Waterborne two-component photocurable coating, and preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of coatings. Disclosed are a waterborne two-component photocurable coating, and a preparation method therefor and a use thereof. Preparation raw materials for the waterborne two-component photocurable coating of the present invention comprise: an acrylic monomer, an acrylate monomer, an initiator, an isocyanate monomer, a hydroxy vinyl ether, a bio-based material, a hydrophilic modifier, an epoxy resin, an acrylamide-based monomer, and a neutralizer. In the preparation raw materials, the bio-based material is a vegetable oil containing three or more epoxy groups, and the epoxy resin is an epoxy resin containing three or more epoxy groups. A double-bond-containing component of the waterborne two-component photocurable coating is a polyacrylate dispersion containing vinyl ether double bonds and acrylamide double bonds, and an epoxy-containing component of the waterborne two-component photocurable coating is a hydrophilically modified epoxy resin. A paint film of the waterborne two-component photocurable coating of the present invention has the characteristics of high flexibility, good chemical resistance, excellent adhesion to various substrates, etc.

Description

Water-based two-component photocuring coating, preparation method and application thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of coating, in particular relates to a water-based two-component photocuring coating, preparation method and application thereof. BACKGROUND

[0002] Water-based coating mainly includes water-based single-component coating, water-based polyurethane two-component coating, and water-based photocuring coating which has developed rapidly in recent years. The film performance of single-component water-based coating, such as water resistance, chemical resistance and hardness, is greatly different from that of solvent-based coating, which seriously limits the popularization and application of water-based coating. The mechanical properties, water resistance and chemical resistance of water-based polyurethane two-component coating are close to those of solvent-based coating, but due to the problem of activation period, it is not suitable for reciprocating mechanical spraying and electrostatic spraying, and its drying speed is slow, which affects the construction efficiency. The mechanical properties, water resistance and chemical resistance of water-based photocuring coating are better than those of solvent-based products, there is no activation period, it is suitable for various mechanical spraying, and after drying for 0.5-2 hours after construction, it can be cured by ultraviolet light curing machine and then packed. The main component of water-based photocuring coating is water-based photocuring resin. At present, the main products in the market are free radical photocuring polyurethane dispersions, which are mainly prepared by end-capping polyurethane prepolymer with hydroxyl-containing acrylic monomers. The end-capping process limits the molecular weight of the prepolymer, and the double bond is only at both ends of the polymer. The characteristics of this process cause the products on the market to have the problems of poor storage stability and low reaction activity. In addition, the free radical photocuring film has a large shrinkage rate and poor adhesion to many substrates. The above shortcomings greatly limit the popularization and application of water-based photocuring coating.

[0003] Therefore, it is necessary to develop a water-based photocuring resin with good storage stability and good adhesion to various substrates. SUMMARY

[0004] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a water-based two-component photocuring coating, preparation method and application thereof. The film of the water-based two-component photocuring 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, and can be applied to high-grade wood coating, automobile coating, metal anticorrosive coating and other industrial protective coating.

[0005] The present application also provides a water-based two-component photocuring coating.

[0006] The present application also provides the application of a water-based two-component photocuring coating in the field of wood product preparation, automobile manufacturing or metal product corrosion prevention.

[0007] The first aspect of the present application provides a preparation method of a water-based two-component photocuring coating, raw materials for preparing the water-based two-component photocuring coating comprising: a double-bond-containing component cationic photocuring polyacrylate dispersion and an epoxy-group-containing component hydrophilically modified epoxy resin;

[0008] The preparation method of the double-bond-containing component cationic photocuring polyacrylate dispersion comprises:

[0009] A1. uniformly mixing acrylic monomers, acrylate monomers, vinyl monomers, and initiators to form a mixed solution A;

[0010] A2. reacting diisocyanate and hydroxy vinyl ether to obtain a vinyl and isocyanate group-containing prepolymer B;

[0011] A3. reacting a bio-based material and a hydrophilic modifier to obtain a hydrophilically modified bio-based material C;

[0012] A4. mixing a blocked cationic thermal initiator, a cationic photoinitiator, and a free radical photoinitiator to form a mixture D;

[0013] A5. mixing the hydrophilically modified bio-based material C, the mixed solution A, a polymerization inhibitor, an acrylamide monomer, the vinyl and isocyanate group-containing prepolymer B, the mixture D, and a neutralizing agent, dispersing, filtering, and discharging to obtain the double-bond-containing component cationic photocuring polyacrylate dispersion;

[0014] The preparation method of the epoxy-group-containing component hydrophilically modified epoxy resin comprises:

[0015] B1. mixing and reacting an epoxy resin, a hydrophilic modifier, and a neutralizing agent to form the epoxy-group-containing component hydrophilically modified epoxy resin.

[0016] The embodiments according to the first aspect of the present application have at least the following beneficial effects:

[0017] The present application introduces a cationic photocuring system and an epoxy group, reduces the shrinkage of the paint film, and improves the adhesion of the paint film on various substrates; the double-bond-containing component cationic photocuring polyacrylate dispersion and the epoxy-group-containing hydrophilically modified epoxy resin are packaged separately, which ensures the storage stability of the photocuring coating and can adjust the addition proportion of the epoxy-group-containing component according to the performance requirements when used.

[0018] The closed cationic thermal initiator, the cationic photoinitiator and the photocuring polyacrylate resin are dispersed together in the application, since the component does not contain a high-activity epoxy group, the part of initiator can make the photocuring group inside the latex particle react more fully under the premise of ensuring storage stability, the initiator added during the preparation of the paint can initiate the polymerization of the photocuring group at the interface of the latex particle, the reaction degree of the photocuring group can be further improved, and the paint film resistance is improved; the closed cationic thermal initiator can provide another curing mode for the paint film curing while ensuring the storage stability.

[0019] In some embodiments of the application, the preparation method of the double-bond-containing component cationic photocuring polyacrylate dispersion includes:

[0020] A1. 1.5-2.5 parts by mass of acrylic acid monomer, 20-30 parts by mass of acrylic ester monomer, 5-11 parts by mass of vinyl monomer and 0.4-0.6 parts by mass of initiator are mixed to form a mixed solution A;

[0021] A2. 18-30 parts by mass of diisocyanate and 12-20 parts by mass of hydroxyl vinyl ether are reacted to obtain a vinyl and isocyanate group-containing prepolymer B;

[0022] A3. 18-26 parts by mass of bio-based material and 5-6 parts by mass of hydrophilic modifier are reacted to obtain a hydrophilic modified bio-based material C;

[0023] A4. 0.3-0.5 parts by mass of closed cationic thermal initiator, 0.3-0.6 parts by mass of cationic photoinitiator and 0.3-0.5 parts by mass of free radical photoinitiator are mixed to form a mixture D;

[0024] A5. The hydrophilic modified bio-based material C, the mixed solution A, the polymerization inhibitor, 6-10 parts by mass of acrylamide monomer, the vinyl and isocyanate group-containing prepolymer B, the mixture D and the neutralizing agent are mixed, dispersed, filtered and discharged to obtain a double-bond-containing component cationic photocuring polyacrylate dispersion;

[0025] The preparation method of the epoxy group-containing component hydrophilic modified epoxy resin includes:

[0026] B1. 12-20 parts by mass of epoxy resin, 8-15 parts by mass of hydrophilic modifier and a neutralizing agent are mixed and reacted to form an epoxy group-containing component hydrophilic modified epoxy resin.

[0027] In some embodiments of the application, the molar ratio of the hydrophilic modifier to the neutralizing agent is 1:0.7-0.9.

[0028] In some embodiments of the application, the preparation method of the double-bond-containing component cationic photocuring polyacrylate dispersion includes:

[0029] A1. In mass fraction, 1.5-2.5 parts of acrylic monomer, 20-30 parts of acrylic ester monomer, 5-11 parts of vinyl monomer, and 0.4-0.6 parts of initiator are mixed to form a mixed solution A;

[0030] A2. In mass fraction, 18-30 parts of diisocyanate is heated to 50-70℃, and 12-20 parts of hydroxyl vinyl ether is added dropwise at a constant pressure within 15-30 minutes. The reaction is continued for 0.8-1.5 hours to obtain a prepolymer B containing vinyl and isocyanate groups.

[0031] A3. In mass fraction, 18-26 parts of bio-based material is added to a four-necked flask equipped with a thermometer, a condenser, and a stirring paddle. The bio-based material is stirred and heated, and the temperature is raised to 55-75℃. 5-6 parts of a hydrophilic modifier is added, and the reaction is continued for 30-90 minutes to obtain a hydrophilically modified bio-based material C.

[0032] A4. In mass fraction, 0.3-0.5 parts of a blocked cationic thermal initiator, 0.3-0.6 parts of a cationic photoinitiator, and 0.3-0.5 parts of a free radical photoinitiator are mixed to form a mixture D.

[0033] A5. In mass fraction, the hydrophilically modified bio-based material C1 is heated to 130-150℃, and the mixed solution A is added dropwise at a constant pressure within 3-4 hours. After the dropwise addition is completed, the mixture is stirred and incubated for 20-40 minutes. The temperature is lowered to 60-80℃, 0.01 parts of a polymerization inhibitor is added, 6-10 parts of an acrylamide monomer is added, and the reaction is continued for 30-60 minutes. The temperature is lowered to 45-55℃, the prepolymer B is added, and the reaction is continued for 30-40 minutes. The mixture D is added, and after stirring for 5-10 minutes, 2-3.5 parts of a neutralizing agent is added. After stirring for 3-5 minutes, 135-180 parts of deionized water is added and dispersed at a high speed for 10-20 minutes. The filtrate is obtained to obtain a cationic photopolymerizable polyacrylate dispersion containing double bonds.

