in the reaction system until the content of -NCO groups was about 0.1 wt% to stop the reaction, and 200 g of acetone was added. The temperature was lowered until the temperature of the reaction system reached 40 ° C. 7.5 g of triethylamine (TEA) (B6) was added to the reaction system, and after stirring for 5 minutes, 575 g of water was further added to carry out dispersion emulsification to obtain a translucent emulsion, and the emulsion was rotated. The acetone was removed from the evaporator to obtain a 5# emulsion having a solid content of about 40%, and the particle diameter of the emulsion was measured to be 70 nm. 1# Emulsion is an aqueous dispersion of the composition prepared in the comparative example.

The pH value and viscosity change of the 1-5# emulsion obtained from each of Examples 1-4 and Comparative Example 1 at 25 ° C are shown in Table 1; the pH value of the emulsion of 1 to 5 # emulsion at 50 ° C and The viscosity changes are shown in Table 2.

Table 1 pH and viscosity of emulsion when stored at 25 ° C

It can be seen from Table 1 that the 1~5# emulsion is stored at room temperature 25 ° C. Due to the relatively low temperature, the various compounds in each emulsion are relatively stable, and the pH value and viscosity are relatively stable. Therefore, there was no significant difference in emulsion stability and viscosity change of the emulsions of Examples 1 to 4 of the present invention and Comparative Example 1 under storage conditions of 25 ° C, that is, the composition of the present invention and the composition obtained in Comparative Example 1, There is no significant difference in the stability of the person.

Among them, the emulsion, that is, the aqueous dispersion of the composition.

Table 2 pH and viscosity of emulsion when stored at 50 ° C

It can be seen from Table 2 that under higher storage temperature and alkaline environment, the hydrolysis of ester compounds such as acrylate into acrylic acid in the emulsion leads to a decrease in pH, which leads to a decrease in the ionization degree of hydrophilic acidic groups, and an electric double layer of emulsion particles. The thickness becomes small, and the viscosity of the emulsion also slightly decreases because no thickener is added. However, as can be seen from Table 2, under the storage conditions of 50 ° C, the emulsions of Examples 1-4 of the present invention have a relatively slow decline in pH and viscosity compared to the emulsion of Comparative Example 1, ie, with Comparative Example 1 The stability of the composition of the invention is slightly improved compared to the resulting composition. Among them, the emulsion, that is, the aqueous dispersion of the composition.

In summary, the composition prepared by the present invention, although stable at room temperature of 25 ° C, has no significant difference with respect to the stability of the composition of Comparative Example 1, but at a higher temperature of 50 ° C, its stability is relative to the pair. The stability of the composition of the ratio 1 was slightly improved, which indicates that the composition prepared by the present invention is more resistant to high temperature environments than the composition of Comparative Example 1, and has a slightly better stability at higher temperature environments.

Coating preparation

1 to 5# emulsions were prepared according to the formulation shown in Table 3 according to the conventional method.

Table 3 paint formula

raw material name	Parts by weight
Emulsion	78.00
BYK-028	0.30
BYK-348	0.30
Deionized water	19.0
Ts-100	0.7
Vesmody TM U604	0.80
Irgcure 500	0.90
total	100.00

The pH and viscosity changes of the 1~5# coatings stored at 25 °C are shown in Table 4. The pH and viscosity changes of the 1~5# coatings stored at 50 °C are shown in Table 5.

Table 4 pH and viscosity of coatings stored at 25 ° C

It can be seen from Table 4 that the coating material is relatively stable due to the low storage temperature, and its pH value and viscosity are relatively stable. There were no significant differences in the stability and viscosity changes of the coatings obtained from the emulsions of Examples 1-4 and Comparative Example 1 of the present invention.

Table 5 pH and viscosity at 50 ° C storage

It can be seen from Table 5 that the storage temperature is high, and the polyfunctional free acrylate in the coating is hydrolyzed in a high-temperature alkaline environment, and the acrylic acid content in the coating system is greatly increased, resulting in a decrease in pH, resulting in a decrease in the ionization degree of the hydrophilic compound, and the surface of the emulsion particles. The hydrophobicity of the associative thickener increases the association of emulsion particles in the coating system, resulting in an increase in the viscosity of the coating. In the coating materials of Examples 1-4, the tendency of the pH value to decrease was small, and the viscosity increase tendency was also small; in the coating material of Comparative Example 1, the pH value decreased greatly, and the viscosity increase tendency was also large.

