Light-cured epoxy-acrylic acid-polyurethane hybrid dispersion as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of coatings, and discloses a light-cured epoxy-acrylic acid-polyurethane hybrid dispersion as well as a preparation method and application thereof. The light-cured epoxy-acrylic acid-polyurethane hybrid dispersion is prepared from the following raw materials: a hydrophilic chain extender, an acrylic monomer, an acrylate monomer, a vinyl monomer, epoxy resin, polyol, an isocyanate monomer, a bio-based material, a hydrophilic modifier, an acrylamide monomer, a neutralizer and an initiator. A paint film of a water-based light-cured bio-based paint prepared from the light-cured epoxy-acrylic acid-polyurethane hybrid 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 a light-cured epoxy-acrylic-polyurethane hybrid dispersion and a preparation method and application thereof. Background Art

[0002] At present, most coatings except for interior and exterior wall coatings are still solvent-based coatings, containing more than 50% organic solvents. These solvents will volatilize into the atmosphere during the construction process, polluting the environment and damaging human health. In addition, organic solvents themselves will bring safety hazards. Therefore, environmentally friendly water-based coatings are the development trend. Water-based coatings mainly include water-based single-component coatings, water-based two-component coatings, and water-based light-curing coatings that have developed rapidly in recent years. The film properties of single-component water-based coatings, such as water resistance, chemical resistance and hardness, are far behind those of solvent-based coatings, which seriously limits the promotion and application of water-based coatings. The mechanical properties, water resistance and chemical resistance of two-component water-based coatings are close to those of solvent-based coatings, 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, affecting construction efficiency. The mechanical properties, water resistance and chemical resistance of water-based light-curing coatings are better than those of solvent-based products. They are single-component packaging, ready for use after opening the barrel, and have no activation period. They are suitable for various mechanical spraying. After drying for 0.5 to 2 hours after construction and curing in a UV curing machine, they can be packaged off the line. Therefore, water-based light-curing coatings will replace two-component water-based coatings and become the first choice for high-end water-based coatings in the future. At present, water-based light-curing coatings have the problems of poor storage stability and poor adhesion to many substrates.

[0003] Therefore, there is an urgent need to provide a water-based photocurable coating with good storage stability and good adhesion to substrates. 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 provides a method for preparing a photocurable epoxy-acrylic-polyurethane hybrid dispersion, and the paint film of the water-based photocurable bio-based coating prepared by using the dispersion as a raw material 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, and can be applied to high-end wood coatings, automotive coatings, metal anticorrosive coatings and other industrial protective coatings.

[0005] The present invention also provides a photocurable epoxy-acrylic-polyurethane hybrid dispersion.

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

[0007] The present invention also provides an application of a 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 a photocurable epoxy-acrylic-polyurethane hybrid dispersion, the preparation method comprising the following steps:

[0009] S1. The hydrophilic chain extender and the neutralizer are mixed to form a mixture A;

[0010] S2. The acrylic monomer, acrylate monomer, vinyl monomer, free radical polymerization low temperature thermal initiator, epoxy resin are mixed to form a mixed solution B;

[0011] S3. The macromolecular diol, the mixture A, the diisocyanate, the small molecule chain extender and the mixed solution B are mixed to form a prepolymer C;

[0012] S4. mixing the bio-based material and the hydrophilic modifier to obtain a hydrophilic modified bio-based material D;

[0013] S5. The acrylic acid monomer, the acrylate monomer, the vinyl monomer, and the free radical polymerization high temperature thermal initiator are mixed to form a mixed solution E;

[0014] S6. The diisocyanate and the hydroxy vinyl ether are mixed and reacted to obtain a prepolymer F containing a vinyl group and an isocyanate group;

[0015] S7. The blocked cationic thermal initiator, the cationic photoinitiator and the free radical photoinitiator are mixed to form a mixture G;

[0016] S8. Mix and disperse the hydrophilically modified bio-based material D, the mixed solution E, the inhibitor, the acrylamide-based monomer, the prepolymer C, the prepolymer F, the mixture G, and the neutralizer to obtain a photocurable epoxy-acrylic-polyurethane hybrid dispersion.

[0017] The embodiments according to the first aspect of the present invention have at least the following beneficial effects:

[0018] 1. The present invention introduces a cationic photocuring system and an epoxy group into a photocurable epoxy-acrylic-polyurethane hybrid dispersion, thereby reducing the shrinkage rate of the paint film and improving the adhesion of the paint film to various substrates; wherein the epoxy resin and the acrylate are grafted and polymerized, thereby improving the compatibility of the epoxy resin and the polyacrylate resin; and the blocked cationic thermal initiator, the cationic photoinitiator and the free radical photoinitiator are co-dispersed with the resin, thereby further improving the reaction degree of the photocurable group, thereby improving the resistance of the paint film.

[0019] 2. 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.

[0020] 3. Conventional water-based photocurable coatings only add photoinitiators during the coating preparation stage, resulting in the inability of the photocurable groups inside the latex particles to fully react. The present invention disperses the blocked cationic thermal initiator, cationic photoinitiator, free radical photoinitiator and resin together, which can make the photocurable groups inside the latex particles react more fully. The addition of blocked cationic thermal initiators can provide another curing method for the paint film while ensuring storage stability. When the water-based photocurable coating is a solid color coating, ultraviolet rays cannot penetrate the paint film, resulting in the inability to cure the bottom layer of the paint film. The paint film to which the blocked cationic thermal initiator is added can cure the bottom layer of the paint film after baking. Some woods have a high oil content, such as pine wood. When baked, the oil will emerge from the substrate, causing defects such as blistering of the paint film. Since such oils contain double bonds and epoxy groups, the blocked cationic thermal initiator can cause the oil to cure during baking, thereby avoiding paint film defects.

[0021] 4. The epoxy resin of the present invention undergoes graft polymerization with acrylate and addition reaction with isocyanate, thereby improving the compatibility of the epoxy resin with polyacrylate resin and polyurethane resin, and improving the gloss and transparency of the paint film.