[0034] The preparation method of the hydrophilically modified epoxy resin containing epoxy groups includes:

[0035] B1. In mass fraction, 12-20 parts of an epoxy resin and 8-15 parts of a hydrophilic modifier are mixed. The reaction temperature is controlled at 40-45℃, and the reaction is continued for 1-2 hours. 3-5 parts of a neutralizing agent is added and stirred for 3-5 minutes to form a hydrophilically modified epoxy resin containing epoxy groups.

[0036] In some embodiments of the present application, the bio-based material contains more than three epoxy groups. The preferred bio-based material of the present application contains more than three epoxy groups. It can be ensured that one hydrophilic modifier and no less than one double bond-containing monomer can be grafted on each bio-based material.

[0037] In the present application, the groups that can participate in photocuring include vinyl ether double bonds, acryloxy double bonds and epoxy groups. Free radical photoinitiators can initiate the polymerization of acryloxy double bonds, cationic photoinitiators can initiate the polymerization of vinyl ether double bonds and epoxy groups, and when both types of photoinitiators are added at the same time, the above groups can be copolymerized. The polymerization initiated by free radical photoinitiators has a large shrinkage, obvious oxygen inhibition and poor adhesion to many substrates, while the polymerization initiated by cationic photoinitiators has a small shrinkage, no oxygen inhibition and excellent adhesion of epoxy groups to a variety of substrates, which can fully compensate for the shortcomings of free radical photocuring.

[0038] In addition, conventional water-based photocurable coatings only add photoinitiators during the coating preparation stage, and this method has the disadvantage that the internal light-curing groups of the latex particles cannot be fully reacted. In the present application, a blocked cationic thermal initiator, a cationic photoinitiator, a free radical polymerization photoinitiator and a photocurable polyacrylate resin are dispersed together. Since this component does not contain highly active epoxy groups, the initiators in this part can make the light-curing groups inside the latex particles react more fully under the premise of ensuring storage stability. The initiators added during coating preparation can initiate the polymerization of light-curing groups at the interface of the latex particles, which can further improve the reaction degree of the light-curing groups and thus improve the film resistance.

[0039] Thirdly, the addition of a blocked cationic thermal initiator can provide another curing method for film curing while ensuring storage stability. When the water-based photocurable coating is a solid color coating, ultraviolet light cannot penetrate the film, thereby causing the bottom layer of the film to be unable to cure. The film with a blocked cationic thermal initiator can be cured by baking to cure the bottom layer of the film. Some wood has a high oil content, such as pine, and the oil will come out of the substrate during baking, causing film defects such as blistering. Since such oils contain double bonds and epoxy groups, the blocked cationic thermal initiator can initiate the curing of the oil during baking, thereby avoiding causing film defects.

[0040] In some embodiments of the present application, the acrylic monomer includes at least one of acrylic acid AA and methacrylic acid MAA.

[0041] In some embodiments of the present application, the acrylic ester monomer includes a methacrylic ester monomer, and the methacrylic ester monomer includes at least one of methyl methacrylate MMA, butyl acrylate BA, isobornyl acrylate IBOA, cyclohexyl methacrylate CHMA and butyl methacrylate BNMA.

[0042] In some embodiments of the present application, the vinyl monomer includes at least one of styrene St and vinyl acetate VAc.

[0043] In some embodiments of the application, the initiator includes at least one of di-t-amyl peroxide DTAP and di-t-butyl peroxide DTBP.

[0044] In some embodiments of the application, 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 application, the hydroxyl vinyl ether includes at least one of 4-hydroxybutyl vinyl ether HBVE, triethylene glycol divinyl ether DVE, and cyclohexyl-1,4-dimethanol monovinyl ether.

[0046] In some embodiments of the application, the bio-based material includes at least one of GreenSoft D, GreenSoft H, and ELO EPOXOL® 9-5™.

[0047] In some embodiments of the application, the hydrophilic modifier includes at least one of cyclohexylaminoethanesulfonic acid CHES, cyclohexylaminopropanesulfonic acid CAPS, and cyclohexylaminobutanesulfonic acid CABS.

[0048] In some embodiments of the application, the blocked cationic thermal initiator includes at least one of CTI-100, CTI-200, CTI-300, and Vicbase TC3631.

[0049] In some embodiments of the application, the cationic photoinitiator includes at least one of HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976, and Omnirad 250.

[0050] In some embodiments of the application, the acrylamide monomer includes at least one of diacetone acrylamide DAAM, N-butoxymethyl acrylamide, and hydroxyethyl acrylamide.

[0051] In some embodiments of the application, the neutralizing agent includes at least one of triethylamine TEA, N,N-dimethylethanolamine DMEA, and N,N-dimethylcyclohexylamine DMCHA.

[0052] In some embodiments of the present application, the epoxy resin comprises at least one of tetraglycidyl diaminodimethylene benzene MF-4101, 4,5-epoxy tetrahydrophthalic acid diglycidyl ester MF-3286, and triglycidyl-p-aminophenol MF-3102.

[0053] In some embodiments of the present application, the bio-based content of the double bond containing component cationic photocuring polyacrylate dispersion is ≥10%; the pH is 6.5-7.5; the particle size is <110 nm; and the solid content is 38-41%.

[0054] The present application has the following advantages: the prepared cationic photocuring polyacrylate dispersion has high bio-based content, good storage stability, good appearance, high reactivity, good resistance, and excellent adhesion to various substrates; and the prepared hydrophilic modified epoxy resin has the characteristics of water dispersibility and high reactivity.

[0055] In some embodiments of the present application, the preparation method comprises the following steps:

[0056] The double bond containing component cationic photocuring polyacrylate dispersion and the hydrophilic modified epoxy resin are mixed in a ratio of 100: (5-15) after dispersion to obtain the water-based two-component photocuring coating.

[0057] In some embodiments of the present application, the raw materials for preparing the bio-based material comprise plant oil containing three or more epoxy groups.

[0058] The hydrophilic modifier comprises a monomer containing secondary amino groups and sulfonic acid groups.

[0059] The epoxy resin comprises an epoxy resin containing three or more epoxy groups.

[0060] In some embodiments of the present application, the neutralizing agent comprises a tertiary amine neutralizing agent.

[0061] In some embodiments of the present application, the hydroxy vinyl ether comprises at least one of 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, and cyclohexyl-1,4-dimethanol monovinyl ether.

[0062] In some embodiments of the present application, the epoxy resin comprises at least one of tetraglycidyl diaminodimethylene benzene, 4,5-epoxy tetrahydrophthalic acid diglycidyl ester, and triglycidyl-p-aminophenol.

[0063] In some embodiments of the present application, the raw materials for preparing the water-based two-component photocuring coating further comprise an auxiliary agent, and the auxiliary agent comprises a film-forming auxiliary agent, a dispersant, titanium white, a defoaming agent, a thickening agent, and a wetting agent.

[0064] In some embodiments of the present application, the raw materials for preparing the water-based two-component photocuring coating include: a cationic photocuring polyacrylate dispersion, a free radical photoinitiator, a cationic photoinitiator, water, a film-forming aid, a dispersant, titanium white, an antifoaming agent, a thickening agent, and a wetting agent.

[0065] In some embodiments of the present application, the free radical photoinitiator includes at least one of Darocur 1173, Irgacure 2959, Irgacure 500, Lucirin TPO-L, and Irgacure 819-DW.

[0066] In some embodiments of the present application, the cationic photoinitiator includes at least one of HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976, and Omnirad 250.

[0067] In some embodiments of the present application, the film-forming aid includes at least one of propylene glycol methyl ether PM, propylene glycol n-butyl ether PnB, dipropylene glycol methyl ether DPM, and dipropylene glycol n-butyl ether DPnB.

[0068] In some embodiments of the present application, the dispersant includes at least one of DISPERBYK-191 and DISPERS 755W.

[0069] In some embodiments of the present application, the titanium white includes at least one of NTR-606 and Ti-Pure R-902+.

[0070] In some embodiments of the present application, the antifoaming agent includes at least one of polyether siloxane copolymer antifoaming agent TEGO-800, TEGO-805, TEGO-815, TEGO-825, modified polysiloxane copolymer solution BYK-019, and BYK-020.

[0071] In some embodiments of the present application, the thickening agent includes at least one of nonionic polyurethane associative thickening agent RM-8W, hydrophobically modified alkali-swellable associative thickening agent TT-935, alkali-swellable non-associative thickening agent ASE-60, nonionic associative thickening agent TEGO ViscoPlus 3000, TEGO ViscoPlus 3030, and TEGO ViscoPlus 3060.

[0072] In some embodiments of the present application, the wetting agent comprises at least one of polyether siloxane copolymer TEGO-245, non-ionic organic surfactant TEGO-500 and polyether modified polysiloxane solution BYK-346.

[0073] In some embodiments of the present application, the raw materials for preparing the water-based two-component photocuring coating include, by weight parts:

[0074] Cationic photocuring polyacrylate dispersion 50-70 parts;

[0075] Radical photoinitiator 1-3 parts;

[0076] Cationic photoinitiator 0.5-1.5 parts;

[0077] Water 10-30 parts;

[0078] Film-forming aid 2-4 parts;

[0079] Dispersant 0.3-1.0 parts;

[0080] Titanium white 10-20 parts;

[0081] Defoaming agent 0.05-0.2 parts;

[0082] Thickening agent 0.5-0.8 parts;

[0083] Wetting agent 0.05-0.2 parts.

