Epoxy modified light-cured polyacrylate dispersion as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of coatings, and discloses an epoxy modified light-cured polyacrylate dispersion as well as a preparation method and application thereof. The epoxy modified light-cured polyacrylate dispersion is prepared from the following raw materials: an acrylic monomer, an acrylate monomer, an initiator, an isocyanate monomer, hydroxyl vinyl ether, a bio-based material, a hydrophilic modifier, epoxy resin, an acrylamide monomer and a neutralizer. The solid content of the epoxy modified light-cured polyacrylate dispersion is 38 to 41 percent; the bio-based content of the epoxy modified light-cured polyacrylate dispersion is greater than or equal to 15%; the particle size of the epoxy modified light-cured polyacrylate dispersion is 1t; the wavelength is 110nm. A paint film of a water-based light-cured bio-based paint prepared from the epoxy modified light-cured polyacrylate dispersion has the characteristics of high flexibility, good chemical resistance, excellent adhesion to various substrates and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and particularly relates to an epoxy-modified light-cured polyacrylate dispersion and a preparation method and application thereof. Background Art

[0002] Water-based paints have gradually become the mainstream choice in the paint market due to their environmental protection, safety, excellent construction performance and wide applicability. Water-based paints mainly include water-based single-component paints, water-based two-component paints, and water-based light-curing paints that have developed rapidly in recent years. The film properties of single-component water-based paints, such as water resistance, chemical resistance and hardness, are quite different from those of solvent-based paints, which seriously limits the promotion and application of water-based paints. The mechanical properties, water resistance and chemical resistance of two-component water-based paints are close to those of solvent-based paints, but due to the problem of activation period, they are not suitable for reciprocating mechanical spraying and electrostatic spraying, and their drying speed is slow, which affects the construction efficiency. The film mechanical properties, water resistance and chemical resistance of water-based light-curing paints are better than those of solvent-based products. They are single-component packaging, ready to use after opening the barrel, and have no activation period. They are suitable for various mechanical spraying, and they can be packaged offline after drying for 0.5 to 2 hours after construction and curing with a UV curing machine. In the future, water-based light-curing paints will replace two-component water-based paints and become the first choice for high-end water-based paints. At present, the main products on the market are free radical photocurable polyurethane dispersions, which are mainly obtained by capping polyurethane prepolymers with hydroxyl-containing acrylic monomers. The capping process limits the molecular weight of the prepolymer, and the double bonds are only at both ends of the polymer. This process feature causes the products on the market to have problems such as poor storage stability and low reactivity. In addition, the paint film of free radical photocuring has a large shrinkage rate and poor adhesion to many substrates. The above shortcomings have greatly limited the promotion and application of water-based photocurable coatings, so they need to be developed.

[0003] Therefore, it is urgent to provide a water-based photocurable resin with good adhesion for developing water-based photocurable coatings. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes an epoxy-modified photocurable polyacrylate dispersion and a preparation method and application thereof. The present invention introduces a cationic photocurable system and an epoxy group into a photocurable water-based resin, reduces the shrinkage of the paint film, and improves the adhesion of the paint film to various substrates; the paint film of the water-based photocurable bio-based coating prepared in this way has the advantages of high gloss, high transparency, excellent water resistance and chemical resistance, high crosslinking density, high flexibility and excellent adhesion to various substrates.

[0005] The invention also provides an epoxy-modified light-cured polyacrylate dispersion.

[0006] The invention also provides a water-based bio-based photocurable coating.

[0007] The present invention also provides the use of water-based bio-based light-curing coating in the fields of wood product preparation, automobile manufacturing or metal product corrosion protection.

[0008] The first aspect of the present invention provides a method for preparing an epoxy-modified light-curable polyacrylate dispersion, the preparation method comprising the following steps:

[0009] S1. The acrylic acid monomer, the acrylate monomer, the vinyl monomer, and the initiator are mixed to obtain a mixed solution A;

[0010] S2. The diisocyanate and the hydroxy vinyl ether are mixed and reacted to obtain a prepolymer B containing a vinyl group and an isocyanate group;

[0011] S3: mixing the bio-based material and the hydrophilic modifier to obtain a hydrophilic modified bio-based material C;

[0012] S4. mixing the epoxy resin and the hydrophilic modifier to obtain a prepolymer D;

[0013] S5. The blocked cationic thermal initiator, the cationic photoinitiator and the free radical photoinitiator are mixed to form a mixture E;

[0014] S6. The hydrophilic modified bio-based material C, the polymerization inhibitor, the acrylamide monomer, the prepolymer B, the prepolymer D, the mixture E and the neutralizer are dispersed and reacted to obtain an epoxy-modified light-curable polyacrylate dispersion;

[0015] Wherein, the bio-based material is a plant oil containing three or more epoxy groups;

[0016] The hydrophilic modifier is a monomer containing a secondary amino group and a sulfonic acid group;

[0017] The epoxy resin is an epoxy resin containing three or more epoxy groups;

[0018] The neutralizing agent is a tertiary amine;

[0019] The hydrophilic modifiers in step S3 and step S4 are the same or different.

[0020] The embodiments according to the first aspect of the present invention have at least the following beneficial effects:

[0021] On one hand, the present invention provides an epoxy-modified photocurable polyacrylate dispersion and a preparation method thereof. A cationic photocurable system and an epoxy group are introduced into a photocurable water-based resin, thereby reducing the shrinkage rate of the paint film and improving the adhesion of the paint film to various substrates. The hydrophilic modified epoxy resin is mixed with a polyacrylate prepolymer and then dispersed together. Compared with the polyacrylate prepolymer, the modified epoxy resin has a smaller molecular weight and a lower viscosity, so the viscosity of the polyacrylate prepolymer can be reduced and the dispersion stability can be improved. The ratio of the secondary amine group generated by the reaction of the isocyanate group and the epoxy group of the epoxy resin is controlled to ensure the storage stability of the dispersion. The closed epoxy resin is added to the epoxy resin to form a polyacrylate prepolymer. The cationic thermal initiator, cationic photoinitiator and free radical photoinitiator are dispersed together with the resin to further improve the reaction degree of the photocurable group, thereby improving the resistance of the paint film; the addition of a blocked cationic thermal initiator can provide another curing method for the paint film while ensuring storage stability. In the present invention, both the epoxy resin and the polyacrylate resin are hydrophilically modified, which can make the two mixed more uniformly, thereby improving the performance of the paint film. If the epoxy resin is not hydrophilically modified, a core-shell structure will be formed, in which the shell layer is a hydrophilic polyacrylate and the core layer is an epoxy resin. The separation of the two phases will result in poor performance such as poor transparency of the paint film.