[0022] In some embodiments of the present invention, the preparation method comprises the following steps:

[0023] S1. Mix 2 to 2.5 parts of a hydrophilic chain extender and 0.5 to 1.0 parts of a neutralizing agent to form a mixture A, in parts by mass;

[0024] S2. By weight, 1.5 to 2.5 parts of acrylic acid monomer, 30 to 36 parts of acrylate monomer, 6 to 9 parts of vinyl monomer, 0.3 to 0.6 parts of free radical polymerization low temperature thermal initiator, and 20 to 25 parts of epoxy resin are mixed to form a mixed solution B;

[0025] S3. By weight, 10 to 25 parts of a macromolecular diol and a mixture A, 6 to 12 parts of a diisocyanate, 1 to 3 parts of a small molecule chain extender and a mixture B are mixed to form a prepolymer C;

[0026] S4. By weight, 18 to 26 parts of the bio-based material and 5 to 6 parts of the hydrophilic modifier are reacted to obtain a hydrophilic modified bio-based material D;

[0027] S5. In parts by mass, 2 to 3 parts of acrylic acid monomer, 15 to 25 parts of acrylate monomer, 3 to 9 parts of vinyl monomer, and 0.3 to 0.6 parts of free radical polymerization high temperature thermal initiator are mixed to form a mixed solution E;

[0028] S6. By weight, 15 to 30 parts of diisocyanate and 11 to 20 parts of hydroxy vinyl ether are mixed and reacted to obtain a prepolymer F containing a vinyl group and an isocyanate group;

[0029] S7. In parts by mass, 0.5 to 1.0 parts of a blocked cationic thermal initiator, 1.0 to 1.5 parts of a cationic photoinitiator and 0.5 to 1.0 parts of a free radical photoinitiator are mixed to form a mixture G;

[0030] S8. In parts by mass, the hydrophilic modified bio-based material D, the mixed solution E, 0.01 parts of an inhibitor, 5 to 10 parts of an acrylamide-based monomer, a prepolymer F, a mixture G, and 3 to 6 parts of a neutralizer are mixed and dispersed to react to obtain a photocurable epoxy-acrylic-polyurethane hybrid dispersion.

[0031] In some embodiments of the present invention, the preparation method comprises the following steps:

[0032] S1. Mix 2 to 2.5 parts of a hydrophilic chain extender and 0.5 to 1.0 parts of a neutralizing agent to form a mixture A, in parts by mass;

[0033] S2. In parts by mass, 1.5 to 2.5 parts of acrylic acid monomer, 30 to 36 parts of acrylate monomer, 6 to 9 parts of vinyl monomer, 0.3 to 0.6 parts of free radical polymerization low temperature thermal initiator, and 20 to 25 parts of epoxy resin are mixed to form a mixed solution B;

[0034] S3. In a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, 10 to 25 parts of a macromolecular diol and a mixture A are added, stirring is started, heated to 70 to 80 ° C, stabilized for 5 to 15 minutes, 6 to 12 parts of a diisocyanate are added, and after reacting for 25 to 60 minutes, 1 to 3 parts of a small molecule chain extender are added, and the reaction is continued for 25 to 60 minutes, the temperature is lowered to 50 to 75 ° C, and the mixture B is added dropwise at a constant pressure within 4 hours, and the temperature is raised to 75 to 85 ° C, and the temperature is kept for 2 to 3 hours to form a prepolymer C;

[0035] S4. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 18 to 26 parts of a bio-based material are added, stirred and 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 D;

[0036] S5. In parts by mass, 2 to 3 parts of acrylic acid monomer, 15 to 25 parts of acrylate monomer, 3 to 9 parts of vinyl monomer, and 0.3 to 0.6 parts of free radical polymerization high temperature thermal initiator are mixed to form a mixed solution E;

[0037] S6. When 15 to 30 parts of diisocyanate are heated to 40 to 60°C, 11 to 20 parts of hydroxy vinyl ether are added dropwise at a constant pressure within 10 to 30 minutes, and the reaction is continued for 0.5 to 1 hour to obtain a prepolymer F containing a vinyl group and an isocyanate group;

[0038] S7. In parts by mass, 0.5 to 1.0 parts of a blocked cationic thermal initiator, 1.0 to 1.5 parts of a cationic photoinitiator and 0.5 to 1.0 parts of a free radical photoinitiator are mixed to form a mixture G;

[0039] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D is heated to 130-150°C, the mixed solution E is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 20-40 minutes, cooled to 60-80°C, 0.01 parts of inhibitor are added, 5-10 parts of acrylamide monomer are added, the reaction is continued for 30-60 minutes, cooled to 45-55°C, C is added, and F is added after stirring for 10-20 minutes. After continuing the reaction for 30-60 minutes, G is added, and 3-6 parts of neutralizer are added after stirring for 3-5 minutes. After stirring for 3-5 minutes, 280-330 parts of deionized water are added and dispersed at high speed for 10-20 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion.

[0040] In some embodiments of the present invention, the hydrophilic chain extender includes at least one of dimethylol propionic acid DMPA, dimethylol butyric acid DMBA and Ymer N120.

[0041] In some embodiments of the present invention, the neutralizing agent comprises a tertiary amine neutralizing agent.

[0042] In some embodiments of the present invention, the tertiary amine neutralizer includes at least one of triethylamine TEA, N,N-dimethylethanolamine and N,N-dimethylcyclohexylamine DMCHA.

[0043] In some embodiments of the present invention, the acrylic acid monomer includes at least one of acrylic acid AA and methacrylic acid MAA.

[0044] In some embodiments of the present invention, the acrylate monomer includes a methacrylate monomer, and the methacrylate monomer includes at least one of methyl methacrylate MMA, butyl acrylate BA, isobornyl acrylate IBOA, cyclohexyl methacrylate CHMA, and benzyl methacrylate BZMA.