[0084] In some embodiments of the present application, the method for preparing the double-bond-containing component of the water-based two-component photocuring coating includes the following steps:

[0085] After the water and the film-forming aid are premixed and added to the cationic photocuring polyacrylate dispersion, the photoinitiator, the dispersant, the titanium white, the defoaming agent, the thickening agent and the wetting agent are sequentially added, and dispersed for 10-30 minutes, and then filtered to obtain the double-bond-containing component of the water-based two-component photocuring coating. The double-bond-containing component and the hydrophilic modified epoxy resin are mixed uniformly at a ratio of 100: (5-10), and thus the water-based two-component photocuring coating is obtained.

[0086] Here, the ratio of the double-bond-containing component and the hydrophilic modified epoxy resin, the double-bond-containing component includes the double-bond-containing component cationic photocuring polyacrylate dispersion and other aids.

[0087] The second aspect of the present application provides a water-based two-component photocuring coating prepared by the above-mentioned method.

[0088] The third aspect of the present application provides the use of the water-based two-component photocuring coating in the field of wood product preparation, automobile manufacturing or metal product corrosion prevention.

[0089] The paint film of the water-based two-component photocuring coating obtained by the application 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-grade woodware coatings, automobile coatings, metal anticorrosive coatings and other industrial protective coatings. Embodiments of the application

[0090] In order to make the skilled in the art more clearly understand the technical solutions described in the application, the following examples are listed for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the application.

[0091] The raw materials, reagents or devices used in the following examples, unless otherwise specified, can be obtained from conventional commercial channels or can be obtained by existing known methods.

[0092] The following examples are further limited, the acrylic monomer is the acrylic acid AA or methacrylic acid MAA of the Sanmu Company;

[0093] The methacrylate monomer is the methyl methacrylate MMA, butyl acrylate BA, isobornyl acrylate IBOA, cyclohexyl methacrylate CHMA and / or benzyl methacrylate BNMA of the Sanmu Company;

[0094] The vinyl monomer is the styrene St, vinyl acetate VAc of the Sanmu Company;

[0095] The initiator is the di-tert-pentyl peroxide DTAP or di-tert-butyl peroxide DTBP of the Jinjinle Company;

[0096] The diisocyanate monomer is the isophorone diisocyanate IPDI, toluene diisocyanate TDI, hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI, 4,4'-dicyclohexylmethane diisocyanate HMDI of the Wanhua Company;

[0097] The bio-based material is one of the special epoxy soybean oil GreenSoft D, special epoxy soybean oil GreenSoft H, epoxy linseed oil ELO EPOXOL® 9-5™ of the Xingbang High Polymer Material Co., Ltd.;

[0098] The hydrophilic modifier is one of the cyclohexylaminoethanesulfonic acid CHES, cyclohexylaminopropanesulfonic acid CAPS or cyclohexylaminobutanesulfonic acid CABS of the Aladdin Company;

[0099] The blocked cationic thermal initiator is one of the CTI-100, CTI-200, CTI-300 of the Shenzhen Youyang Company or the Vicbase TC3631 of the Shenzhen City Kaigi Application Material Co., Ltd.;

[0100] The cationic photoinitiator is one or more of HRcure-9387, HRcure-9392, HRcure-9388, HRcure-262, HRcure-261, HRcure-6992, HRcure-6976 of HUIRAN HENGTONG CO., LTD. or Omnirad 250 of IGM RESINS, INC.;

[0101] Further limited, the acrylamide monomer is one of diacetone acrylamide DAAM, N-butoxymethyl acrylamide or hydroxyethyl acrylamide;

[0102] Further limited, the neutralizing agent is one of triethylamine TEA, N,N-dimethylethanolamine DMEA or N,N-dimethylcyclohexylamine DMCHA of DOW CHEMICAL;

[0103] Further limited, the epoxy resin is one of tetraglycidyl diaminodimethylene benzene MF-4101, 4,5-epoxy tetrahydrophthalic acid diglycidyl ester MF-3286 and triglycidyl-p-aminophenol MF-3102 of Hubei Zhenzhengfeng New Material Co., Ltd.

[0104] Example 1

[0105] A two-component photocuring coating 1:

[0106] The cationic photocuring polyacrylate dispersion is prepared by the following steps:

[0107] A1. In mass fraction, 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, 10.7 parts of styrene St and 0.6 parts of di-tert-amyl peroxide DTAP are mixed uniformly to form a mixed solution A1, which is ready for use;

[0108] A2. In mass fraction, 23.9 parts of isophorone diisocyanate IPDI is heated to 50°C, and 14.2 parts of triethylene glycol divinyl ether DVE is added at a constant pressure within 15 minutes. Continue to react for 1 hour to obtain a prepolymer B1 containing vinyl and isocyanate groups, which is ready for use;

[0109] A3. In mass fraction, 25.2 parts of special epoxy soybean oil GreenSoft D is added to a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, stirred and heated, and the temperature is raised to 73°C. 5.6 parts of cyclohexylaminopropyl sulfonic acid CAPS is added and reacted for 75 minutes to obtain a hydrophilic modified bio-based material C1, which is ready for use;

[0110] A4. 0.4 parts of blocked cationic thermal initiator CTI-100, 0.5 parts of cationic photoinitiator HRcure-9387 and 0.4 parts of free radical photoinitiator Darocur 1173 were mixed uniformly to form a mixture D1, ready for use;

[0111] A5. The hydrophilically modified bio-based material C1 was added dropwise into the mixture A1 at a constant pressure within 4 hours when heated to 150°C at a mass fraction, after the dropwise addition, the mixture was stirred and kept for 30 minutes, then cooled to 80°C, 0.01 parts of polymerization inhibitor MEHQ was added, 9.7 parts of diacetone acrylamide DAAM was added, and the reaction was continued for 40 minutes, then cooled to 50°C, B1 was added, and the reaction was continued for 30 minutes, then D1 was added, 2.5 parts of triethylamine TEA was added after stirring for 5 minutes, 178 parts of deionized water was added after stirring for 5 minutes, and the mixture was dispersed at a high speed for 10 minutes, then the product was filtered out, and a cationic photopolymerizable polyacrylate dispersion containing double bonds was obtained, ready for use.

[0112] The preparation method of the hydrophilically modified epoxy resin containing epoxy groups is as follows:

[0113] B1. 17.2 parts of MF-4101 and 9.0 parts of cyclohexylaminopropyl sulfonic acid CAPS (0.04 mol) were mixed uniformly at a mass fraction, the reaction temperature was controlled at 40°C, the reaction was carried out for 1.5 hours, 3.3 parts of triethylamine TEA (0.033 mol) was added and stirred for 5 minutes, and a hydrophilically modified epoxy resin containing epoxy groups was obtained, ready for use.

[0114] Example 2

[0115] A two-component photocurable coating 2:

[0116] The cationic photopolymerizable polyacrylate dispersion was prepared by the following steps:

[0117] A1. 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 and 0.5 parts of di-tert-butyl peroxide DTBP were mixed uniformly to form a mixture A2, ready for use;

[0118] A2. 28.2 parts of hydrogenated MDI was heated to 70°C, and 18.3 parts of 4-hydroxybutyl vinyl ether cyclohexyl-1,4-dimethanol monovinyl ether was added dropwise at a constant pressure within 30 minutes, and the reaction was continued for 1.5 hours to obtain a prepolymer B2 containing vinyl and isocyanate groups, ready for use;

[0119] A3. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 18.5 parts by mass of epoxidized linseed oil ELO EPOXOL® 9-5™ was added, stirred and heated, the temperature was raised to 65°C, 5.9 parts by mass of cyclohexylaminobutanesulfonic acid CABS was added, and the reaction was carried out for 90 minutes to obtain a hydrophilically modified bio-based material C2, which was ready for use;

[0120] A4. 0.5 parts by mass of a blocked cationic thermal initiator CTI-200, 0.5 parts by mass of a cationic photoinitiator HRcure-9388 and 0.3 parts by mass of a free radical photoinitiator Irgacure 2959 were mixed uniformly to form a mixture D2, which was ready for use;

[0121] A5. The hydrophilically modified bio-based material C2 was heated to 145°C and added dropwise to the mixture A2 at a constant pressure within 4 hours. After the dropwise addition was completed, the mixture was stirred and kept at temperature for 40 minutes, the temperature was lowered to 70°C, 0.01 parts by mass of a polymerization inhibitor MEHQ was added, 6.6 parts by mass of hydroxyethyl acrylamide was added, and the reaction was continued for 50 minutes. The temperature was lowered to 55°C, B2 was added, and the reaction was continued for 35 minutes. D2 was added, and 2.2 parts by mass of N,N-dimethylethanolamine DMEA was added after 7 minutes of stirring. After 5 minutes of stirring, 176 parts by mass of deionized water was added and dispersed at high speed for 15 minutes. The product was filtered to obtain a cationic photopolymerizable polyacrylate dispersion containing double bonds, which was ready for use.

[0122] The method for preparing the hydrophilically modified epoxy resin containing epoxy groups was as follows:

[0123] B1. 15.2 parts by mass of MF-3286 and 10.6 parts by mass of cyclohexylaminoethanesulfonic acid CHES were mixed uniformly, and the reaction temperature was controlled at 40°C. The reaction was carried out for 2 hours, 3.6 parts by mass of N,N-dimethylethanolamine DMEA was added and stirred for 3 minutes to form a hydrophilically modified epoxy resin containing epoxy groups, which was ready for use.

[0124] Example 3

[0125] A two-component photocurable coating 3:

[0126] The cationic photopolymerizable polyacrylate dispersion was prepared by the following steps:

[0127] A1. 1.8 parts by mass of acrylic acid AA, 11.2 parts by mass of methyl methacrylate MMA, 7.5 parts by mass of butyl acrylate BA, 6.3 parts by mass of butyl methacrylate BNMA, 8.7 parts by mass of styrene St and 0.4 parts by mass of di-tert-butyl peroxide DTBP were mixed uniformly to form a mixture A3, which was ready for use.