[0022] On the other hand, the present invention provides a water-based photocurable bio-based coating and a preparation method thereof. The paint film of the water-based photocurable bio-based coating has the advantages of high gloss, high transparency, excellent water resistance and chemical resistance, high crosslinking density, high flexibility and excellent adhesion to various substrates. It can be applied to high-end wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings.

[0023] In the present invention, the groups that can participate in photocuring include vinyl ether double bonds, acryloyloxy double bonds and epoxy groups. Free radical photoinitiators can initiate polymerization of acryloyloxy double bonds, and cationic photoinitiators can initiate polymerization of vinyl ether double bonds and epoxy groups. When the two types of photoinitiators are added at the same time, the above groups can copolymerize. The polymerization shrinkage rate initiated by free radical photoinitiators is large, oxygen inhibition is obvious, and the adhesion to many substrates is poor, while the polymerization shrinkage rate initiated by cationic photoinitiators is small, there is no oxygen inhibition, and its epoxy group has excellent adhesion to a variety of substrates, which can fully make up for the shortcomings of free radical photocuring.

[0024] In addition, conventional water-based photocurable coatings only add photoinitiators during the coating preparation stage, and this method has the disadvantage that the photocurable groups inside the latex particles cannot fully react. The present invention disperses the blocked cationic thermal initiator, cationic photoinitiator and free radical photoinitiator with the resin, and this part of the initiator can make the photocurable groups inside the latex particles react more fully. The initiator added during the coating preparation can initiate the polymerization of the photocurable groups at the interface of the latex particles, which can further improve the reaction degree of the photocurable groups, thereby improving the resistance of the paint film.

[0025] Third, the addition of a blocked cationic thermal initiator can provide another curing method for the paint film while ensuring storage stability. When the water-based light-curing paint is a solid color paint, ultraviolet rays cannot penetrate the paint film, resulting in the failure of the bottom layer of the paint film to cure. The paint film with a blocked cationic thermal initiator can cure the bottom layer of the paint film after baking. Some woods have a high oil content, such as pine. When baked, the oil will come out of the base material, causing defects such as blistering in the paint film. Since this type of oil contains double bonds and epoxy groups, the blocked cationic thermal initiator can cause the oil to cure during baking, thereby avoiding paint film defects.

[0026] In some embodiments of the present invention, the preparation method comprises the following steps:

[0027] S1. In parts by mass, 1.5 to 2.5 parts of acrylic acid monomer, 20 to 30 parts of acrylate monomer, 5 to 11 parts of vinyl monomer, and 0.4 to 0.6 parts of initiator are mixed to form a mixed solution A;

[0028] S2. In parts by mass, 8 to 15 parts of diisocyanate are heated to 50 to 70 ° C, and 5 to 9 parts of hydroxy vinyl ether are added dropwise, and the reaction is continued for 0.8 to 1.5 hours to obtain a prepolymer B containing a vinyl group and an isocyanate group;

[0029] S3. In parts by mass, 18 to 26 parts of the bio-based material are heated to 55 to 75° C., 5 to 6 parts of a hydrophilic modifier are added, and the reaction is performed to obtain a hydrophilic modified bio-based material C;

[0030] S4. In parts by mass, 10 to 25 parts of an epoxy resin and 10 to 15 parts of a hydrophilic modifier are mixed, the reaction temperature is controlled to be 40 to 45 ° C, and the reaction forms a prepolymer D;

[0031] S5. In parts by mass, 0.3 to 0.5 parts of a blocked cationic thermal initiator, 0.3 to 0.6 parts of a cationic photoinitiator and 0.3 to 0.5 parts of a free radical photoinitiator are mixed to form a mixture E;

[0032] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C is heated to 130-150°C, the mixed solution A is added dropwise within 3-4 hours. After the addition is completed, the mixture is stirred and kept warm for 20-40 minutes. The mixture is cooled to 60-80°C, 0.01 parts of polymerization inhibitor MEHQ are added, 6-10 parts of acrylamide monomer are added, the reaction is continued for 30-60 minutes, the mixture is cooled to 45-55°C, prepolymer B containing vinyl and isocyanate groups is added, the reaction is continued for 30-40 minutes, prepolymer D is added, the mixture is stirred for 5-10 minutes, 5-8 parts of neutralizer are added after stirring for 3-5 minutes, 180-210 parts of deionized water are added after stirring for 3-5 minutes, and the mixture is dispersed for 10-20 minutes. The epoxy-modified light-curing polyacrylate dispersion is obtained by filtering the material.

[0033] In some embodiments of the present invention, the preparation method comprises the following steps:

[0034] S1. In parts by mass, 1.5 to 2.5 parts of acrylic acid monomer, 20 to 30 parts of acrylate monomer, 5 to 11 parts of vinyl monomer, and 0.4 to 0.6 parts of initiator are mixed to form a mixed solution A;

[0035] S2. When 8 to 15 parts of diisocyanate are heated to 50 to 70°C, 5 to 9 parts of hydroxy vinyl ether are added dropwise at a constant pressure within 15 to 30 minutes, and the reaction is continued for 0.8 to 1.5 hours to obtain a prepolymer B containing vinyl and isocyanate groups;

[0036] S3. In parts by mass, 18 to 26 parts of the bio-based material are heated to 55 to 75° C., 5 to 6 parts of a hydrophilic modifier are added, and the reaction is carried out for 30 to 90 minutes to obtain a hydrophilic modified bio-based material C;

[0037] S4. In parts by mass, 10 to 25 parts of epoxy resin and 10 to 15 parts of a hydrophilic modifier are mixed, the reaction temperature is controlled to be 40 to 45 ° C, and the reaction is carried out for 1.5 to 2 hours to form a prepolymer D;

[0038] S5. In parts by mass, 0.3 to 0.5 parts of a blocked cationic thermal initiator, 0.3 to 0.6 parts of a cationic photoinitiator and 0.3 to 0.5 parts of a free radical photoinitiator are mixed to form a mixture E;

[0039] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C is heated to 130-150°C, the mixed solution A is added dropwise within 3-4 hours. After the addition is completed, the mixture is stirred and kept warm for 20-40 minutes. The mixture is cooled to 60-80°C, 0.01 parts of polymerization inhibitor MEHQ are added, 6-10 parts of acrylamide monomer are added, the reaction is continued for 30-60 minutes, the mixture is cooled to 45-55°C, prepolymer B containing vinyl and isocyanate groups is added, the reaction is continued for 30-40 minutes, prepolymer D is added, the mixture is stirred for 5-10 minutes, 5-8 parts of neutralizer are added after stirring for 3-5 minutes, 180-210 parts of deionized water are added after stirring for 3-5 minutes, and the mixture is dispersed for 10-20 minutes. The epoxy-modified light-curing polyacrylate dispersion is obtained by filtering the material.