[0045] In some embodiments of the present invention, the vinyl monomer includes at least one of styrene St and vinyl acetate VAc.

[0046] In some embodiments of the present invention, the low-temperature initiator includes at least one of benzoyl peroxide BPO, azobisisobutyronitrile AIBN and azobisisoheptanenitrile ABVN.

[0047] In some embodiments of the present invention, the epoxy resin comprises a bisphenol epoxy resin.

[0048] The present invention selects bisphenol epoxy resin with moderate epoxy group reactivity to avoid the reaction between the epoxy group and the secondary amine group, thereby ensuring the storage stability of the dispersion.

[0049] In some embodiments of the present invention, the macromolecular diol includes at least one of polyether diol, polybutylene adipate diol and polycarbonate diol.

[0050] 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.

[0051] In some embodiments of the present invention, the small molecule chain extender includes at least one of 1,4-butanediol BDO, 2,4-diethyl-1,5-pentanediol PD-9, ethyl butyl propanediol BEPD, 1,6-hexanediol HDO and neopentyl glycol NPG.

[0052] 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 ELO 9-5 TM At least one of .

[0053] 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.

[0054] In some embodiments of the present invention, the free radical polymerization high temperature initiator includes at least one of di-tert-amyl peroxide DTAP and di-tert-butyl peroxide DTBP.

[0055] In some embodiments of the present invention, the raw materials for preparing the bio-based material include vegetable oil containing three or more epoxy groups;

[0056] The hydrophilic modifier includes a monomer containing a secondary amino group and a sulfonic acid group;

[0057] The epoxy resin includes a bisphenol type epoxy resin.

[0058] The preferred bio-based material of the present invention contains more than three epoxy groups, which can ensure that one hydrophilic modifier and no less than one double bond-containing monomer can be grafted onto each bio-based material.

[0059] In some embodiments of the present invention, the inhibitor comprises p-hydroxyanisole (MEHQ).

[0060] 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.

[0061] In some embodiments of the present invention, the blocked cationic thermal initiator includes at least one of CTI-100, CTI-200, CTI-300 and Vicbase TC3631.

[0062] 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.

[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] The second aspect of the present invention provides a photocurable epoxy-acrylic-polyurethane hybrid dispersion, which is prepared by the preparation method.

[0065] In some embodiments of the present invention, the bio-based content of the photocurable epoxy-acrylic-polyurethane hybrid dispersion is ≥ 9%; the pH is 6.5-7.5; the particle size is < 110 nm, and the solid content is 38-41%.

[0066] The light-curing epoxy-acrylic-polyurethane hybrid dispersion prepared by the present invention has the characteristics of large molecular weight, high bio-based content, good storage stability, good appearance, high reaction activity, good tolerance, excellent adhesion to various substrates, etc.; and the preparation method has the advantages of simple operation, easy control and low cost, and can prepare light-curing epoxy-acrylic-polyurethane hybrid dispersions in batches.

[0067] The third aspect of the present invention provides a water-based photocurable bio-based coating, and the raw materials for preparing the water-based photocurable bio-based coating include the photocurable epoxy-acrylic-polyurethane hybrid dispersion.

[0068] In some embodiments of the present invention, a waterborne photocurable bio-based coating comprises the following components in parts by weight:

[0069]

[0070]

[0071] The present invention disperses the blocked cationic thermal initiator, cationic photoinitiator, free radical photoinitiator and resin together, which can make the photocurable groups inside the latex particles react more fully. The initiator added during the preparation of the coating 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.

[0072] In some embodiments of the present invention, the photoinitiator includes at least one of Darocur 1173, Irgacure 2959, Irgacure 500, Lucirin TPO-L, and Irgacure 819-DW.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In some embodiments of the present invention, the dispersant includes at least one of DISPERBYK-191 and DISPERS 755W.

[0077] In some embodiments of the present invention, the titanium dioxide includes at least one of NTR-606 and Ti-Pure R-902+.

[0078] In some embodiments of the present invention, the defoaming agent includes at least one of TEGO-800, TEGO-805, TEGO-815, TEGO-825, modified polysiloxane copolymer solution BYK-019 and BYK-020.

[0079] In some embodiments of the present invention, the thickener includes at least one of a nonionic polyurethane associative thickener RM-8W, a hydrophobically modified alkali-swellable associative thickener TT-935, an alkali-swellable non-associative thickener ASE-60, and nonionic associative thickeners TEGO ViscoPlus 3000, TEGO ViscoPlus 3030, and TEGO ViscoPlus 3060.

[0080] In some embodiments of the present invention, the wetting agent includes at least one of polyether siloxane copolymer TEGO-245, nonionic organic surfactant TEGO-500, and polyether modified polysiloxane solution BYK-346.

[0081] In some embodiments of the present invention, the method for preparing the water-based cationic light-curable bio-based coating comprises the following steps:

[0082] Water and a film-forming aid are premixed and added to a photocurable epoxy-acrylic-polyurethane hybrid dispersion, and then a photodispersant, titanium dioxide, an initiator, a defoamer, a thickener and a wetting agent are added in sequence, dispersed for 10-30 minutes, and filtered to obtain a water-based photocurable bio-based coating.

[0083] A fourth aspect of the present invention provides an application of a water-based photocurable bio-based coating in the fields of wood product preparation, automobile manufacturing or metal product corrosion protection.

[0084] In the water-based photocurable bio-based coating of the present invention, 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 cross-linking density, high flexibility and excellent adhesion to various substrates, and can be applied to high-end wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings. DETAILED DESCRIPTION

[0085] 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.

[0086] 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.