[0128] A2. 18.1 parts of hexamethylene diisocyanate HDI was heated to 60°C, and 12.5 parts of 4-hydroxybutyl vinyl ether HBVE was added dropwise at constant pressure within 25 minutes, and the reaction was continued for 1.3 hours to obtain a vinyl group and isocyanate group-containing prepolymer B3, which was ready for use;

[0129] A3. 24.2 parts of special epoxy soybean oil GreenSoft H was added into a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, and stirred and heated, and the temperature was raised to 70°C, and 5.2 parts of cyclohexylaminoethanesulfonic acid CHES was added, and the reaction was continued for 60 minutes to obtain a hydrophilic modified bio-based material C3, which was ready for use;

[0130] A4. 0.3 parts of a blocked cationic thermal initiator CTI-300, 0.6 parts of a cationic photoinitiator Omnirad 250 and 0.3 parts of a free radical photoinitiator Irgacure 500 were uniformly mixed to form a mixture D3, which was ready for use;

[0131] A5. The hydrophilic modified bio-based material C3 was heated to 140°C, and the mixture A3 was added dropwise at constant pressure within 4 hours, and after the dropping was completed, the stirring and incubation were continued for 40 minutes, and the temperature was lowered to 75°C, and 0.01 parts of a polymerization inhibitor MEHQ was added, and 9.0 parts of N-butoxymethyl acrylamide was added, and the reaction was continued for 45 minutes, and the temperature was lowered to 50°C, and B3 was added, and the reaction was continued for 30 minutes, and D3 was added, and after stirring for 5 minutes, 3.2 parts of N,N-dimethylcyclohexylamine DMCHA was added, and after stirring for 5 minutes, 164 parts of deionized water was added and dispersed at high speed for 20 minutes, and the filtrate was obtained to obtain a double bond-containing component cationic photopolymerizable polyacrylate dispersion, which was ready for use.

[0132] The preparation method of the epoxy group-containing component hydrophilic modified epoxy resin is as follows:

[0133] B1. 12.4 parts of MF-3102 and 10.5 parts of cyclohexylaminobutanesulfonic acid CABS were uniformly mixed, and the reaction temperature was controlled at 45°C, and the reaction was continued for 1.5 hours, and 4.5 parts of N,N-dimethylcyclohexylamine DMCHA was added, and stirring was continued for 5 minutes to form an epoxy group-containing component hydrophilic modified epoxy resin, which was ready for use.

[0134] Example 4

[0135] Example 4 prepared a water-based two-component photocurable coating 1, and the cationic photopolymerizable polyacrylate dispersion 1 and the hydrophilic modified epoxy resin 1 were prepared in Example 1, and the specific steps were as follows:

[0136] The double bond-containing component of the water-based two-component photocurable coating was composed of the following components in weight parts:

[0137] The cationic photopolymerizable polyacrylate dispersion 160 parts;

[0138] Free radical photoinitiator Darocur 1173 30.5 parts;

[0139] Free radical photoinitiator Lucirin TPO-L 1.0 part;

[0140] Cationic photoinitiator Omnirad 250 1.0 part;

[0141] Water 18.3 parts;

[0142] Dipropylene glycol butyl ether 0.5 parts;

[0143] Dipropylene glycol methyl ether 2 parts;

[0144] DISPERS 755W 0.5 parts;

[0145] Titanium dioxide NTR-606 15 parts;

[0146] TEGO-800 0.2 parts;

[0147] RM-8W 0.8 parts;

[0148] TEGO-245 0.2 parts;

[0149] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 1 is added into a stirring kettle, the stirring speed is 700 r / min, the water, the dipropylene glycol butyl ether and the dipropylene glycol methyl ether are premixed and then added into the stirring kettle, the Darocur 1173, the Lucirin TPO-L, the Omnirad 250, the DISPERS 755W, the titanium dioxide NTR-606, the TEGO-800, the RM-8W and the TEGO-245 are sequentially added, and the mixture is dispersed for 20 minutes, and then filtered to obtain a double-bond-containing component of the water-based two-component photocuring coating; the double-bond-containing component and the hydrophilic modified epoxy resin prepared in the example 1 are uniformly mixed at a ratio of 100:6, and thus a water-based two-component photocuring coating 1 is obtained.

[0150] After the paint film prepared from the water-based two-component photocuring coating 1 is dried at 50℃ for 2 hours, the mercury lamp of a photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2 for curing, and the film is baked at 100℃ for 2 hours after curing.

[0151] Example 5

[0152] Example 2 was prepared into a waterborne two-component photocurable coating 2, cationic photocurable polyacrylate dispersion 2 and hydrophilic modified epoxy resin 2, the specific steps were as follows:

[0153] The double bond containing component of the waterborne two-component photocurable coating was composed of the following components in parts by weight:

[0154] Cationic photocurable polyacrylate dispersion 260 parts;

[0155] Free radical photoinitiator Irgacure 2959 0.7 parts;

[0156] Free radical photoinitiator Irgacure 819-DW 0.8 parts;

[0157] Cationic photoinitiator HRcure-6992 1.0 parts;

[0158] Water 17.8 parts;

[0159] Propylene glycol butyl ether 1 part;

[0160] Propylene glycol methyl ether 2 parts;

[0161] DISPERBYK-191 0.5 parts;

[0162] Titanium dioxide Ti-Pure R-902+ 15 parts;

[0163] TEGO-805 0.2 parts;

[0164] TT-935 0.8 parts;

[0165] BYK-346 0.2 parts;

[0166] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 2 is added into a stirring kettle, the stirring speed is 700 r / min, the water, propylene glycol butyl ether and propylene glycol methyl ether are premixed and then added into the stirring kettle, Irgacure 2959, Irgacure 819-DW, HRcure-6992, DISPERBYK-191, titanium dioxide Ti-Pure R-902+, TEGO-805, TT-935 and BYK-346 are sequentially added, and the mixture is dispersed for 20 minutes, and then filtered to obtain the double-bond-containing component of the water-based two-component photocuring coating; the double-bond-containing component and the hydrophilic modified epoxy resin prepared in Example 2 are uniformly mixed at a ratio of 100:6, and thus the water-based two-component photocuring coating 2 is obtained.

[0167] After the paint film prepared from the water-based two-component photocuring coating 2 is dried at 50℃ for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2 for curing, and the film is baked at 100℃ for 2 hours after curing.

[0168] Example 6

[0169] Example 6

[0170] The double-bond-containing component of the water-based two-component photocuring coating is composed of the following components in parts by weight:

[0171] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0172] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0173] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0174] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0175] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0176] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0177] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0178] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0179] The cationic photocuring polyacrylate dispersion 3 and the hydrophilic modified epoxy resin 3 are prepared in Example 3, and the specific steps are as follows:

[0180] TEGO-815 0.2 parts;

[0181] TEGO ViscoPlus 30000.8 parts;

[0182] TEGO-500 0.2 parts;

[0183] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 3 is added into a stirred kettle, the stirring speed is 700 r / min, the water, dipropylene glycol butyl ether and propylene glyol methyl ether are premixed and then added into the stirred kettle, the Irgacure 500, Irgacure 819-DW, Omnirad 250, DISPERBYK-191, titanium white NTR-606, TEGO-815, TEGO ViscoPlus 3000 and TEGO-500 are sequentially added, and the dispersion is carried out for 20 minutes, and the water-based two-component photocuring coating containing double bonds is obtained by filtration; the water-based two-component photocuring coating containing double bonds and the hydrophilic modified epoxy resin prepared in Example 3 are uniformly mixed at a ratio of 100:6, and the water-based two-component photocuring coating 3 is obtained.

[0184] After the paint film prepared from the water-based two-component photocuring coating 3 is dried at 50℃ for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2 for curing, and the film is baked at 100℃ for 2 hours after curing.

[0185] Comparative Example 1

[0186] A two-component photocuring coating 4:

[0187] In this comparative example, the amount of the prepolymer containing vinyl and isocyanate groups is halved, and the cationic photocuring polyacrylate dispersion is prepared by the following steps:

[0188] A1. 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, 10.7 parts of styrene St and 0.6 parts of di-t-amyl peroxide DTAP are uniformly mixed to form a mixed solution A4, which is ready for use;

[0189] A2. 11.9 parts of isophorone diisocyanate IPDI is heated to 50℃, and 7.1 parts of triethylene glycol divinyl ether DVE is added dropwise at a constant pressure within 15 minutes, and the reaction is continued for 1 hour to obtain a prepolymer B4 containing vinyl and isocyanate groups, which is ready for use;

[0190] A3. 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 was added, stirred and heated, the temperature was raised to 73°C, 5.6 parts of cyclohexylaminopropanesulfonic acid CAPS was added, and the reaction was carried out for 75 minutes to obtain a hydrophilically modified bio-based material C4, which was ready for use;

[0191] A4. In mass parts, 0.4 parts of blocked cationic thermal initiator CTI-100, 0.5 parts of cationic photoinitiator HRcure-9387 and 0.4 parts of free radical photoinitiator Darocur 1173 were mixed uniformly to form a mixture D4, which was ready for use;

[0192] A5. In mass parts, the hydrophilically modified bio-based material C4 was heated to 150°C and added dropwise to the mixed solution A4 in 4 hours, after the dropwise addition was completed, the mixture was stirred and kept 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 was added, the reaction was continued for 40 minutes, the temperature was lowered to 50°C, 19 parts of B4 was added, the reaction was continued for 30 minutes, 1.3 parts of D4 was added, 2.5 parts of triethylamine TEA was added after stirring for 5 minutes, 149 parts of deionized water was added and dispersed at high speed for 10 minutes, and the filtrate was obtained to obtain a cationic photopolymerizable polyacrylate dispersion containing double bonds, which was ready for use.