[0040] In some embodiments of the present invention, the acrylic acid monomer includes acrylic acid AA or methacrylic acid MAA;

[0041] In some embodiments of the present invention, the acrylate monomer includes an acrylate monomer and a methacrylate monomer.

[0042] In some embodiments of the present invention, the methacrylate monomer includes at least one of methyl methacrylate MMA, butyl acrylate BA, isobornyl acrylate IBOA, cyclohexyl methacrylate CHMA, and benzyl methacrylate BZMA.

[0043] In some embodiments of the present invention, the vinyl monomer includes at least one of styrene St and vinyl acetate VAc.

[0044] In some embodiments of the present invention, the diisocyanate monomer includes at least one of isophorone diisocyanate IPDI, toluene diisocyanate TDI, hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI and 4,4'-dicyclohexylmethane diisocyanate HMDI.

[0045] In some embodiments of the present invention, the initiator includes at least one of di-tert-amyl peroxide and di-tert-butyl peroxide.

[0046] In some embodiments of the present invention, the hydroxy vinyl ether includes at least one of 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, and cyclohexyl-1,4-dimethanol monovinyl ether.

[0047] In some embodiments of the present invention, the epoxy resin includes at least one of tetraglycidyldiaminodimethylenebenzene, diglycidyl 4,5-epoxytetrahydrophthalate, and triglycidyl-p-aminophenol.

[0048] In some embodiments of the present invention, the bio-based material includes special epoxy soybean oil GreenSoft D, special epoxy soybean oil GreenSoft H and epoxy linseed oil. 9-5 TM At least one of .

[0049] In some embodiments of the present invention, the hydrophilic modifier includes at least one of cyclohexylaminoethanesulfonic acid CHES, cyclohexylaminopropanesulfonic acid CAPS and cyclohexylaminobutanesulfonic acid CABS.

[0050] In some embodiments of the present invention, the blocked cationic thermal initiator comprises a blocked phosphate cationic thermal initiator.

[0051] In some embodiments of the present invention, the blocked cationic thermal initiator includes at least one of Vicbase TC3631, CTI-100, CTI-200 and CTI-300.

[0052] In some embodiments of the present invention, the cationic photoinitiator includes at least one of HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976 and Omnirad250.

[0053] In some embodiments of the present invention, the free radical photoinitiator includes at least one of Darocur 1173, Irgacure 2959, Irgacure 500, Lucirin TPO-L, and Irgacure 819-DW.

[0054] In some embodiments of the present invention, the acrylamide-based monomer includes at least one of diacetone acrylamide (DAAM), N-butoxymethyl acrylamide and hydroxyethyl acrylamide.

[0055] In some embodiments of the present invention, the sulfonic acid group neutralizing agent includes at least one of triethylamine TEA and N,N-dimethylcyclohexylamine DMCHA.

[0056] The second aspect of the present invention provides an epoxy-modified light-curable polyacrylate dispersion, which is prepared by the preparation method. The epoxy-modified light-curable polyacrylate dispersion has a biobased content of ≥15%, a pH of 6-7, a particle size of <110nm, and a solid content of 38-41%.

[0057] The epoxy-modified polyacrylate dispersion of the invention has a bio-based content of ≥15%; a pH value of 6-7, and weak acidity is beneficial to improving the storage stability of the dispersion; a particle size of <110 nm can make the appearance of the dispersion achieve a semi-transparent effect, and the epoxy-modified light-curing polyacrylate dispersion prepared in this way has the characteristics of large molecular weight, high bio-based content, good storage stability, good appearance, high reaction activity, good resistance, excellent adhesion to various substrates, and the like; and the preparation method has the advantages of simple operation, easy control and low cost, and can prepare epoxy-modified light-curing polyacrylate dispersions in batches.

[0058] The third aspect of the present invention provides a water-based bio-based photocurable coating, the preparation raw materials of which include epoxy-modified photocurable polyacrylate dispersion.

[0059] In some embodiments of the present invention, the following raw materials are included in parts by weight:

[0060]

[0061] In some embodiments of the present invention, the following raw materials are included in parts by weight:

[0062]

[0063] In some embodiments of the present invention, the free radical photoinitiator includes at least one of Darocur 1173, Irgacure 2959, Irgacure 500, Lucirin TPO-L, and Irgacure 819-DW.

[0064] In some embodiments of the present invention, the cationic photoinitiator includes at least one of HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976 and Omnirad250.

[0065] In some embodiments of the present invention, the film-forming aid includes at least one of propylene glycol methyl ether PM, propylene glycol butyl ether PnB, dipropylene glycol methyl ether and DPM dipropylene glycol butyl ether DPnB.

[0066] In some embodiments of the present invention, the dispersant includes at least one of DISPERBYK-191 and DISPERS 755W.

[0067] In some embodiments of the present invention, the titanium dioxide includes at least one of NTR-606 and Ti-Pure R-902+.

[0068] In some embodiments of the present invention, the defoaming agent includes at least one of a polyether siloxane copolymer defoaming agent and a modified polysiloxane copolymer solution.

[0069] In some embodiments of the present invention, the polyether siloxane copolymer defoamer includes TEGO-800, TEGO-805, TEGO-815, and TEGO-825.

[0070] In some embodiments of the present invention, the modified polysiloxane copolymer solution includes at least one of BYK-019 and BYK-020.