In summary, the coating of the present invention, although stable at room temperature of 25 ° C, has no significant difference with respect to the stability of the composition of Comparative Example 1, but at a higher temperature of 50 ° C, its stability is relative to Comparative Example 1 The stability of the composition was significantly improved, which indicates that the coating of the present invention is more resistant to high temperature environments than the coating of Comparative Example 1, and has a higher stability in higher temperature environments.

Coating performance test

The coating was coated on a glass plate with a 100 um bar coater, dried in an oven at 50 ° C for 15 minutes, irradiated with ultraviolet light, and the radiation intensity was 430 mJ/cm 2 . After the coating was cured, the pencil hardness was tested. And gloss;

Pencil hardness is a performance index reflecting the hardness and scratch resistance of the coating. The pencil hardness is tested according to the standard GB6379-86;

Gloss test: three-angle gloss meter, model MN268, purchased from Tianjin Qili Technology Co., Ltd.; spray two sprays on pine board with spray gun, the first spray amount is 85g/m2, after drying for 15 minutes in 50°C oven Irradiated by ultraviolet light, the radiation intensity is 430mJ/cm2. After the coating is solidified and cooled, it is sanded with 400 mesh sandpaper and washed and dried. The second spray is sprayed at 75g/m2 and dried in an oven at 50°C for 15 minutes. After curing with ultraviolet radiation, the radiation intensity was 430 mJ/cm2, and the chemical resistance of the prepared coating was tested, including ethanol resistance, acetic acid resistance and red wine resistance.

The coating performance test results are shown in Table 6.

Table 6 Coating performance test results

(Note: Tolerance test standard: HG/T 38280, alcohol resistance, acetic acid resistance and red wine resistance are applicable; chemical resistance test results are best 5 points, 1 point is the worst)

As can be seen from Table 6, the gloss of the coating of the present invention is remarkably lowered relative to the coating of Comparative Example 1, which fully demonstrates the post-chain extension process of the present invention using a diamine chain extender, which significantly increases the molecular weight of the substance in the system. Further, the arrangement of the matting agent is relatively uniform, and the low gloss of the coating material is further achieved. In Comparative Example 1, the end-capping process of the monohydroxy acrylate limits the increase of the molecular weight, and the arrangement of the matting agent is uneven, so the coating material The gloss is higher.

Claims (14)

1. An aqueous radiation curable urethane acrylate composition, characterized in that the composition comprises urethane acrylate oligomer A in a weight fraction of 20-80 and water-dispersed polyurethane polymer in a weight fraction of 20-80 Matter B;

   Wherein, the urethane acrylate oligomer A comprises the following raw materials:

   Polyisocyanate A1, the polyisocyanate A1 parts by weight of 25-75, preferably 41-55;

   Acrylate and/or methacrylate compound A2, said acrylate and/or methacrylate compound A2 comprising at least one active hydrogen reactive with said polyisocyanate A1 and at least one acrylate and/or The acrylate group, the acrylate and / or methacrylate compound A2 parts by weight of 25-75, preferably 41-55;

   Small molecule polyol A3, the small molecule polyol A3 has a molecular weight of 60-400, a hydroxyl functionality of 2-4, and a weight fraction of 0-6, preferably 2-4;

   The water-dispersible polyurethane polymer B comprises the following raw materials:

   Diisocyanate B1, the diisocyanate B1 parts by weight of 20-60, preferably 30-50;

   An alkyl acid hydrophilic compound B2 containing at least one active hydrogen reactive with isocyanate B1 and at least one hydrophilic acidic group, the weight of said alkyl acid hydrophilic compound B2 The number of parts is 3-15, preferably 5-10;

   Small molecule polyol B3, the small molecule polyol B3 has a molecular weight of 60-400, a hydroxyl functionality of 2-4, and a weight fraction of 0-10, preferably 2-5;

   a polymer polyol B4, the polymer polyol B4 being a polyester diol and/or a polyether diol having a weight average molecular weight of 400-4000, in parts by weight of 25-70, preferably 35-50;

   An acrylate and/or methacrylate compound B5 comprising at least one active hydrogen reactive with the diisocyanate B1 and at least one acrylate group and/or a methacrylate group, the acrylate and / or methacrylate compound B5 parts by weight of 0-30, preferably 5-15;

   The neutralizing agent B6, the molar ratio of the neutralizing agent B6 to the hydrophilic acidic group contained in the alkyl acid hydrophilic compound B2 is (0.5-1.0): 1.0, preferably (0.7-0.8): 1 ;