[0087] The hydrophilic chain extender used in the following examples is dimethylol propionic acid DMPA, dimethylol butyric acid DMBA from Aladdin or Ymer N120 from Perstorp;

[0088] It is further specified that the acrylic acid monomers are acrylic acid AA and methacrylic acid MAA of Sanmu Company;

[0089] It is further defined that the (meth)acrylate monomers are methyl methacrylate MMA, butyl acrylate BA, isobornyl acrylate IBOA, cyclohexyl methacrylate CHMA, and benzyl methacrylate BZMA of Sanmu Company;

[0090] The vinyl monomer is styrene St or vinyl acetate VAc from Sanmu Company;

[0091] It is further specified that the low-temperature initiator is benzoyl peroxide BPO, azobisisobutyronitrile AIBN, and azobisisoheptanenitrile ABVN produced by Jinjinle Company;

[0092] It is further defined that the epoxy resin is one of E-54, E-51, E-44, E-42, E-39-D and E-35 of Baling Petrochemical Company.

[0093] It is further defined that the macromolecular diol is one of the polyether diol N220, polybutylene adipate diol PBA2000, and polycarbonate diol PCDL2000 with a molecular weight of 1000 to 2000 produced by Perstorp.

[0094] It is further specified that the diisocyanate monomers are isophorone diisocyanate IPDI, toluene diisocyanate TDI, hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI, and 4,4'-dicyclohexylmethane diisocyanate HMDI of Wanhua Company.

[0095] It is further specified that the small molecule diol chain extenders are 1,4-butanediol BDO, 2,4-diethyl-1,5-pentanediol PD-9, ethyl butyl propanediol BEPD, 1,6-hexanediol HDO, and neopentyl glycol NPG from Aladdin.

[0096] Further defined, bio-based materials are special epoxy soybean oil GreenSoft D, special epoxy soybean oil GreenSoft H, epoxy linseed oil ELO produced by Xingbang Polymer Materials Co., Ltd. 9-5 TM One of a kind.

[0097] It is further defined that the hydrophilic modifier is one of cyclohexylaminoethanesulfonic acid CHES, cyclohexylaminopropanesulfonic acid CAPS or cyclohexylaminobutanesulfonic acid CABS from Aladdin.

[0098] It is further specified that the high temperature initiator is di-tert-amyl peroxide DTAP or di-tert-butyl peroxide DTBP produced by Jinjinle Company.

[0099] It is further defined that the blocked cationic thermal initiator is one of CTI-100, CTI-200, CTI-300 of Shenzhen Youyang Company and Vicbase TC3631 of Shenzhen Keyi Applied Materials Co., Ltd.

[0100] It is further defined that the cationic photoinitiator is HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976 from Huiren Hengtong Company, and Omnirad250 from IGM Company.

[0101] It is further defined that the free radical photoinitiator is one or more of Darocur 1173, Irgacure 2959, Irgacure 500, Lucirin TPO-L, and Irgacure 819-DW from IGM;

[0102] It is further defined that the acrylamide-based monomer is diacetone acrylamide DAAM, N-butoxymethyl acrylamide, and hydroxyethyl acrylamide.

[0103] It is further specified that the sulfonic acid neutralizing agent is triethylamine TEA, N,N-dimethylethanolamine, or N,N-dimethylcyclohexylamine DMCHA from Dow Chemical.

[0104] Basic performance tests include: epoxy modified light-curing polyacrylate 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 group concentrations are obtained by theoretical calculations, and the double bond and epoxy group concentrations are the ratio of the amount of double bond or epoxy group substance to the mass of the solid content of the emulsion or coating, in mol / 100g.

[0105] Example 1

[0106] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 1 is prepared by the following steps:

[0107] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A1 and set aside;

[0108] S2. In parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide, 22.5 parts of epoxy resin E51 were mixed to form a mixed solution B1 for standby use;

[0109] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A1 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and 2.3 parts of ethyl butyl propylene glycol BEPD were added after reacting for 50 minutes, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B1 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C1 for standby use;

[0110] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D1 for standby use;

[0111] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E1 and set aside;

[0112] S6. In parts by mass, 22.2 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 13.2 parts of triethylene glycol divinyl ether DVE-3 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 F1, which was set aside;

[0113] S7. In parts by mass, 0.8 parts of a blocked cationic thermal initiator CTI-100, 1.0 parts of a cationic photoinitiator HRcure9387 and 0.8 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture G1 for standby use;

[0114] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D1 is heated to 150°C, the mixed solution E1 is dripped into it at a constant pressure within 4 hours. After dripping, 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, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, C1 is added, F1 is added after stirring for 15 minutes, the reaction is continued for 30 minutes, G1 is added, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 5 minutes, 305 parts of deionized water are added after stirring for 5 minutes, and the mixture is dispersed at high speed for 10 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 1.

[0115] Example 2

[0116] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 2 is prepared by the following steps:

[0117] S1. In parts by mass, 1.0 part of Ymer N120, 1.4 parts of dimethylol propionic acid DMPA and 1.0 parts of triethylamine TEA were mixed to form a mixture A2 for later use;

[0118] S2. In parts by mass, 2.5 parts of methacrylic acid MAA, 8.8 parts of methyl methacrylate MMA, 20 parts of butyl acrylate BA, 6.2 parts of cyclohexyl methacrylate CHMA, 6.3 parts of styrene St, 0.5 parts of azobisisobutyronitrile AIBN, 25 parts of epoxy resin E44 were mixed to form a mixed solution B2 for standby use;

[0119] S3. In a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, 15 parts of polyether diol N220 and mixture A2 were added, stirring was started, heated to 75 ° C, stabilized for 10 minutes, 11.1 parts of isophorone diisocyanate IPDI were added, and 2.5 parts of PD-9 were added after reacting for 60 minutes. The reaction was continued for 60 minutes, cooled to 60 ° C, and the mixed solution B2 was dripped at a constant pressure within 4 hours, heated to 85 ° C, and kept warm for 2 hours to form a prepolymer C2 for standby use;

[0120] S4. 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, 5.9 parts of cyclohexylaminobutanesulfonic acid CABS were added, and the reaction was carried out for 60 minutes to obtain a hydrophilic modified bio-based material D2 for standby use;