[0071] In some embodiments of the present invention, the thickener includes at least one of a nonionic polyurethane associative thickener, a hydrophobically modified alkali-swellable associative thickener, an alkali-swellable non-associative thickener, and a nonionic associative thickener.

[0072] In some embodiments of the present invention, the nonionic polyurethane associative thickener comprises RM-8W.

[0073] In some embodiments of the present invention, the hydrophobically modified alkali-swellable associative thickener includes TT-935.

[0074] In some embodiments of the present invention, the alkali-swellable non-associative thickener comprises ASE-60.

[0075] In some embodiments of the present invention, the nonionic associative thickener includes at least one of TEGO ViscoPlus 3000, TEGO ViscoPlus 3030, and TEGO ViscoPlus 3060.

[0076] In some embodiments of the present invention, the wetting agent includes at least one of a polyether siloxane copolymer, a nonionic organic surfactant, and a polyether-modified polysiloxane solution.

[0077] In some embodiments of the present invention, the polyether siloxane copolymer includes TEGO-245.

[0078] In some embodiments of the present invention, the nonionic organic surfactant includes TEGO-500.

[0079] In some embodiments of the present invention, the polyether-modified polysiloxane solution includes BYK-346.

[0080] In some embodiments of the present invention, the preparation method of the water-based photocurable bio-based coating comprises premixing water and a film-forming aid, adding the premixed water and the film-forming aid to an epoxy-modified photocurable polyacrylate dispersion, and then sequentially adding a dispersant, titanium dioxide, a photoinitiator, a defoamer, a thickener and a wetting agent, dispersing for 10-30 minutes, and filtering to obtain a water-based photocurable bio-based coating.

[0081] The paint film of the water-based photocurable bio-based paint obtained by the present invention has the advantages of high gloss, high transparency, excellent water resistance and chemical resistance, high crosslinking density, good flexibility, excellent adhesion to various substrates, etc., and can be applied to high-end wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings.

[0082] A fourth aspect of the present invention provides an application of a water-based bio-based photocurable coating in the fields of wood product preparation, automobile manufacturing or metal product corrosion protection. DETAILED DESCRIPTION

[0083] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0084] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0085] The acrylic monomer used in the following examples is acrylic acid AA or methacrylic acid MAA from Sanmu Company;

[0086] The (meth)acrylate monomer is methyl methacrylate MMA, butyl acrylate BA, isobornyl acrylate IBOA, cyclohexyl methacrylate CHMA and / or benzyl methacrylate BZMA from Sanmu Company; the vinyl monomer is styrene St or vinyl acetate VAc from Sanmu Company;

[0087] The initiator is di-tert-amyl peroxide DTAP or di-tert-butyl peroxide DTBP from Jinjinle Company;

[0088] The diisocyanate monomers are isophorone diisocyanate IPDI, toluene diisocyanate TDI, hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI, and 4,4'-dicyclohexylmethane diisocyanate HMDI produced by Wanhua Company;

[0089] Hydroxy vinyl ethers are 4-hydroxybutyl vinyl ether HBVE, triethylene glycol divinyl ether DVE, and cyclohexyl-1,4-dimethanol monovinyl ether;

[0090] The bio-based materials are special epoxy soybean oil GreenSoft D, special epoxy soybean oil GreenSoft H, and epoxy linseed oil from Xingbang Polymer Materials Co., Ltd. 9-5 TM ;

[0091] The hydrophilic modifier is CHES, CAPS or CABS produced by Aladdin;

[0092] The epoxy resins are tetraglycidyl diaminodimethylenebenzene MF-4101, 4,5-epoxytetrahydrophthalic acid diglycidyl ester MF-3286, and triglycidyl-p-aminophenol MF-3102 from Hubei Zhenzhengfeng New Materials Co., Ltd.

[0093] The blocked cationic thermal initiator is CTI-100, CTI-200, CTI-300 from Shenzhen Youyang Company or Vicbase TC3631 from Shenzhen Keyi Applied Materials Co., Ltd.;

[0094] The initiation temperature of the blocked cationic thermal initiator is 70-100°C.

[0095] The cationic photoinitiator is HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976 from Huiren Hengtong or Omnirad250 from IGM;

[0096] The free radical photoinitiators were Darocur 1173, Irgacure 2959, Irgacure 500, Lucirin TPO-L, and Irgacure 819-DW from IGM;

[0097] The acrylamide-based monomer is diacetone acrylamide DAAM, N-butoxymethyl acrylamide or hydroxyethyl acrylamide;

[0098] The sulfonic acid neutralizing agent is triethylamine TEA or N,N-dimethylcyclohexylamine DMCHA from Dow Chemical.

[0099] Basic performance tests include: cationic light-cured bio-based polyurethane dispersions are tested in accordance with GB / T11175-2002 "Test Methods for Synthetic Resin Emulsions", and the appearance, pH, solid content, and viscosity of the emulsion are tested. The average particle size of the dispersion is measured using a nanoparticle size analyzer (ZS Nano S). The double bond and epoxy concentrations are obtained by theoretical calculations, and the double bond and epoxy concentrations are the ratio of the amount of double bond or epoxy substance to the mass of the solid content of the emulsion or coating, in mol / 100g.

[0100] Example 1

[0101] An epoxy-modified light-curable polyacrylate dispersion 1 is prepared by the following steps:

[0102] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A1 for standby use;

[0103] S2. In parts by mass, 11.1 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 6.6 parts of triethylene glycol divinyl ether DVE were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing a vinyl group and an isocyanate group B1 for standby use;

[0104] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73 ° C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C1 for standby use;

[0105] S4. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D1, which was set aside;

[0106] S5. In parts by mass, 0.4 parts of a blocked cationic thermal initiator CTI-100, 0.5 parts of a cationic photoinitiator HRcure-9387 and 0.4 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture E1 for standby use;

[0107] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C1 is heated to 150°C, the mixed liquid A1 is dripped into it at a constant pressure within 4 hours. After the dripping is completed, the mixture is stirred and kept warm for 30 minutes, the temperature is lowered to 80°C, 0.01 parts of inhibitor MEHQ are added, 9.7 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, 17.7 parts of B1 are added, the reaction is continued for 30 minutes, 32.2 parts of D1 are added, 1.3 parts of E1 are added after stirring for 5 minutes, 6.1 parts of triethylamine TEA are added after stirring for 5 minutes, 201 parts of deionized water are added after stirring for 10 minutes, and the material is filtered to obtain epoxy-modified light-cured polyacrylate dispersion 1.