   The diamine chain extender B7, the diamine chain extender B7, has a weight fraction of from 1 to 7, preferably from 3-5.
2. The composition according to claim 1, wherein the polyisocyanate A1 is selected from one or more of aliphatic, alicyclic, aromatic and araliphatic diisocyanates and derivatives thereof; The derivative comprises iminooxadiazinedione, isocyanurate, uretdione, carbamate, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, a diisocyanate derivative of a ureide or carbodiimide structure; preferably a polyisocyanate having a functionality of -NCO groups of ≥ 3, more preferably an adduct of TDI with trimethylolpropane, HDI biuret, HDI trimerization One or more of a body, an IPDI trimer, and a TDI trimer, further preferably an HDI trimer.
3. The composition according to claim 1 or 2, characterized in that the diisocyanate B1 is selected from one or more of aliphatic, alicyclic, aromatic and araliphatic diisocyanates, preferably HDI, H One or more of ₁₂ MDI, IPDI, TDI and TMXDI, more preferably H ₁₂ MDI.
4. The composition according to any one of claims 1 to 3, wherein in the alkyl acid hydrophilic compound B2, the active hydrogen reactive with the diisocyanate B1 is selected from a hydroxyl group and/or An amino group, the hydrophilic acidic group being selected from a carboxyl group and/or a sulfonic acid group; and the alkyl acid hydrophilic compound B2 is preferably a monohydroxycarboxylic acid, a dihydroxycarboxylic acid, a monoaminocarboxylic acid, a diaminocarboxylic acid, One or more of monohydroxysulfonic acid, dihydroxysulfonic acid, monosulfamic acid, and diaminosulfonic acid; further preferably dimethylolpropionic acid, dimethylolbutanoic acid, hydroxypivalic acid, N- (2-Aminoethyl)-β-alanine, 2-(2-aminoethylamino)ethanesulfonic acid, ethylenediaminepropylsulfonic acid, ethylenediaminebutylsulfonic acid, 1,2-propane Amine-β-ethanesulfonic acid, 1,3-propanediamine-β-ethanesulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, and 3,5 One or more of di-aminobenzoic acid, still more preferably dimethylolpropionic acid and/or dimethylolbutanoic acid.
5. The composition according to any one of claims 1 to 4, wherein the small molecule polyols A3 and B3 are each independently selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and 1, 2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, new Pentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, glycerol, pentaerythritol, α-hydroxybutyl-ε-hydroxycaproate, ω-hydroxyhexyl -γ-hydroxybutyrate, bis(β-hydroxyethyl) adipate and p-phenylene One or more of bis(β-hydroxyethyl)carboxylate; preferably 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene One or more of an alcohol, 1,6-hexanediol, neopentyl glycol, glycerol, trimethylolpropane, and 1,4-cyclohexanedimethanol; further preferably neopentyl glycol.
6. The composition according to any one of claims 1 to 5, wherein in the polymer polyol B4, the polyether diol is selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetrahydrofuran ether One or more of the alcohols, preferably polyhexamethylene adipate diol, polyadipate neopentyl glycol hexanediol diol, polybutylene adipate diol , polydiethylene adipate diethylene glycol diol, polyadipate neopentyl glycol diol, polycarbonate diol, polyhexylene phthalate diol, polyortylene One or more of neopentyl glycol dicarboxylate diol, polycaprolactone diol, and hydroxyl group-containing polyacrylate diol; preferably, the polymer polyol B4 is selected from a weight average molecular weight of 1000 One or more of a polytetrahydrofuran ether diol of -2000 and a polypentylene glycol neoprene diol having a weight average molecular weight of from 1000 to 2000; further preferably, the polymer polyol B4 is a poly A mixture obtained by combining a tetrahydrofuran ether glycol and a poly(hexane) adipate diol in a weight ratio of 1:4 to 4:1, preferably in a ratio of 1:1 by weight.
7. The composition according to any one of claims 1 to 6, wherein the acrylate and/or methacrylate compounds A2 and B5 each contain 1-2 hydroxyl groups and 1-10 acrylates. And/or methacrylate groups; said A2 and B5 are each independently selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, glycidyl acrylate, 1,3-acrylic acid Butylene glycol ester, 1,3-butylene glycol methacrylate, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol acrylate, methacrylic acid Pentylene glycol ester, bisphenol A glycidyl diacrylate, bisphenol A glycidyl dimethacrylate, ethylene oxide modified bisphenol A glycidyl diacrylate, ethylene oxide modified bisphenol A glycidyl dimethacrylate, trimethylolethane diacrylate, glycerol diacrylate, glycerol dimethacrylate, trimethylolethane dimethacrylate, trishydroxyl Propane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, and hydroxyl group One or more of polyester acrylate oligomers; preferably C One of hydroxyethyl enoate, hydroxyethyl methacrylate, hydroxypropyl acrylate, glycidyl acrylate, pentaerythritol triacrylate, trimethylolpropane diacrylate, and dipentaerythritol pentaacrylate or A variety; more preferably pentaerythritol triacrylate.
8. The composition according to any one of claims 1 to 7, wherein the -NCO group in the diisocyanate B1 and the alkyl acid hydrophilic compound B2, optionally the small molecule polyol B3 The molar ratio of the total amount of active hydrogen which can react with the diisocyanate B1 in the polymer polyol B4 and the optional acrylate and/or methacrylate compound B5 is (1.1-1.8): 1, preferably (1.2-1.5): 1.
9. The composition according to any one of claims 1 to 8, wherein the neutralizing agent B6 is selected from the group consisting of organic tertiary amines or inorganic base compounds; the organic tertiary amine compound is preferably trimethylamine, three Isopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, diethylethanolamine, N-methylmorpholine, pyridine, triethylamine and N,N-dimethylethanolamine One or more of them; the inorganic base compound is preferably an alkali metal hydroxide, and the alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide.
10. The composition according to any one of claims 1 to 9, wherein the diamine chain extender B7 is selected from the group consisting of aliphatic and/or alicyclic diamines having 2 to 10 carbon atoms. Preference is given to one of ethylenediamine, propylenediamine, butanediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, hexamethylenediamine and isophoronediamine or A variety of, further preferred is isophorone diamine.
11. A method of preparing a composition according to any one of claims 1 to 10, characterized in that it comprises the steps of:

    (1) reacting the polyisocyanate A1, the acrylate and/or methacrylate compound A2 and the optional small molecule polyol A3, and after complete reaction, obtaining an acrylate and/or methacrylate-terminated urethane acrylate Oligomer A;

    (2) reacting a diisocyanate B1, an alkyl acid hydrophilic compound B2, an optional small molecule polyol B3, a polymer polyol B4, and an optional acrylate and/or methacrylate compound B5, after complete reaction a prepolymer of a water-dispersible polyurethane terminated with a -NCO group;

    (3) mixing the urethane acrylate oligomer A obtained in the step (1) and the prepolymer of the water-dispersible polyurethane obtained in the step (2), and adding a neutralizing agent B6 to the obtained mixture for neutralization. After adding water and dispersing, adding a diamine chain extender B7 for chain extension, An aqueous dispersion of a mixture of urethane acrylate oligomer A and water-dispersible polyurethane polymer B, ie an aqueous dispersion of the composition; or

    (I) reacting the polyisocyanate A1, the acrylate and/or methacrylate compound A2 and the optional small molecule polyol A3, and after complete reaction, obtaining an acrylate and/or methacrylate terminated urethane acrylate Oligomer A;

    (II) continuing to add to the oligomer A a diisocyanate B1, an alkyl acid hydrophilic compound B2, an optional small molecule polyol B3, a polymer polyol B4, and optionally an acrylate and/or methyl group. After the acrylate compound B5 is completely reacted, the neutralizer B6 is added thereto for neutralization, and after water dispersion, the diamine chain extender B7 is added for chain extension to obtain a urethane acrylate oligomer A and a water-dispersed polyurethane polymerization. An aqueous dispersion of the mixture of B, i.e., an aqueous dispersion of the composition.
12. The method according to claim 11, wherein the molar ratio of the diamine chain extender B7 to the terminal-NCO group of the water-dispersed polyurethane prepolymer obtained in the step (2) is (0.3-1.0). ): 1, preferably (0.85 - 0.95): 1.
13. The method according to claim 11 or 12, wherein the composition has a particle diameter of 60 to 300 nm, preferably 80 to 180 nm; a pH of 7.5 to 9 and a viscosity of 10 to 500 cps.
14. An aqueous coating characterized in that the coating comprises the following parts by weight:

    

    Wherein the composition is a composition according to any one of claims 1 to 10 or a composition obtained according to the production method according to any one of claims 11 to 13.