[0121] S5. In parts by mass, in parts by mass, 2.5 parts of methacrylic acid MAA, 7.5 parts of methyl methacrylate MMA, 6.8 parts of butyl acrylate BA, 5.5 parts of cyclohexyl methacrylate CHMA, 6.2 parts of styrene St, 0.3 parts of di-tert-butyl peroxide DTBP were mixed to form a mixed solution E2 and set aside;

[0122] S6. In parts by mass, 16.5 parts of hexamethylene diisocyanate HDI were heated to 60 ° C, and 16.7 parts of cyclohexyl-1,4-dimethanol monovinyl ether were added dropwise at a constant pressure within 10 minutes, and the reaction was continued for 0.5 hours to obtain a prepolymer F2 containing a vinyl group and an isocyanate group, which was set aside;

[0123] S7. In parts by mass, 0.6 parts of a blocked cationic thermal initiator CTI-200, 1.1 parts of a cationic photoinitiator HRcure9388 and 0.6 parts of a free radical photoinitiator Irgacure2959 were mixed to form a mixture G2 for standby use;

[0124] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D2 is heated to 140°C, the mixed solution E2 is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 25 minutes. The temperature is lowered to 70°C, 0.01 parts of inhibitor MEHQ are added, 8.4 parts of N-butoxymethyl acrylamide are added, the reaction is continued for 50 minutes, the temperature is lowered to 45°C, C2 is added, F2 is added after stirring for 10 minutes, the reaction is continued for 45 minutes, G2 is added, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 3 minutes, 312 parts of deionized water are added after stirring for 3 minutes, and the dispersion is dispersed at high speed for 15 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 2.

[0125] Example 3

[0126] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 3 is prepared by the following steps:

[0127] S1. In parts by mass, 1.1 parts of Ymer N120, 1.2 parts of dimethylol propionic acid DMPA and 0.9 parts of triethylamine TEA were mixed to form a mixture A3 and set aside;

[0128] S2. In parts by mass, 2.3 parts of methacrylic acid AA, 7.5 parts of methyl methacrylate MMA, 18.7 parts of butyl acrylate BA, 7.5 parts of Bian methacrylate BNMA, 7.5 parts of styrene St, 0.6 parts of azobisisoheptanenitrile ABVN, 20 parts of epoxy resin E35 were mixed to form a mixed solution B3 and set aside;

[0129] S3. In a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, 15 parts of polycarbonate diol PCDL2000 and mixture A3 were added, stirring was started, heated to 70°C, stabilized for 15 minutes, 10.4 parts of hydrogenated MDI were added, and after reacting for 60 minutes, 1.0 parts of 1,4-butanediol BDO were added, and the reaction was continued for 60 minutes, and the temperature was lowered to 60°C. The mixed solution B3 was added dropwise at a constant pressure within 4 hours, and the temperature was raised to 75°C, and the temperature was kept for 3 hours to form a prepolymer C3 for standby use;

[0130] S4. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 18.5 parts of epoxy linseed oil ELO were added. 9-5 TM , stirring and heating, raising the temperature to 70°C, adding 5.2 parts of cyclohexylaminoethanesulfonic acid CHES, reacting for 30 minutes, and obtaining a hydrophilic modified bio-based material D3 for standby use;

[0131] S5. In parts by mass, in parts by mass, 2.5 parts of methacrylic acid MAA, 6.2 parts of methyl methacrylate MMA, 8.8 parts of butyl acrylate BA, 7.5 parts of Bian methacrylate BNMA, 3.8 parts of styrene St, 0.4 parts of di-tert-butyl peroxide DTBP were mixed to form a mixed solution E3 and set aside;

[0132] S6. When 26.7 parts of hydrogenated MDI were heated to 50 ° C, 11.8 parts of 4-hydroxybutyl vinyl ether HBVE were added dropwise at a constant pressure within 20 minutes, and the reaction was continued for 1 hour to obtain a prepolymer containing vinyl and isocyanate groups F3, which was set aside;

[0133] S7. In parts by mass, 0.7 parts of a blocked cationic thermal initiator CTI-300, 1.3 parts of a cationic photoinitiator HRcure6992 and 0.5 parts of a free radical photoinitiator Irgacrue500 were mixed to form a mixture G3 for standby use;

[0134] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D3 is heated to 145°C, the mixed solution E3 is dripped into it at a constant pressure within 4 hours. After dripping, the mixture is stirred and kept warm for 40 minutes. The temperature is lowered to 75°C, 0.01 parts of polymerization inhibitor MEHQ are added, 6.2 parts of hydroxyethyl acrylamide are added, the reaction is continued for 60 minutes, the temperature is lowered to 50°C, C3 is added, F3 is added after stirring for 15 minutes, the reaction is continued for 40 minutes, G3 is added, 5.7 parts of N,N-dimethylcyclohexylamine DMCHA are added after stirring for 5 minutes, 299 parts of deionized water are added after stirring for 5 minutes, and the mixture is dispersed at high speed for 20 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 3.

[0135] Comparative Example 1

[0136] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 4, the difference between this comparative example and the example is that the addition ratio of epoxy resin E51 is too high, which is prepared by the following steps:

[0137] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A4 and set aside;

[0138] S2. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide, 45 parts of epoxy resin E51 were mixed to form a mixed solution B4 and set aside;

[0139] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A4 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and 2.3 parts of ethyl butyl propylene glycol BEPD were added after reacting for 50 minutes, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B1 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C4 for standby use;

[0140] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D4 for standby use;

[0141] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E4 and set aside;

[0142] S6. In parts by mass, 24.5 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 14.6 parts of triethylene glycol divinyl ether DVE-3 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 F4, which was set aside;

[0143] S7. In parts by mass, 0.8 parts of a blocked cationic thermal initiator CTI-100, 1.0 parts of a cationic photoinitiator HRcure9387 and 0.8 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture G4 for standby use;

[0144] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D4 is heated to 150°C, the mixed solution E4 is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 30 minutes. The temperature is lowered to 80°C, 0.01 parts of inhibitor MEHQ are added, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, C4 is added, F4 is added after stirring for 15 minutes, the reaction is continued for 30 minutes, G4 is added, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 5 minutes, 345 parts of deionized water are added after stirring for 5 minutes, and the dispersion is dispersed at high speed for 10 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 4.