[0108] Example 2

[0109] An epoxy-modified light-curable polyacrylate dispersion 2 is prepared by the following steps:

[0110] S1. In parts by mass, 2.2 parts of methacrylic acid MAA, 12.5 parts of methyl methacrylate MMA, 6.3 parts of butyl acrylate BA, 7.5 parts of cyclohexyl methacrylate CHMA, 7.5 parts of styrene St, 0.5 parts of di-tert-butyl peroxide DTBP were mixed to form a mixed solution A2 for standby use;

[0111] S2. In parts by mass, 8.4 parts of hexamethylene diisocyanate HDI were heated to 60 ° C, and 5.8 parts of 4-hydroxybutyl vinyl ether HBVE were added dropwise at a constant pressure within 25 minutes, and the reaction was continued for 0.8 hours to obtain a prepolymer containing a vinyl group and an isocyanate group B2 for standby use;

[0112] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 24.2 parts of special epoxy soybean oil GreenSoft H were added, stirred and heated to 65°C, 5.2 parts of cyclohexylaminoethanesulfonic acid CHES were added, and the reaction was carried out for 90 minutes to obtain a hydrophilic modified bio-based material C2 for standby use;

[0113] S4. In parts by mass, 14.9 parts of MF-3286 and 10.4 parts of cyclohexylaminoethanesulfonic acid CHES were mixed uniformly, the reaction temperature was controlled to 45 ° C, and the reaction was carried out for 2 hours to form a prepolymer D2, which was set aside;

[0114] S5. In parts by mass, 0.4 parts of a blocked cationic thermal initiator CTI-200, 0.6 parts of a cationic photoinitiator HRcure-9388 and 0.3 parts of a free radical photoinitiator Irgacure 2959 were mixed to form a mixture E2 for standby use;

[0115] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C2 is heated to 140°C, the mixed solution A2 is dripped into it at a constant pressure within 3.5 hours. After dripping, the mixture is stirred and kept warm for 40 minutes. The temperature is lowered to 70°C, 0.01 parts of polymerization inhibitor MEHQ are added, 9.0 parts of N-butoxymethyl acrylamide are added, the reaction is continued for 50 minutes, the temperature is lowered to 45°C, 14.2 parts of B2 are added, the reaction is continued for 40 minutes, 25.3 parts of D2 are added, 1.3 parts of E2 are added after stirring for 7 minutes, 5.3 parts of N,N-dimethylethanolamine DMEA are added after stirring for 3 minutes, 181 parts of deionized water are added after stirring for 3 minutes, and the mixture is dispersed at high speed for 15 minutes. The epoxy-modified light-curing polyacrylate dispersion 2 is obtained by filtering the material.

[0116] Example 3

[0117] An epoxy-modified light-curable polyacrylate dispersion 3 is prepared by the following steps:

[0118] S1. In parts by mass, 1.8 parts of acrylic acid AA, 11.3 parts of methyl methacrylate MMA, 7.5 parts of butyl acrylate BA, 6.3 parts of Bian methacrylate BNMA, 8.7 parts of styrene St, 0.4 parts of di-tert-butyl peroxide DTBP were mixed to form a mixed solution A3 and set aside;

[0119] S2. In parts by mass, 13.1 parts of hydrogenated MDI were heated to 70 ° C, and 8.5 parts of cyclohexyl-1,4-dimethanol monovinyl ether were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 0.8 hours to obtain a prepolymer containing vinyl and isocyanate groups B3, which was set aside;

[0120] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, add 18.5 parts of epoxy linseed oil by mass. 9-5 TM , stirring and heating, raising the temperature to 60° C., adding 5.9 parts of cyclohexylaminobutanesulfonic acid CABS, reacting for 90 minutes, and obtaining a hydrophilic modified bio-based material C3 for standby use;

[0121] S4. In parts by mass, 13.9 parts of MF-3102 and 11.8 parts of cyclohexylaminobutanesulfonic acid CABS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 2 hours to form a prepolymer D3, which was set aside;

[0122] S5. In parts by mass, 0.5 parts of a blocked cationic thermal initiator CTI-300, 0.5 parts of a cationic photoinitiator Omnirad250 and 0.3 parts of a free radical photoinitiator Irgacure 500 were mixed to form a mixture E3 for standby use;

[0123] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C3 is heated to 145°C, the mixed solution A3 is dripped into it at a constant pressure within 4 hours. After dripping, the mixture is stirred and kept warm for 35 minutes. The temperature is lowered to 75°C, 0.01 parts of polymerization inhibitor MEHQ are added, 6.6 parts of hydroxyethyl acrylamide are added, the reaction is continued for 60 minutes, the temperature is lowered to 55°C, 21.6 parts of B3 are added, the reaction is continued for 35 minutes, 25.7 parts of D3 are added, 1.3 parts of E3 are added after stirring for 5 minutes, 7.6 parts of N,N-dimethylcyclohexylamine DMCHA are added after stirring for 5 minutes, 185 parts of deionized water are added after stirring for 20 minutes, and the material is filtered to obtain epoxy-modified light-cured polyacrylate dispersion 3.

[0124] Comparative Example 1

[0125] An epoxy-modified photocurable polyacrylate dispersion 4, the difference between this comparative example and the embodiment is that in step S2, isophorone diisocyanate IPDI and triethylene glycol divinyl ether DVE are added in excess, and it is prepared by the following steps:

[0126] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A4 for standby use;

[0127] S2. In parts by mass, 35.0 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 20.8 parts of triethylene glycol divinyl ether DVE were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing a vinyl group and an isocyanate group B4, set aside;

[0128] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73°C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C4 for standby use;

[0129] S4. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D4, which was set aside;

[0130] S5. In parts by mass, 0.4 parts of a blocked cationic thermal initiator CTI-100, 0.5 parts of a cationic photoinitiator HRcure-9387 and 0.4 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture E4 for standby use;