[0193] The preparation method of the hydrophilically modified epoxy resin containing epoxy groups is as follows:

[0194] B1. In mass parts, 17.2 parts of MF-4101 and 9 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly, the reaction temperature was controlled at 40°C, the reaction was carried out for 1.5 hours, 3.3 parts of triethylamine TEA was added and stirred for 5 minutes to form a hydrophilically modified epoxy resin containing epoxy groups, which was ready for use.

[0195] Comparative Example 2

[0196] A two-component photocurable coating 5:

[0197] In this comparative example, the hydrophilically modified epoxy resin and the polyacrylate prepolymer were dispersed together, and the cationic photopolymerizable polyacrylate dispersion was prepared by the following steps:

[0198] A1. In mass parts, 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, 10.7 parts of styrene St, and 0.6 parts of di-tert-amyl peroxide DTAP were mixed uniformly to form a mixed solution A5, which was ready for use;

[0199] A2. When 23.9 parts of isophorone diisocyanate IPDI is heated to 50°C, 14.2 parts of triethylene glycol divinyl ether DVE is added at a constant pressure within 15 minutes, and the reaction is continued for 1 hour to obtain a prepolymer B5 containing a vinyl group and an isocyanate group, which is ready for use;

[0200] A3. 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 is added, stirred and heated, and the temperature is raised to 73°C. 5.6 parts of cyclohexylaminopropyl sulfonic acid CAPS is added, and the reaction is continued for 75 minutes to obtain a hydrophilically modified bio-based material C5, which is ready for use;

[0201] A4. 17.2 parts of MF-4101 and 9.0 parts of cyclohexylaminopropyl sulfonic acid CAPS are mixed uniformly, and the reaction temperature is controlled at 40°C. The reaction is continued for 1.5 hours to form a mixture D5, which is ready for use;

[0202] A5. 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 Darocur 1173 are mixed uniformly to form a mixture E5, which is ready for use.

[0203] The preparation method of the epoxy group-containing component hydrophilically modified epoxy resin is as follows:

[0204] B1. When the hydrophilically modified bio-based material C5 is heated to 150°C, the mixed solution A5 is added at a constant pressure within 4 hours. After the addition is completed, the mixture is stirred and kept at 150°C for 30 minutes. The temperature is lowered to 80°C, 0.01 parts of a polymerization inhibitor MEHQ is added, 9.7 parts of diacetone acrylamide DAAM is added, and the reaction is continued for 40 minutes. The temperature is lowered to 50°C, B5 is added, and the reaction is continued for 30 minutes. D5 is added, stirred for 5 minutes, E5 is added, stirred for 5 minutes, 5.8 parts of triethylamine TEA is added, stirred for 5 minutes, and 222 parts of deionized water is added and dispersed at a high speed for 10 minutes. The filtrate is obtained to obtain a cationic photocurable polyacrylate dispersion, which is ready for use.

[0205] Comparative Example 3

[0206] A two-component photocurable coating 6 is prepared by the following steps:

[0207] This comparative example does not add an acrylamide monomer and is prepared by the following steps:

[0208] A1. 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, 10.7 parts of styrene St, and 0.6 parts of di-tert-amyl peroxide DTAP are mixed uniformly to form a mixed solution A6, which is ready for use;

[0209] A2. With mass fraction, 11.1 parts of isoflurone diisocyanate IPDI is heated to 50℃, and 6.6 parts of triethylene glycol divinyl ether DVE is added at a constant pressure within 15 minutes. Continue to react for 1 hour to obtain a vinyl and isocyanate group-containing prepolymer B6, ready for use;

[0210] A3. With mass fraction, 25.2 parts of special epoxy soybean oil GreenSoft D is added to a four-necked flask equipped with a thermometer, condenser and stirring paddle, stirred and heated, and the temperature is raised to 73℃. 5.6 parts of cyclohexyl amino propyl sulfonic acid CAPS is added and reacted for 75 minutes to obtain a hydrophilic modified bio-based material C6, ready for use;

[0211] A4. With mass fraction, 0.4 parts of blocked cationic thermal initiator CTI-100, 0.5 parts of cationic photoinitiator HRcure-9387 and 0.4 parts of free radical photoinitiator Darocur1173 are mixed uniformly to form a mixture D6, ready for use;

[0212] A5. With mass fraction, the hydrophilic modified bio-based material C6 is heated to 150℃, and the mixed solution A6 is added at a constant pressure within 4 hours. After the drop is completed, it is stirred and kept for 30 minutes. The temperature is lowered to 50℃, 0.01 parts of polymerization inhibitor MEHQ is added, B6 is added, and the reaction is continued for 30 minutes. D6 is added, stirred for 5 minutes, then 2.5 parts of triethylamine TEA is added, stirred for 5 minutes, then 133 parts of deionized water is dispersed at high speed for 10 minutes, and the filtrate is obtained. A double bond component cationic photopolymerization acrylate dispersion is obtained, ready for use.

[0213] The preparation method of the epoxy group-containing component hydrophilic modified epoxy resin is:

[0214] B1. With mass fraction, 17.2 parts of MF-4101 and 9 parts of cyclohexyl amino propyl sulfonic acid CAPS are mixed uniformly, and the reaction temperature is controlled at 40℃. React for 1.5 hours, add 3.3 parts of triethylamine TEA and stir for 5 minutes to form an epoxy group-containing component hydrophilic modified epoxy resin, ready for use.

[0215] Comparative Example 4

[0216] A two-component photocurable coating 7:

[0217] This comparative example does not add a blocked cationic thermal initiator, which is prepared by the following steps:

[0218] A1. In mass fraction, 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, 10.7 parts of styrene St, and 0.6 parts of di-tert-amyl peroxide DTAP were uniformly mixed to form a mixed solution A7, ready for use;

[0219] A2. In mass fraction, 23.9 parts of isophorone diisocyanate IPDI was heated to 50°C, and 14.2 parts of triethylene glycol divinyl ether DVE was added dropwise at a constant pressure within 15 minutes. The reaction was continued for 1 hour to obtain a prepolymer B7 containing vinyl and isocyanate groups, ready for use.

[0220] A3. In mass fraction, 25.2 parts of special epoxy soybean oil GreenSoft D was added to a four-necked flask equipped with a thermometer, condenser, and stirring paddle, stirred and heated, and the temperature was raised to 73°C. 5.6 parts of cyclohexylaminopropyl sulfonic acid CAPS was added, and the reaction was continued for 75 minutes to obtain a hydrophilically modified bio-based material C7, ready for use.

[0221] A4. In mass fraction, 0.5 parts of cationic photoinitiator HRcure-9387 and 0.4 parts of free radical photoinitiator were uniformly mixed to form a mixture D7, ready for use.

[0222] A5. In mass fraction, the hydrophilically modified bio-based material C7 was heated to 150°C, and the mixed solution A7 was added dropwise at a constant pressure within 4 hours. After the dropwise addition was completed, the mixture was stirred and kept at temperature 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 was added, and the reaction was continued for 40 minutes. The temperature was lowered to 50°C, B7 was added, and the reaction was continued for 30 minutes. D7 was added, stirred for 5 minutes, 2.5 parts of triethylamine TEA was added, stirred for 5 minutes, and 177 parts of deionized water was added and dispersed at high speed for 10 minutes. The filtrate was obtained to obtain a cationic photopolymerizable polyacrylate dispersion containing double bonds, ready for use.

[0223] The preparation method of the epoxy group-containing component hydrophilically modified epoxy resin is as follows:

[0224] B1. In mass fraction, 17.2 parts of MF-4101 and 9.0 parts of cyclohexylaminopropyl sulfonic acid CAPS were uniformly mixed, and the reaction temperature was controlled at 40°C. The reaction was continued for 1.5 hours, 3.3 parts of triethylamine TEA was added and stirred for 5 minutes to form a hydrophilically modified epoxy resin containing epoxy groups, ready for use.

[0225] Comparative Example 5

[0226] A two-component photocurable coating 8:

[0227] In this comparative example, the hydrophilically modified epoxy resin neutralizer was added in excess, and the cationic photopolymerizable polyacrylate dispersion was prepared by the following steps:

[0228] A1. In mass fraction, 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, 10.7 parts of styrene St, and 0.6 parts of di-tert-amyl peroxide DTAP were uniformly mixed to form a mixed solution A8, which was ready for use;

[0229] A2. In mass fraction, 23.9 parts of isophorone diisocyanate IPDI was heated to 50°C, and 14.2 parts of triethylene glycol divinyl ether DVE was added dropwise at a constant pressure within 15 minutes. The reaction was continued for 1 hour to obtain a prepolymer B8 containing vinyl and isocyanate groups, which was ready for use;

[0230] A3. In mass fraction, 25.2 parts of special epoxy soybean oil GreenSoft D was added to a four-necked flask equipped with a thermometer, a condenser, and a stirring paddle, and stirred and heated. The temperature was raised to 73°C, and 5.6 parts of cyclohexylaminopropyl sulfonic acid CAPS was added. The reaction was continued for 75 minutes to obtain a hydrophilically modified bio-based material C8, which was ready for use;

[0231] A4. In mass fraction, 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 were uniformly mixed to form a mixture D8, which was ready for use;

[0232] A5. In mass fraction, the hydrophilically modified bio-based material C8 was added dropwise into the mixed solution A8 at a constant pressure within 4 hours while heating to 150°C. After the dropwise addition was completed, the mixture was stirred and kept at temperature for 30 minutes. The temperature was lowered to 80°C, 0.01 parts of a polymerization inhibitor MEHQ was added, and 9.7 parts of diacetone acrylamide DAAM was added. The reaction was continued for 40 minutes. The temperature was lowered to 50°C, B8 was added, and the reaction was continued for 30 minutes. D8 was added, and 2.5 parts of triethylamine TEA was added after stirring for 5 minutes. After stirring for 5 minutes, 178 parts of deionized water was added and dispersed at a high speed for 10 minutes. The filtrate was obtained to obtain a cationic photopolymerizable polyacrylate dispersion containing double bonds, which was ready for use.