[0145] Comparative Example 2

[0146] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 5, which is different from the comparative example in that no epoxy resin is added, is prepared by the following steps:

[0147] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A5 and set aside;

[0148] S2. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide were mixed to form a mixed solution B5 and set aside;

[0149] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A5 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and 2.3 parts of ethyl butyl propylene glycol BEPD were added after reacting for 50 minutes, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B5 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C5 for standby use;

[0150] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D5 for standby use;

[0151] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E5 and set aside;

[0152] S6. In parts by mass, 21.9 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 13 parts of triethylene glycol divinyl ether DVE-3 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 F5, which was set aside;

[0153] S7. In parts by mass, 0.8 parts of a blocked cationic thermal initiator CTI-100, 1.0 parts of a cationic photoinitiator HRcure9387 and 0.8 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture G5 for standby use;

[0154] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D5 is heated to 150°C, the mixed solution E5 is dripped into it at a constant pressure within 4 hours. After dripping, it is stirred and kept warm for 30 minutes, then cooled to 80°C, 0.01 parts of inhibitor MEHQ are added, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is cooled to 50°C, C5 is added, F5 is added after stirring for 15 minutes, the reaction is continued for 30 minutes, G5 is added, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 5 minutes, 271 parts of deionized water are added after stirring for 5 minutes, and the dispersion is dispersed at high speed for 10 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 5.

[0155] Comparative Example 3

[0156] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 6, the difference between this comparative example and the embodiment is that the added epoxy resin is non-bisphenol A type epoxy resin, which is prepared by the following steps:

[0157] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A6 for later use;

[0158] S2. In parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide, 22.5 parts of epoxy resin MF-4101 were mixed to form a mixed solution B6 for standby use;

[0159] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A6 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and 2.3 parts of ethyl butyl propylene glycol BEPD were added after reacting for 50 minutes, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B6 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C6 for standby use;

[0160] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D6 for standby use;

[0161] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E6 for standby use;

[0162] S6. In parts by mass, 21.9 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 13 parts of triethylene glycol divinyl ether DVE-3 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 F6 for standby use;

[0163] S7. In parts by mass, 0.8 parts of a blocked cationic thermal initiator CTI-100, 1.0 parts of a cationic photoinitiator HRcure9387 and 0.8 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture G6 for standby use;

[0164] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D6 is heated to 150°C, the mixed solution E6 is dripped into it at a constant pressure within 4 hours. After dripping, 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, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, C6 is added, F6 is added after stirring for 15 minutes, the reaction is continued for 30 minutes, G6 is added, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 5 minutes, 305 parts of deionized water are added after stirring for 5 minutes, and the mixture is dispersed at high speed for 10 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 6.

[0165] Comparative Example 4

[0166] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 7 is prepared by the following steps:

[0167] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A7 and set aside;

[0168] S2. In parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide, 22.5 parts of epoxy resin E51 were mixed to form a mixed solution B7 for standby use;

[0169] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A7 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and after reacting for 50 minutes, 7.5 parts of ethyl butyl propylene glycol BEPD were added, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B7 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C7 for standby use;

[0170] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D7 for standby use;

[0171] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E7 and set aside;

[0172] S6. When 36.6 parts of isophorone diisocyanate IPDI were heated to 50 ° C, 21.7 parts of triethylene glycol divinyl ether DVE-3 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 F7, which was set aside;

[0173] S7. In parts by mass, 0.8 parts of a blocked cationic thermal initiator CTI-100, 1.0 parts of a cationic photoinitiator HRcure9387 and 0.8 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture G7 for standby use;

[0174] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D7 is heated to 150°C, the mixed solution E7 is dripped into it at a constant pressure within 4 hours. After dripping, the mixture is stirred and kept warm for 30 minutes. The temperature is lowered to 80°C, 0.01 parts of polymerization inhibitor MEHQ are added, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, C7 is added, F7 is added after stirring for 15 minutes, the reaction is continued for 30 minutes, G1 is added, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 5 minutes, 348 parts of deionized water are added after stirring for 5 minutes, and the mixture is dispersed at high speed for 10 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 7.

[0175] Comparative Example 5

[0176] A photocurable epoxy-acrylic-polyurethane hybrid dispersion 8, which is different from the comparative example in that no blocked cationic thermal initiator is added, is prepared by the following steps:

[0177] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A8 and set aside;

[0178] S2. In parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide, 22.5 parts of epoxy resin E51 were mixed to form a mixed solution B8 and set aside;

[0179] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A8 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and 2.3 parts of ethyl butyl propylene glycol BEPD were added after reacting for 50 minutes, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B8 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C8 for standby use;

[0180] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D8 for standby use;

[0181] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E8 and set aside;

[0182] S6. In parts by mass, 22.2 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 13.2 parts of triethylene glycol divinyl ether DVE-3 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 F8, which was set aside;

[0183] S7. In parts by mass, 1.0 parts of a cationic photoinitiator HRcure9387 and 0.8 parts of a free radical photoinitiator Darocur1173 were mixed to form a mixture G8 for later use;

[0184] S8. In terms of mass fractions, when the hydrophilic modified bio-based material D8 is heated to 150°C, the mixed solution E8 is dripped into it at a constant pressure within 4 hours. After dripping, the mixture is stirred and kept warm for 30 minutes, then cooled to 80°C, 0.01 parts of polymerization inhibitor MEHQ are added, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is cooled to 50°C, C8 is added, F8 is added after stirring for 15 minutes, G8 is added after continuing the reaction for 30 minutes, 3.8 parts of N,N-dimethylethanolamine DMEA are added after stirring for 5 minutes, 304 parts of deionized water are added after stirring for 5 minutes, and the material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 8.