[0131] S6. In terms of mass fractions, the hydrophilic modified bio-based material C4 is heated to 150°C and then the mixed solution A4 is dripped into the mixed solution at a constant pressure within 4 hours. After the dripping is completed, the mixture is stirred and kept warm for 30 minutes, the temperature is lowered to 80°C, 0.01 parts of polymerization inhibitor MEHQ is added, 9.7 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, 55.8 parts of B4 are added, the reaction is continued for 30 minutes, 32.2 parts of D4 are added, 1.3 parts of E4 are added after stirring for 5 minutes, 6.1 parts of triethylamine TEA are added after stirring for 5 minutes, 258 parts of deionized water are added after stirring for 10 minutes, and the material is filtered to obtain epoxy-modified light-curable polyacrylate dispersion 4;

[0132] Comparative Example 2

[0133] An epoxy-modified light-curable polyacrylate dispersion 5, the difference between Comparative Example 2 and Example 1 is that no vinyl ether double-bond monomer is included, which is prepared by the following steps:

[0134] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A5 for standby use;

[0135] S2. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73°C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C5 for standby use;

[0136] S3. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D5, set aside;

[0137] S4. In parts by mass, 0.4 parts of a blocked cationic thermal initiator CTI-100, 0.5 parts of a cationic photoinitiator HRcure-9387 and 0.4 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture E5 for standby use;

[0138] S5. In terms of mass fractions, the hydrophilic modified bio-based material C5 was heated to 150°C and then the mixed solution A5 was dripped into the mixed solution at a constant pressure within 4 hours. After the dripping was completed, the mixture was stirred and kept warm for 30 minutes, cooled to 80°C, 0.01 parts of polymerization inhibitor MEHQ was added, 9.7 parts of diacetone acrylamide DAAM were added, the reaction was continued for 40 minutes, cooled to 50°C, 32.2 parts of D5 were added, 1.3 parts of E5 were added after stirring for 5 minutes, 6.1 parts of triethylamine TEA were added after stirring for 5 minutes, 174 parts of deionized water were added after stirring for 5 minutes, and the mixture was dispersed at high speed for 10 minutes. The epoxy-modified light-curable polyacrylate dispersion 5 was obtained by filtering the material;

[0139] Comparative Example 3

[0140] An epoxy-modified light-curable polyacrylate dispersion 6, in which the epoxy resin addition ratio is too high compared with Example 1 in Comparative Example 3, is prepared by the following steps:

[0141] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A6 for standby use;

[0142] S2. In parts by mass, 11.1 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 6.6 parts of triethylene glycol divinyl ether DVE were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing a vinyl group and an isocyanate group B6, set aside;

[0143] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73°C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C6 for standby use;

[0144] S4. In parts by mass, 42.2 parts of MF-4101 and 22.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D6, which was set aside;

[0145] S5. In parts by mass, 0.4 parts of a blocked cationic thermal initiator CTI-100, 0.5 parts of a cationic photoinitiator HRcure-9387 and 0.4 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture E6 for standby use;

[0146] S6. In terms of mass fractions, the hydrophilic modified bio-based material C6 was heated to 150°C and then the mixed solution A6 was dripped into the mixed solution at a constant pressure within 4 hours. After the dripping was completed, the mixture was stirred and kept warm for 30 minutes, the temperature was lowered to 80°C, 0.01 parts of polymerization inhibitor MEHQ was added, 9.7 parts of diacetone acrylamide DAAM were added, the reaction was continued for 40 minutes, the temperature was lowered to 50°C, 17.7 parts of B6 were added, the reaction was continued for 30 minutes, 64.3 parts of D6 were added, 1.3 parts of E6 were added after stirring for 5 minutes, 10.1 parts of triethylamine TEA were added after stirring for 5 minutes, 255 parts of deionized water were added after stirring for 10 minutes, and the epoxy-modified light-curable polyacrylate dispersion 6 was obtained by filtering the material;

[0147] Comparative Example 4

[0148] An epoxy-modified light-curable polyacrylate dispersion 7, in which a photoinitiator and a blocked thermal initiator are not dispersed together with the resin but are only added in the coating preparation stage, is prepared by the following steps:

[0149] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A7 for standby use;

[0150] S2. In parts by mass, 11.1 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 6.6 parts of triethylene glycol divinyl ether DVE were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing a vinyl group and an isocyanate group B7, set aside;

[0151] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73°C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C7 for standby use;

[0152] S4. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D7, which was set aside;

[0153] S5. In terms of mass fractions, the hydrophilic modified bio-based material C7 was heated to 150°C and then the mixed solution A7 was dripped into the mixed solution at a constant pressure within 4 hours. After the dripping was completed, the mixture was stirred and kept warm for 30 minutes, cooled to 80°C, 0.01 parts of polymerization inhibitor MEHQ was added, 9.7 parts of diacetone acrylamide DAAM were added, and the reaction was continued for 40 minutes, cooled to 50°C, 17.7 parts of B7 were added, and the reaction was continued for 30 minutes, 32.2 parts of D7 were added, and 6.1 parts of triethylamine TEA were added after stirring for 5 minutes. After stirring for 5 minutes, 199 parts of deionized water were added and dispersed at high speed for 10 minutes, and the material was filtered to obtain epoxy-modified light-curable polyacrylate dispersion 7;

[0154] Comparative Example 5

[0155] An epoxy-modified light-curable polyacrylate dispersion 8, in which no blocked cationic thermal initiator is added compared to Example 1, is prepared by the following steps:

[0156] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A8 for standby use;

[0157] S2. In parts by mass, 11.1 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 6.6 parts of triethylene glycol divinyl ether DVE were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing a vinyl group and an isocyanate group B8, set aside;

[0158] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73°C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C8 for standby use;

[0159] S4. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D8, which was set aside;

[0160] S5. In parts by mass, 0.5 parts of cationic photoinitiator HRcure-9387 and 0.4 parts of free radical photoinitiator Darocur1173 were mixed to form a mixture E8 for later use;

[0161] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C8 is heated to 150°C, the mixed liquid A8 is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 30 minutes, cooled to 80°C, 0.01 parts of inhibitor MEHQ are added, 9.7 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, cooled to 50°C, 17.7 parts of B8 are added, the reaction is continued for 30 minutes, 32.2 parts of D8 are added, 0.9 parts of E8 are added after stirring for 5 minutes, 6.1 parts of triethylamine TEA are added after stirring for 5 minutes, 200 parts of deionized water are added after stirring for 10 minutes, and the material is filtered to obtain epoxy-modified light-cured polyacrylate dispersion 8.