[0233] The preparation method of the hydrophilically modified epoxy resin containing epoxy groups is as follows:

[0234] B1. In mass fraction, 16.8 parts of MF-4101 and 8.8 parts of cyclohexylaminopropyl sulfonic acid CAPS were uniformly mixed. The reaction temperature was controlled at 40°C, and the reaction was continued for 1.5 hours. 4 parts of triethylamine TEA was added and stirred for 5 minutes to form a hydrophilically modified epoxy resin containing epoxy groups, which was ready for use.

[0235] Comparative Example 6

[0236] A two-component photocurable coating 9:

[0237] In the present comparative example, the addition ratio of the hydrophilic modified epoxy resin is different from that of the examples, wherein the cationic photo-curable polyacrylate dispersion is prepared by the following steps:

[0238] A1. In mass fraction, 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, 10.7 parts of styrene St, and 0.6 parts of di-tert-amyl peroxide DTAP were uniformly mixed to form a mixed solution A9, which was ready for use;

[0239] A2. In mass fraction, 23.9 parts of isophorone diisocyanate IPDI was heated to 50°C, and 14.2 parts of triethylene glycol divinyl ether DVE was added dropwise at a constant pressure within 15 minutes. The reaction was continued for 1 hour to obtain a prepolymer B9 containing vinyl and isocyanate groups, which was ready for use;

[0240] A3. In mass fraction, 25.2 parts of special epoxy soybean oil GreenSoft D was added to a four-necked flask equipped with a thermometer, a condenser, and a stirring paddle, and stirred and heated. The temperature was raised to 73°C, and 5.6 parts of cyclohexylaminopropyl sulfonic acid CAPS was added. The reaction was continued for 75 minutes to obtain a hydrophilic modified bio-based material C9, which was ready for use;

[0241] A4. In mass fraction, 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 were uniformly mixed to form a mixture D9, which was ready for use;

[0242] A5. In mass fraction, the hydrophilic modified bio-based material C9 was heated to 150°C, and the mixed solution A9 was added dropwise at a constant pressure within 4 hours. After the dropwise addition was completed, the mixture was stirred and kept at temperature for 30 minutes. The temperature was lowered to 80°C, 0.01 parts of a polymerization inhibitor MEHQ was added, 9.7 parts of diacetone acrylamide DAAM was added, and the reaction was continued for 40 minutes. The temperature was lowered to 50°C, B9 was added, and the reaction was continued for 30 minutes. D9 was added, stirred for 5 minutes, 2.5 parts of triethylamine TEA was added, stirred for 5 minutes, and then 178 parts of deionized water was added and dispersed at high speed for 10 minutes. The filtrate was obtained to obtain a cationic photo-curable polyacrylate dispersion containing double bonds, which was ready for use.

[0243] The preparation method of the epoxy group-containing component hydrophilic modified epoxy resin is as follows:

[0244] B1. In mass fraction, 8.6 parts of MF-4101 and 4.5 parts of cyclohexylaminopropyl sulfonic acid CAPS were uniformly mixed, and the reaction temperature was controlled at 40°C. The reaction was continued for 1.5 hours, 1.6 parts of triethylamine TEA was added and stirred for 5 minutes to form an epoxy group-containing component hydrophilic modified epoxy resin, which was ready for use;

[0245] Comparative Example 7

[0246] A two-component photocuring coating 10:

[0247] In the present comparative example, the proportion of hydrophilic modified epoxy resin added is different from that in the examples, wherein the cationic photocuring polyacrylate dispersion is prepared by the following steps:

[0248] A1. In mass parts, 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, 10.7 parts of styrene St, and 0.6 parts of di-tert-amyl peroxide DTAP were uniformly mixed to form a mixed solution A10, ready for use;

[0249] A2. In mass parts, 23.9 parts of isophorone diisocyanate IPDI was heated to 50°C, and 14.2 parts of triethylene glycol divinyl ether DVE was added at a constant pressure within 15 minutes. The reaction was continued for 1 hour to obtain a prepolymer B10 containing vinyl and isocyanate groups, ready for use;

[0250] A3. In mass parts, 25.2 parts of special epoxy soybean oil GreenSoft D was added to a four-necked flask equipped with a thermometer, a condenser, and a stirring paddle, and stirred and heated. The temperature was raised to 73°C, and 5.6 parts of cyclohexylaminopropyl sulfonic acid CAPS was added. The reaction was continued for 75 minutes to obtain a hydrophilic modified bio-based material C10, ready for use;

[0251] A4. In mass parts, 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 were uniformly mixed to form a mixture D10, ready for use;

[0252] A5. In mass parts, the hydrophilic modified bio-based material C10 was heated to 150°C and added to the mixed solution A10 at a constant pressure within 4 hours. After the drop was completed, the stirring and heat preservation were continued for 30 minutes. The temperature was lowered to 80°C, 0.01 parts of a polymerization inhibitor MEHQ was added, 9.7 parts of diacetone acrylamide DAAM was added, and the reaction was continued for 40 minutes. The temperature was lowered to 50°C, B10 was added, and the reaction was continued for 30 minutes. D10 was added, stirred for 5 minutes, and then 2.5 parts of triethylamine TEA was added. After stirring for 5 minutes, 178 parts of deionized water was dispersed at a high speed for 10 minutes. The filtrate was obtained to obtain a cationic photocuring polyacrylate dispersion containing double bonds, ready for use;

[0253] The preparation method of the epoxy-containing component hydrophilic modified epoxy resin is:

[0254] B1. 34.5 parts of MF-4101 and 18.1 parts of cyclohexylaminopropanesulfonic acid CAPS were mixed uniformly in mass parts, the reaction temperature was controlled at 40°C, and the reaction was carried out for 1.5 hours. Then 6.6 parts of triethylamine TEA was added and stirred for 5 minutes to form a hydrophilic modified epoxy resin containing epoxy groups, which was ready for use;

[0255] Comparative Example 8

[0256] A water-based two-component photocuring coating 4 was prepared, and the cationic photocuring polyacrylate dispersion 4 and the hydrophilic modified epoxy resin 4 were prepared as in Comparative Example 1. The specific steps were as follows:

[0257] The double-bond-containing component of the water-based two-component photocuring coating was composed of the following components in weight parts:

[0258] Cationic photocuring polyacrylate dispersion 460 parts;

[0259] Free radical photoinitiator Darocur 1173 0.5 parts;

[0260] Free radical photoinitiator Lucirin TPO-L 1.0 part;

[0261] Cationic photoinitiator Omnirad 250 1.0 part;

[0262] Water 18.3 parts;

[0263] Dipropylene glycol butyl ether 0.5 parts;

[0264] Dipropylene glycol methyl ether 2 parts;

[0265] DISPERS 755W 0.5 parts;

[0266] Titanium dioxide NTR-606 15 parts;

[0267] TEGO-800 0.2 parts;

[0268] RM-8W 0.8 parts;

[0269] TEGO-245 0.2 parts;

[0270] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 4 is added into a stirring kettle, the stirring speed is 700 r / min, the water, dipropylene glycol butyl ether and dipropylene glycol methyl ether are premixed and then added into the stirring kettle, Darocur 1173, Lucirin TPO-L, Omnirad 250, DISPERS 755W, titanium dioxide NTR-606, TEGO-800, RM-8W and TEGO-245 are sequentially added, and the mixture is dispersed for 20 minutes, and then filtered to obtain the double bond containing component of the water-based two-component photocuring coating; the double bond containing component and the hydrophilic modified epoxy resin prepared in the comparative example 1 are uniformly mixed at a ratio of 100:6, and the water-based two-component photocuring coating 4 is obtained.

[0271] After the paint film prepared from the water-based two-component photocuring coating 4 is dried at 50°C for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2, and the film is cured, and then baked at 100°C for 2 hours.

[0272] Comparative example 9

[0273] A water-based photocuring coating 5 is prepared in the comparative example, the cationic photocuring polyacrylate dispersion 5 is prepared in the comparative example 2, and the specific steps are as follows:

[0274] The double bond containing component of the water-based photocuring coating is composed of the following components in parts by weight:

[0275] The cationic photocuring polyacrylate dispersion 5 is 60 parts;

[0276] The free radical photoinitiator Darocur 1173 is 0.5 parts;

[0277] The free radical photoinitiator Lucirin TPO-L is 1.0 part;

[0278] The cationic photoinitiator Omnirad 250 is 1.0 part;

[0279] The water is 18.3 parts;

[0280] The dipropylene glycol butyl ether is 0.5 part;

[0281] The dipropylene glycol methyl ether is 2 parts;

[0282] The DISPERS 755W is 0.5 part;

[0283] The titanium dioxide NTR-606 is 15 parts;

[0284] TEGO-800 0.2 parts;

[0285] RM-8W 0.8 parts;

[0286] TEGO-245 0.2 parts;

[0287] The preparation method of the water-based photocurable coating is as follows: the cationic photocurable polyacrylate dispersion 5 is added to a stirred kettle, the stirring speed is 700 rpm, the water, dipropylene glycol butyl ether and dipropylene glycol methyl ether are premixed and then added to the stirred kettle, and Darocur 1173, Lucirin TPO-L, Omnirad 250, DISPERS 755W, titanium dioxide NTR-606, TEGO-800, RM-8W and TEGO-245 are sequentially added, dispersed for 20 minutes, and filtered to obtain the water-based photocurable coating 5.