[0185] Comparative Example 6

[0186] An epoxy-modified light-curable polyacrylate dispersion 9, in which the photoinitiator and the blocked thermal initiator are not dispersed together with the resin, but are only added during the coating preparation stage, and the other conditions are the same.

[0187] S1. In parts by mass, 1.3 parts of Ymer N120, 1.1 parts of dimethylolbutyrate DMBA and 0.8 parts of triethylamine TEA were mixed to form a mixture A9 and set aside;

[0188] S2. In parts by mass, 2.0 parts of acrylic acid AA, 6.3 parts of methyl methacrylate MMA, 17.5 parts of butyl acrylate BA, 8.8 parts of isobornyl acrylate IBOA, 8.7 parts of styrene St, 0.6 parts of benzoyl peroxide, 22.5 parts of epoxy resin E51 were mixed to form a mixed solution B9 for standby use;

[0189] S3. In parts by mass, 15 parts of polybutylene adipate diol PBA2000 and mixture A8 were added to a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel, stirring was started, heated to 80 ° C, stabilized for 15 minutes, 6.7 parts of hexamethylene diisocyanate HDI were added, and 2.3 parts of ethyl butyl propylene glycol BEPD were added after reacting for 50 minutes, and the reaction was continued for 50 minutes, cooled to 65 ° C, and the mixture B8 was added dropwise at a constant pressure within 4 hours, heated to 80 ° C, and kept warm for 2 hours to form a prepolymer C9 for standby use;

[0190] S4. 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, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS were added, and the reaction was carried out for 75 minutes to obtain a hydrophilic modified bio-based material D9 for standby use;

[0191] S5. In parts by mass, in parts by mass, 2.0 parts of acrylic acid AA, 8.7 parts of methyl methacrylate MMA, 5 parts of butyl acrylate BA, 4.3 parts of isobornyl acrylate IBOA, 8.3 parts of styrene St, 0.3 parts of di-tert-amyl peroxide DTAP were mixed to form a mixed solution E9 and set aside;

[0192] S6. In parts by mass, 22.2 parts of isophorone diisocyanate IPDI were heated to 50 ° C, and 13.2 parts of triethylene glycol divinyl ether DVE-3 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 F9, which was set aside;

[0193] S7. In terms of mass fractions, when the hydrophilic modified bio-based material D9 is heated to 150°C, the mixed solution E9 is dripped into it at a constant pressure within 4 hours. After dripping, the mixture is stirred and kept warm for 30 minutes. The temperature is lowered to 80°C, 0.01 parts of polymerization inhibitor MEHQ are added, 9.3 parts of diacetone acrylamide DAAM are added, the reaction is continued for 40 minutes, the temperature is lowered to 50°C, C9 is added, F9 is added after stirring for 15 minutes, 3.8 parts of N,N-dimethylethanolamine DMEA are added after the reaction is continued for 30 minutes, 304 parts of deionized water are added after stirring for 5 minutes, and the mixture is dispersed at high speed for 10 minutes. The material is filtered to obtain a light-cured epoxy-acrylic-polyurethane hybrid dispersion 9.

[0194] Test Example 1

[0195] Test Example A water-based photocurable bio-based coating was prepared. The photocurable epoxy-acrylic-polyurethane hybrid dispersion was prepared in the example and the comparative example. The specific steps were as follows:

[0196] The water-based photocurable bio-based coating is composed of the following components in parts by weight:

[0197] 50.8 parts of light-cured epoxy-acrylic-polyurethane hybrid dispersion;

[0198]

[0199]

[0200] The preparation method of the water-based photocurable bio-based coating is as follows: a photocurable epoxy-acrylic-polyurethane hybrid dispersion is added into a stirring kettle at a rotation speed of 700 rpm, water, propylene glycol butyl ether and propylene glycol methyl ether are premixed and added into the stirring kettle, Darocur 1173, Lucirin TPO-L, Omnirad250, BYK-191, titanium dioxide, TEGO-805, TT-935 and BYK-346 are added in sequence, dispersed for 20 minutes, filtered and discharged, and the water-based photocurable bio-based coating is obtained.

[0201] The paint film made of water-based bio-based photocurable coating was dried at 50°C for 2 hours, the mercury lamp was turned on in the photocuring machine, and the UVV energy was adjusted to 600mJ / cm2 for curing. After curing, it was baked at 100°C for 2 hours. Its properties are shown in Table 1.

[0202] The test standards are:

[0203] Coating appearance: visual inspection;

[0204] Pencil hardness: GB / T6739-2006;

[0205] Coating gloss / (60°,%): GB / T9754-2007;

[0206] Water resistance (25℃, 24h): GB / T4893.1-2020;

[0207] Dry heat resistance (70±2℃, 15h): GB / T4893.3-2020;

[0208] Ethanol resistance (50%, 1h): GB / T4893.1-2020;

[0209] Adhesion: GB / T9286-2021;

[0210] Table 1 Performance parameters of cationic photocurable epoxy-acrylic-polyurethane hybrid dispersions and waterborne photocurable bio-based coatings

[0211]

[0212]