[0162] Comparative Example 6

[0163] In this comparative example, an epoxy-modified light-curable polyacrylate dispersion is prepared. The difference between this comparative example and Example 1 is that hydroxy vinyl ether is replaced by hydroxy acrylate, and the other conditions are the same as those in Example 1.

[0164] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A9 for standby use;

[0165] S2. In parts by mass, 11.1 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 6.5 parts of hydroxyethyl methacrylate HEMA were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing a vinyl group and an isocyanate group B9, set aside;

[0166] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73 ° C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C9 for standby use;

[0167] S4. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D9, which was set aside;

[0168] S5. In parts by mass, 0.4 parts of a blocked cationic thermal initiator CTI-100, 0.5 parts of a cationic photoinitiator HRcure-9387 and 0.4 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture E9 for standby use;

[0169] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C9 is heated to 150°C, the mixed liquid A9 is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 30 minutes, cooled to 80°C, 0.01 parts of inhibitor MEHQ are added, 9.7 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, cooled to 50°C, 17.7 parts of B1 are added, the reaction is continued for 30 minutes, 32.2 parts of D9 are added, 1.3 parts of E9 are added after stirring for 5 minutes, 6.1 parts of triethylamine TEA are added after stirring for 5 minutes, 201 parts of deionized water are added after stirring for 10 minutes, and the material is filtered to obtain epoxy-modified light-cured polyacrylate dispersion 9.

[0170] Comparative Example 7

[0171] This comparative example provides an epoxy-modified light-curable polyacrylate dispersion. The difference between the comparative example and Example 1 is that the CTI-100 is replaced by a blocked cationic thermal initiator Vicbase TC3635 having an initiation temperature of 120° C., and the other conditions are the same.

[0172] S1. In parts by mass, 1.8 parts of acrylic acid AA, 13.8 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 10.8 parts of styrene St, 0.6 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution A10 for standby use;

[0173] S2. In parts by mass, 11.1 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 6.6 parts of triethylene glycol divinyl ether DVE were added dropwise at a constant pressure within 15 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing vinyl and isocyanate groups B10 for standby use;

[0174] S3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 25.2 parts of special epoxy soybean oil GreenSoft D were added, stirred and heated to 73 ° C, 5.5 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material C10 for standby use;

[0175] S4. In parts by mass, 21.1 parts of MF-4101 and 11.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled to 40 ° C, and the reaction was carried out for 1.5 hours to form a prepolymer D10, which was set aside;

[0176] S5. In parts by mass, 0.4 parts of a blocked cationic thermal initiator VicbaseTC3635, 0.5 parts of a cationic photoinitiator HRcure-9387 and 0.4 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture E10 for standby use;

[0177] S6. In terms of mass fractions, when the hydrophilic modified bio-based material C10 is heated to 150°C, the mixed liquid A10 is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 30 minutes, cooled to 80°C, 0.01 parts of inhibitor MEHQ are added, 9.7 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, cooled to 50°C, 17.7 parts of B10 are added, the reaction is continued for 30 minutes, 32.2 parts of D10 are added, 1.3 parts of E10 are added after stirring for 5 minutes, 6.1 parts of triethylamine TEA are added after stirring for 5 minutes, 201 parts of deionized water are added after stirring for 10 minutes, and the material is filtered to obtain the epoxy-modified light-cured polyacrylate dispersion 10.

[0178] Test Example 1

[0179] Test Example A cationic light-cured bio-based coating was prepared, and the epoxy-modified light-cured polypropylene resin dispersion was prepared in the example and the comparative example. The specific steps were:

[0180] The cationic light-curing bio-based coating is composed of the following components in parts by weight:

[0181]

[0182]

[0183] The preparation method of the cationic photocurable bio-based coating is as follows: adding the cationic photocurable bio-based polyurethane dispersion into a stirring tank at a rotation speed of 700 rpm, premixing water, propylene glycol butyl ether and propylene glycol methyl ether and adding them into the stirring tank, and sequentially adding DISPERS 755W, Ti-Pure R-902+, Irgacure 2959, Lucirin TPO-L, Omnirad 250, TEGO-825, RM-8W and TEGO-245, dispersing for 20 minutes, filtering the material, and obtaining the cationic photocurable bio-based coating.

[0184] The paint film made of cationic photocurable bio-based coating was dried at 50°C for 2 hours, and the photocuring machine was turned on with a mercury lamp and the UVV energy was adjusted to 600mJ / cm 2 After curing, the product was baked at 100°C for 2h. The properties are shown in Table 1.

[0185] The test standards are:

[0186] Coating appearance: visual inspection;

[0187] Pencil hardness: GB / T6739-2006;

[0188] Coating gloss / (60°,%): GB / T9754-2007;

[0189] Water resistance (25℃, 24h): GB / T4893.1-2020;

[0190] Dry heat resistance (70±2℃, 15h): GB / T4893.3-2020;

[0191] Ethanol resistance (50%, 1h): GB / T4893.1-2020;

[0192] Adhesion: GB / T9286-2021;

[0193] Table 1 Performance parameters of epoxy-modified photocurable polyacrylate dispersion and water-based photocurable bio-based coatings

[0194]

[0195]

[0196]