[0288] After the paint film prepared from the water-based photocurable coating 5 is dried at 50°C for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2for curing, and after curing, the film is baked at 100°C for 2 hours.

[0289] Comparative Example 10

[0290] A water-based two-component photocurable coating 6 is prepared in the comparative example, the cationic photocurable polyacrylate dispersion 6 and the hydrophilic modified epoxy resin 6 are prepared in Comparative Example 3, and the specific steps are as follows:

[0291] The double-bond-containing component of the water-based two-component photocurable coating is composed of the following components in parts by weight:

[0292] Cationic photocurable polyacrylate dispersion 660 parts;

[0293] Free radical photoinitiator Darocur 1173 0.5 parts;

[0294] Free radical photoinitiator Lucirin TPO-L 1.0 part;

[0295] Cationic photoinitiator Omnirad 250 1.0 part;

[0296] Water 18.3 parts;

[0297] Dipropylene glycol butyl ether 0.5 parts;

[0298] Dipropylene glycol methyl ether 2 parts;

[0299] DISPERS 755W 0.5 parts;

[0300] Titan dioxide NTR-606 15 parts;

[0301] TEGO-800 0.2 parts;

[0302] RM-8W 0.8 parts;

[0303] TEGO-245 0.2 parts;

[0304] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 6 is added into a stirring kettle, the stirring speed is 700 r / min, the water, dipropylene glycol butyl ether and dipropylene glycol methyl ether are premixed and then added into the stirring kettle, and Darocur 1173, Lucirin TPO-L, Omnirad 250, DISPERS 755W, titanium dioxide NTR-606, TEGO-800, RM-8W and TEGO-245 are sequentially added, and dispersed for 20 minutes, and then filtered to obtain a double-bond-containing component of the water-based two-component photocuring coating; the double-bond-containing component and the hydrophilic modified epoxy resin prepared in Comparative Example 3 are uniformly mixed at a ratio of 100:6, and thus a water-based two-component photocuring coating 6 is obtained.

[0305] After the paint film prepared from the water-based two-component photocuring coating 6 is dried at 50°C for 2 hours, the mercury lamp of a photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2, and the film is cured, and then baked at 100°C for 2 hours.

[0306] Comparative Example 11

[0307] A water-based two-component photocuring coating 7 is prepared in the comparative example, the cationic photocuring polyacrylate dispersion 7 and the hydrophilic modified epoxy resin 7 are prepared in Comparative Example 4, and the specific steps are as follows:

[0308] The double-bond-containing component of the water-based two-component photocuring coating is composed of the following components in parts by weight:

[0309] Cationic photocuring polyacrylate dispersion 760 parts;

[0310] Free radical photoinitiator Darocur 1173 0.5 parts;

[0311] Lucirin TPO-L 1.0 part;

[0312] Omnirad 250 1.0 part;

[0313] Water 18.3 parts;

[0314] Dipropylene glycol butyl ether 0.5 part;

[0315] Dipropylene glycol methyl ether 2 parts;

[0316] DISPERS 755W 0.5 part;

[0317] Titanium dioxide NTR-606 15 parts;

[0318] TEGO-800 0.2 part;

[0319] RM-8W 0.8 part;

[0320] TEGO-245 0.2 part;

[0321] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 7 is added into a stirring kettle, the stirring speed is 700 r / min, the water, the dipropylene glycol butyl ether and the dipropylene glycol methyl ether are premixed and then added into the stirring kettle, the Darocur 1173, the Lucirin TPO-L, the Omnirad 250, the DISPERS 755W, the titanium dioxide NTR-606, the TEGO-800, the RM-8W and the TEGO-245 are sequentially added, and the mixture is dispersed for 20 minutes, and then filtered to obtain a double-bond-containing component of the water-based two-component photocuring coating; the double-bond-containing component and the hydrophilic modified epoxy resin prepared in the comparative example 4 are uniformly mixed at a ratio of 100:6, and thus a water-based two-component photocuring coating 7 is obtained.

[0322] After the paint film prepared from the water-based two-component photocuring coating 7 is dried at 50℃ for 2 hours, the mercury lamp of a photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2, and the film is cured, and then baked at 100℃ for 2 hours.

[0323] Comparative example 12

[0324] A waterborne two-component photocurable coating 8 was prepared, cationic photocurable polyacrylate dispersion 8 and hydrophilically modified epoxy resin 8 were prepared as in comparative example 5, the specific steps were as follows:

[0325] The double bond containing component of the waterborne two-component photocurable coating consisted of the following components in parts by weight:

[0326] Cationic photocurable polyacrylate dispersion 860 parts;

[0327] Free radical photoinitiator Darocur 1173 30.5 parts;

[0328] Free radical photoinitiator Lucirin TPO-L 1.0 part;

[0329] Cationic photoinitiator Omnirad 250 1.0 part;

[0330] Water 18.3 parts;

[0331] Dipropylene glycol butyl ether 0.5 part;

[0332] Dipropylene glycol methyl ether 2 parts;

[0333] DISPERS 755W 0.5 part;

[0334] Titanium dioxide NTR-606 15 parts;

[0335] TEGO-800 0.2 part;

[0336] RM-8W 0.8 part;

[0337] TEGO-245 0.2 part;

[0338] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 8 is added into a stirring kettle, the stirring speed is 700 r / min, the water, dipropylene glycol butyl ether and dipropylene glycol methyl ether are premixed and then added into the stirring kettle, Darocur 1173, Lucirin TPO-L, Omnirad 250, DISPERS 755W, titanium dioxide NTR-606, TEGO-800, RM-8W and TEGO-245 are sequentially added, and the mixture is dispersed for 20 minutes, and then filtered to obtain the double bond containing component of the water-based two-component photocuring coating; the double bond containing component and the hydrophilic modified epoxy resin prepared in Comparative Example 5 are uniformly mixed at a ratio of 100:6, and the water-based two-component photocuring coating 8 is obtained.

[0339] After the paint film prepared from the water-based two-component photocuring coating 8 is dried at 50℃ for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2 for curing, and the film is baked at 100℃ for 2 hours after curing.

[0340] Comparative Example 13

[0341] A water-based two-component photocuring coating 9 is prepared in Comparative Example 13, the cationic photocuring polyacrylate dispersion 9 and the hydrophilic modified epoxy resin 9 are prepared in Comparative Example 6, and the specific steps are as follows:

[0342] The double bond containing component of the water-based two-component photocuring coating is composed of the following components in parts by weight:

[0343] The cationic photocuring polyacrylate dispersion 960 parts;

[0344] The free radical photoinitiator Darocur 1173 0.5 parts;

[0345] The free radical photoinitiator Lucirin TPO-L 1.0 part;

[0346] The cationic photoinitiator Omnirad 250 1.0 part;

[0347] Water 18.3 parts;

[0348] Dipropylene glycol butyl ether 0.5 part;

[0349] Dipropylene glycol methyl ether 2 parts;

[0350] DISPERS 755W 0.5 part;

[0351] Titanium dioxide NTR-606 15 parts;

[0352] TEGO-800 0.2 parts;

[0353] RM-8W 0.8 parts;

[0354] TEGO-245 0.2 parts;

[0355] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 9 is added into a stirring kettle, the stirring speed is 700 r / min, the water, dipropylene glycol butyl ether and dipropylene glycol methyl ether are premixed and then added into the stirring kettle, and the Darocur 1173, Lucirin TPO-L, Omnirad 250, DISPERS 755W, titanium dioxide NTR-606, TEGO-800, RM-8W and TEGO-245 are sequentially added, and dispersed for 20 minutes, and then filtered to obtain the double bond containing component of the water-based two-component photocuring coating; the double bond containing component and the hydrophilic modified epoxy resin prepared in the comparative example 6 are uniformly mixed at a ratio of 100:3, and thus the water-based two-component photocuring coating 9 is obtained.

[0356] After the paint film prepared from the water-based two-component photocuring coating 9 is dried at 50℃ for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2 for curing, and after curing, the paint film is baked at 100℃ for 2 hours.

[0357] Comparative Example 14

[0358] A water-based two-component photocuring coating 10 is prepared in the comparative example, the cationic photocuring polyacrylate dispersion 10 and the hydrophilic modified epoxy resin 10 are prepared in the comparative example 7, and the specific steps are as follows:

[0359] The double bond containing component of the water-based two-component photocuring coating is composed of the following components in parts by weight:

[0360] Cationic photocuring polyacrylate dispersion 1060 parts;

[0361] Free radical photoinitiator Darocur 1173 0.5 parts;

[0362] Free radical photoinitiator Lucirin TPO-L 1.0 part;

[0363] Cationic photoinitiator Omnirad 250 1.0 part;

[0364] Water 18.3 parts;

[0365] Dipropylene glycol butyl ether 0.5 parts;

[0366] Dipropylene glycol methyl ether 2 parts;

[0367] DISPERS 755W 0.5 parts;

[0368] Titanium dioxide NTR-606 15 parts;

[0369] TEGO-800 0.2 parts;

[0370] RM-8W 0.8 parts;

[0371] TEGO-245 0.2 parts;

[0372] The preparation method of the water-based two-component photocuring coating is as follows: the cationic photocuring polyacrylate dispersion 10 is added into a stirring kettle, the stirring speed is 700 r / min, the water, the dipropylene glycol butyl ether and the dipropylene glycol methyl ether are premixed and then added into the stirring kettle, and the Darocur 1173, the Lucirin TPO-L, the Omnirad 250, the DISPERS 755W, the titanium dioxide NTR-606, the TEGO-800, the RM-8W and the TEGO-245 are sequentially added, and are dispersed for 20 minutes, and then the double-bond-containing component of the water-based two-component photocuring coating is obtained by filtration, and the double-bond-containing component and the hydrophilic modified epoxy resin prepared in the comparative example 7 are uniformly mixed at a ratio of 100:20, so that the water-based two-component photocuring coating 10 is obtained.