[0213] It can be seen from the above table that compared with Example 1, Comparative Example 1 has poor dispersion stability and low paint film gloss due to excessively high addition ratio of epoxy resin E51; Compared with Example 1, Comparative Example 2 has poor adhesion to substrates such as pine, glass, tinplate, and melamine board due to no addition of epoxy resin. In addition, only double bonds of vinyl ethers can be subjected to cationic photocuring, and the concentration of reactive groups is reduced, resulting in poor paint film resistance; Compared with Example 1, Comparative Example 3 has a non-bisphenol A epoxy resin, and its epoxy group has higher reactivity and can react with the secondary amine group of polyurethane, thereby causing poor dispersion stability, and it does not undergo graft polymerization with acrylate, resulting in low paint film gloss. Compared with Example 1, in Comparative Example 4, polyurethane in C7 is OH-terminated (C7 is a reaction of multiple hydroxyl-containing components and isocyanate-containing components. If the total hydroxyl content of the hydroxyl-containing component is higher than the isocyanate group of the isocyanate-containing component, it is a terminal hydroxyl group, otherwise it is a terminal NCO), and polyurethane in C1 is NCO-terminated. NCO will react with the hydroxyl group after the ring opening of epoxy resin or bio-based materials to improve the compatibility of epoxy resin and polyacrylate resin and polyurethane resin. Therefore, the epoxy resin and polyacrylate resin and polyurethane resin of Comparative Example 4 have poor compatibility, thereby making the transparency and resistance of the paint film worse. Compared with Example 1, Comparative Example 5 does not add a blocked cationic thermal initiator, and the deep curing of the paint film is worse than that of Example 1. Therefore, the adhesion and hardness of the paint film are poor. Compared with Example 1, Comparative Example 6 does not add a photoinitiator and a blocked cationic thermal initiator, and the paint film has poor resistance, low hardness, and poor adhesion. It can be seen from Examples 1, 2, and 3 that the present invention discloses a method for preparing an epoxy-acrylic-polyurethane hybrid dispersion, and the paint film made of the prepared cationic photocurable bio-based coating has the advantages of good flexibility, good water resistance and chemical resistance, and excellent adhesion to various substrates, and can be applied to high-end wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings.

[0214] 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 a light-cured epoxy-acrylic-polyurethane hybrid dispersion, characterized in that: The preparation method comprises the following steps: S1. The hydrophilic chain extender and the neutralizer are mixed to form a mixture A; S2. The acrylic monomer, acrylate monomer, vinyl monomer, free radical polymerization low temperature thermal initiator, epoxy resin are mixed to form a mixed solution B; S3. The macromolecular diol, the mixture A, the diisocyanate, the small molecule chain extender and the mixed solution B are mixed to form a prepolymer C; S4. mixing the bio-based material and the hydrophilic modifier to obtain a hydrophilic modified bio-based material D; S5. The acrylic acid monomer, the acrylate monomer, the vinyl monomer, and the free radical polymerization high temperature thermal initiator are mixed to form a mixed solution E; S6. The diisocyanate and the hydroxy vinyl ether are mixed and reacted to obtain a prepolymer F containing a vinyl group and an isocyanate group; S7. The blocked cationic thermal initiator, the cationic photoinitiator and the free radical photoinitiator are mixed to form a mixture G; S8. The hydrophilic modified bio-based material D, the mixed solution E, the polymerization inhibitor, the acrylamide-based monomer, the prepolymer C, the prepolymer F, the mixture G, and the neutralizer are mixed and dispersed to react to obtain a photocurable epoxy-acrylic-polyurethane hybrid dispersion.

2. The preparation method according to claim 1, characterized in that: The preparation method comprises the following steps: S1. Mix 2 to 2.5 parts of a hydrophilic chain extender and 0.5 to 1.0 parts of a neutralizing agent to form a mixture A, in parts by mass; S2. By weight, 1.5 to 2.5 parts of acrylic acid monomer, 30 to 36 parts of acrylate monomer, 6 to 9 parts of vinyl monomer, 0.3 to 0.6 parts of free radical polymerization low temperature thermal initiator, and 20 to 25 parts of epoxy resin are mixed to form a mixed solution B; S3. By weight, 10 to 25 parts of a macromolecular diol and a mixture A, 6 to 12 parts of a diisocyanate, 1 to 3 parts of a small molecule chain extender and a mixture B are mixed to form a prepolymer C; S4. By weight, 18 to 26 parts of the bio-based material and 5 to 6 parts of the hydrophilic modifier are reacted to obtain a hydrophilic modified bio-based material D; S5. In parts by mass, 2 to 3 parts of acrylic acid monomer, 15 to 25 parts of acrylate monomer, 3 to 9 parts of vinyl monomer, and 0.3 to 0.6 parts of free radical polymerization high temperature thermal initiator are mixed to form a mixed solution E; S6. By weight, 15 to 30 parts of diisocyanate and 11 to 20 parts of hydroxy vinyl ether are mixed and reacted to obtain a prepolymer F containing a vinyl group and an isocyanate group; S7. In parts by mass, 0.5 to 1.0 parts of a blocked cationic thermal initiator, 1.0 to 1.5 parts of a cationic photoinitiator and 0.5 to 1.0 parts of a free radical photoinitiator are mixed to form a mixture G; S8. In parts by mass, the hydrophilic modified bio-based material D, the mixed solution E, 0.01 parts of an inhibitor, 5 to 10 parts of an acrylamide-based monomer, a prepolymer F, a mixture G, and 3 to 6 parts of a neutralizer are mixed and dispersed to react to obtain a photocurable epoxy-acrylic-polyurethane hybrid dispersion.

3. The preparation method according to claim 1, characterized in that: The epoxy resin includes a bisphenol type epoxy resin.

4. The preparation method according to claim 1, characterized in that: The raw materials for preparing the bio-based material include vegetable oil containing more than three epoxy groups; The hydrophilic modifier includes a monomer containing a secondary amino group and a sulfonic acid group; The epoxy resin includes a bisphenol type epoxy resin.

5. The preparation method according to claim 1, characterized in that: The neutralizing agent includes a tertiary amine neutralizing agent.

6. 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.

7. The preparation method according to claim 1, characterized in that: The macromolecular diol includes at least one of polyether diol, polybutylene adipate diol and polycarbonate diol.

8. A light-cured epoxy-acrylic-polyurethane hybrid dispersion, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 7.

9. A water-based photocurable bio-based coating, characterized in that: The raw materials for preparing the water-based light-cured bio-based coating include the light-cured epoxy-acrylic-polyurethane hybrid dispersion described in claim 8.

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

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