[0197] As can be seen from the above table, compared with Example 1, Comparative Example 1 has a high content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 with the hydroxyl group of the prepolymer, which reacts with the epoxy group of MF-4101, resulting in poor dispersion stability; Comparative Example 2 has a low content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 with the hydroxyl group of the prepolymer, resulting in poor dispersion stability; Comparative Example 2 has a low content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 with the hydroxyl group of the prepolymer, resulting in poor dispersion stability; Comparative Example 2 has a low content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 with the hydroxyl group of the prepolymer, resulting in poor dispersion stability; Comparative Example 3 has a high content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 with the hydroxyl group of the prepolymer, resulting in poor dispersion stability; Comparative Example 4 has a low ... and the hydroxyl group of the prepolymer, resulting in poor dispersion stability; Comparative Example 5 has a low content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 and the prepolymer, resulting in poor dispersion stability; Comparative Example 5 has a low content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 and the prepolymer, resulting in poor dispersion stability; Comparative Example 1 has a high content of secondary amine groups generated by the reaction of IPDI and DVE and the reaction of B3 and the prepolymer, resulting in poor dispersion stability; Comparative Example 1 has a high content of secondary amine groups generated by the Compared with Example 1, in Comparative Example 6, the hydroxy vinyl ether monomer is replaced with a hydroxy acrylate monomer. The double bond of the hydroxy acrylate mainly participates in free radical curing and is weak in cationic curing. Therefore, only the epoxy group is involved in cationic curing, and the copolymerization of cationic curing and free radical curing is reduced, resulting in poor performance of the paint film such as flexibility, transparency and adhesion. Compared with Example 1, the initiation temperature of the blocked cationic thermal initiator in Comparative Example 7 is 120°C. Since many wooden substrates are easily deformed after the baking temperature exceeds 100°C, the set baking temperature of 100°C is lower than the initiation temperature of 120°C, and the initiator has no initiation effect. Therefore, the performance of the paint film is similar to that of Example 5 without adding a blocked cationic thermal initiator. It can be seen from Examples 1, 2, and 3 that the present invention discloses a method for preparing an epoxy-modified light-cured polyacrylate dispersion, and the paint film made of the prepared cationic light-cured bio-based coating has the advantages of good flexibility, good water resistance and chemical resistance, and excellent adhesion to a variety of substrates, and can be applied to high-end wood coatings, automotive coatings, metal anticorrosive coatings and other industrial protective coatings.

[0198] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A method for preparing an epoxy-modified light-curable polyacrylate dispersion, characterized in that: The preparation method comprises the following steps: S1. The acrylic acid monomer, the acrylate monomer, the vinyl monomer, and the initiator are mixed to obtain a mixed solution A; S2. The diisocyanate and the hydroxy vinyl ether are mixed and reacted to obtain a prepolymer B containing a vinyl group and an isocyanate group; S3: mixing the bio-based material and the hydrophilic modifier to obtain a hydrophilic modified bio-based material C; S4. mixing the epoxy resin and the hydrophilic modifier to obtain a prepolymer D; S5. The blocked cationic thermal initiator, the cationic photoinitiator and the free radical photoinitiator are mixed to form a mixture E; S6. The hydrophilic modified bio-based material C, the polymerization inhibitor, the acrylamide monomer, the prepolymer B, the prepolymer D, the mixture E and the neutralizer are dispersed and reacted to obtain an epoxy-modified light-curable polyacrylate dispersion; Wherein, the bio-based material is a plant oil containing three or more epoxy groups; The hydrophilic modifier is a monomer containing a secondary amino group and a sulfonic acid group; The epoxy resin is an epoxy resin containing three or more epoxy groups; The neutralizing agent is a tertiary amine; The hydrophilic modifiers in step S3 and step S4 are the same or different.

2. The preparation method according to claim 1, characterized in that: The preparation method comprises the following steps: S1. In parts by mass, 1.5 to 2.5 parts of acrylic acid monomer, 20 to 30 parts of acrylate monomer, 5 to 11 parts of vinyl monomer, and 0.4 to 0.6 parts of initiator are mixed to form a mixed solution A; S2. In parts by mass, 8 to 15 parts of diisocyanate are heated to 50 to 70 ° C, and 5 to 9 parts of hydroxy vinyl ether are added dropwise, and the reaction is continued for 0.8 to 1.5 hours to obtain a prepolymer B containing a vinyl group and an isocyanate group; S3. In parts by mass, 18 to 26 parts of the bio-based material are heated to 55 to 75° C., 5 to 6 parts of a hydrophilic modifier are added, and the reaction is performed to obtain a hydrophilic modified bio-based material C; S4. In parts by mass, 10 to 25 parts of an epoxy resin and 10 to 15 parts of a hydrophilic modifier are mixed, the reaction temperature is controlled to be 40 to 45 ° C, and the reaction forms a prepolymer D; S5. In parts by mass, 0.3 to 0.5 parts of a blocked cationic thermal initiator, 0.3 to 0.6 parts of a cationic photoinitiator and 0.3 to 0.5 parts of a free radical photoinitiator are mixed to form a mixture E; S6. In terms of mass fractions, when the hydrophilic modified bio-based material C is heated to 130-150°C, the mixed solution A is added dropwise within 3-4 hours. After the addition is completed, the mixture is stirred and kept warm for 20-40 minutes. The mixture is cooled to 60-80°C, 0.01 parts of polymerization inhibitor MEHQ are added, 6-10 parts of acrylamide monomer are added, the reaction is continued for 30-60 minutes, the mixture is cooled to 45-55°C, prepolymer B containing vinyl and isocyanate groups is added, the reaction is continued for 30-40 minutes, prepolymer D is added, the mixture is stirred for 5-10 minutes, 5-8 parts of neutralizer are added after stirring for 3-5 minutes, 180-210 parts of deionized water are added after stirring for 3-5 minutes, and the mixture is dispersed for 10-20 minutes. The epoxy-modified light-curing polyacrylate dispersion is obtained by filtering the material.

3. The preparation method according to claim 1, characterized in that: The initiator includes at least one of di-tert-amyl peroxide and di-tert-butyl peroxide.

4. The preparation method according to claim 1, characterized in that: The hydroxy vinyl ether includes at least one of 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether and cyclohexyl-1,4-dimethanol monovinyl ether.

5. The preparation method according to claim 1, characterized in that: The epoxy resin includes at least one of tetraglycidyl diaminodimethylene benzene, diglycidyl 4,5-epoxytetrahydrophthalate, and triglycidyl-p-aminophenol.

6. The preparation method according to claim 1, characterized in that: The blocked cationic thermal initiator includes a blocked phosphate cationic thermal initiator.

7. An epoxy-modified light-curable polyacrylate dispersion, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. A water-based bio-based photocurable coating, characterized in that: The preparation raw materials include the epoxy-modified light-curable polyacrylate dispersion described in claim 7.

9. The water-based bio-based photocurable coating according to claim 8, characterized in that: By weight, the preparation comprises the following raw materials in parts by weight:

10. Use of the waterborne bio-based photocurable coating according to claim 8 or 9 in the fields of wood product preparation, automobile manufacturing or metal product corrosion protection.

Images