[0373] After the paint film prepared from the water-based two-component photocuring coating 10 is dried at 50℃ for 2 hours, the mercury lamp of the photocuring machine is turned on, the UVV energy is adjusted to 600 mJ / cm2 for curing, and after curing, the paint film is baked at 100℃ for 2 hours.

[0374] Test example 1

[0375] The basic performance test includes: the photocuring bio-based polyurethane dispersion is tested according to GB / T11175-2002 “Synthetic resin emulsion test method”, the appearance, the pH, the solid content and the viscosity of the emulsion are tested, the double-bond / epoxy group concentration is obtained by theoretical calculation, the double-bond / epoxy group concentration is the ratio of the amount of substance of the double-bond / epoxy group substance to the mass of the solid component of the emulsion or the coating, and the unit is mol / 100g. The average particle size of the emulsion is measured by using a nano particle size analyzer (ZS Nano S).

[0376] Table 1 Performance parameters of cationic photocuring polyacrylate dispersion and hydrophilic modified epoxy resin

[0377]

[0378] As can be seen from the above table, compared with Example 1, the amount of pre-polymer containing vinyl and isocyanate groups in Comparative Example 1 is halved, and there is no obvious difference in the dispersion; compared with Example 1, the hydrophilic modified epoxy resin and the polyacrylate pre-polymer are dispersed together to prepare a single-component dispersion, and the storage stability is poor; compared with Example 1, no acrylamide monomer is added in Comparative Example 3, and the storage stability of the dispersion is poor; compared with Example 1, no blocked cationic thermal initiator is added in Comparative Example 4, and there is no obvious difference in the dispersion; compared with Example 1, an excess of hydrophilic modified epoxy resin neutralizer is added in Comparative Example 5, which makes the storage stability of the epoxy resin worse; compared with Example 1, the only difference between Comparative Examples 6 and 7 is the proportion of the hydrophilic modified epoxy resin; as can be seen from Examples 1, 2 and 3, the preparation method of the epoxy modified photocuring polyacrylate dispersion and the hydrophilic modified epoxy resin is disclosed, and the epoxy modified photocuring polyacrylate dispersion and the hydrophilic modified epoxy resin prepared by the method have good storage stability.

[0379] Test Example 2

[0380] After the paint film of the water-based two-component photocuring coating was dried at 50℃ for 2 hours, the mercury lamp of the photocuring machine was turned on, and the UVA energy was adjusted to 600mJ / cm2 for curing, and the performance was as shown in Table 2.

[0381] The test standard is:

[0382] Coating film appearance: visual inspection;

[0383] Pencil hardness: GB / T6739-2006;

[0384] Coating film gloss / (60°, %): GB / T9754-2007;

[0385] Water resistance(25℃, 24h): GB / T4893.1-2020;

[0386] Dry heat resistance(70±2℃, 15h): GB / T4893.3-2020;

[0387] Ethanol resistance(50%, 1h): GB / T4893.1-2020;

[0388] Adhesion: GB / T9286-2021.

[0389] Table 2 Performance parameters of water-based two-component photocuring coating

[0390]

[0391] From the above table, it can be seen that, compared with Example 4, the pre-polymer containing vinyl and isocyanate group in Comparative Example 8 is halved, the double bond concentration is reduced, the residual hydroxyl group is increased, and the paint film resistance is poor; compared with Example 4, the paint in Comparative Example 9 is a single-component paint, the film performance is close, but the storage stability is poor; compared with Example 4, the acrylamide monomer is not added in Comparative Example 10, the free radical photocuring is reduced, the residual epoxy group is increased, and the paint film resistance is poor; compared with Example 4, the blocked cationic thermal initiator is not added in Comparative Example 11, the paint film resistance and the adhesion to pine, glass and other substrates are slightly poor. Compared with Example 4, the paint film performance of Comparative Example 12 has no obvious difference, but the storage stability of the epoxy component is poor. Compared with Example 4, the addition ratio of the hydrophilic modified epoxy resin in Comparative Example 13 is reduced, the paint film resistance, pine adhesion and melamine board adhesion are poor; compared with Example 4, the addition ratio of the hydrophilic modified epoxy resin in Comparative Example 14 is too high, the adhesion of the paint film to glass, ceramic tile and melamine board is poor. From Examples 4, 5 and 6, it can be seen that the paint film prepared from the water-based two-component photocuring coating disclosed in the application has the advantages of good flexibility, good water and chemical resistance, excellent adhesion to various substrates, and can be applied to high-grade woodware coatings, automobile coatings, metal anticorrosion coatings and other industrial protective coatings.

[0392] The above has described the embodiments of the application in detail, but the application is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the purpose of the application. In addition, the embodiments of the application and the features in the embodiments can be combined with each other without conflict.

Claims

1. A method for preparing an aqueous two-component photocuring coating, characterized by, The preparation raw materials of the water-based two-component photocuring coating include: a double-bond-containing component cationic photocuring polyacrylate dispersion and an epoxy-group-containing component hydrophilic modified epoxy resin; The preparation method of the double-bond-containing component cationic photocuring polyacrylate dispersion includes: A1. uniformly mixing acrylic monomers, acrylate monomers, vinyl monomers and initiators to form a mixed solution A; A2. reacting diisocyanate and hydroxy vinyl ether to obtain a vinyl and isocyanate group-containing prepolymer B; A3. reacting a bio-based material and a hydrophilic modifier to obtain a hydrophilic modified bio-based material C; A4. mixing a blocked cationic thermal initiator, a cationic photoinitiator and a free radical photoinitiator to form a mixture D; A5. mixing and dispersing the hydrophilic modified bio-based material C, the mixed solution A, a polymerization inhibitor, an acrylamide monomer, the vinyl and isocyanate group-containing prepolymer B, the mixture D and a neutralizing agent to obtain the double-bond-containing component cationic photocuring polyacrylate dispersion; The preparation method of the epoxy-group-containing component hydrophilic modified epoxy resin includes: B1. mixing and reacting an epoxy resin, a hydrophilic modifier and a neutralizing agent to obtain the epoxy-group-containing component hydrophilic modified epoxy resin.

2. The production method according to claim 1, characterized by, The preparation method of the double-bond-containing component cationic photocuring polyacrylate dispersion includes: A1. mixing 1.5-2.5 parts of acrylic monomers, 20-30 parts of acrylate monomers, 5-11 parts of vinyl monomers and 0.4-0.6 parts of initiators to form a mixed solution A; A2. reacting 18-30 parts of diisocyanate and 12-20 parts of hydroxy vinyl ether to obtain a vinyl and isocyanate group-containing prepolymer B; A3. reacting 18-26 parts of a bio-based material and 5-6 parts of a hydrophilic modifier to obtain a hydrophilic modified bio-based material C; A4. mixing 0.3-0.5 parts of a blocked cationic thermal initiator, 0.3-0.6 parts of a cationic photoinitiator and 0.3-0.5 parts of a free radical photoinitiator to form a mixture D; A5. mixing and dispersing the hydrophilic modified bio-based material C, the mixed solution A, a polymerization inhibitor, 6-10 parts of an acrylamide monomer, the vinyl and isocyanate group-containing prepolymer B, the mixture D and a neutralizing agent to obtain the double-bond-containing component cationic photocuring polyacrylate dispersion; The preparation method of the epoxy-group-containing component hydrophilic modified epoxy resin includes: B1. mixing and reacting 12-20 parts of an epoxy resin, 8-15 parts of a hydrophilic modifier and 3-5 parts of a neutralizing agent to obtain the epoxy-group-containing component hydrophilic modified epoxy resin.

3. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: Mixing the double-bond-containing component cationic photocuring polyacrylate dispersion and the hydrophilic modified epoxy resin in a weight ratio of 100: (5-15) to obtain the water-based two-component photocuring coating.

4. The preparation method according to claim 1, characterized in that, The preparation raw materials of the bio-based material include a plant oil containing three or more epoxy groups; The hydrophilic modifier includes a monomer containing a secondary amino group and a sulfonic acid group; The epoxy resin includes an epoxy resin containing three or more epoxy groups.

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

6. The method of claim 1, wherein, 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 epoxy resin includes at least one of tetraglycidyl diaminodimethylene benzene, 4,5-epoxy tetrahydrophthalic acid diglycidyl ester and triglycidyl-p-aminophenol.

8. The method of claim 1, wherein, The preparation raw material of the water-based two-component photocuring coating further includes an auxiliary agent, and the auxiliary agent includes a film forming auxiliary agent, a dispersant, titanium white powder, a defoaming agent, a thickening agent and a wetting agent.

9. A waterborne two-component photocuring coating, characterized by, Prepared by the preparation method in any one of claims 1-8.

10. Application of the water-based two-component photocuring coating in claim 9 in the field of wood product preparation, automobile manufacturing or metal product corrosion prevention.

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