阅读说明：本技术 一种底面合一电泳漆耐磨树脂及其制备方法 (Primer-topcoat integrated electrophoretic paint wear-resistant resin and preparation method thereof ) 是由 万涛 章树芳 杜建伟 刘元 雷坤 陈文俊 于 2021-10-15 设计创作，主要内容包括：本发明属于电泳漆制备技术领域,一种底面合一电泳漆耐磨树脂及其制备方法,主要包括以下重量百分比的组分：丙烯酸树脂10％-30％；改性环氧树脂1％-15％；改性橡胶0.5％-1％；硬单体2％-8％；N-甲基乙醇胺2％-8％；溶剂2％-8％；乳酸3-8％；乙二醇己醚1-5％；聚醚硅氧烷0.05-1％；水50-60％,本发明在在环氧结构上引入网状丙烯酸树脂主链,能有效地增加漆膜的柔韧性,抗拉裂；调节丙烯酸树脂分子量的树脂分布,增加边缘覆盖性能；同时掺杂改性橡胶树脂,即达到增强防腐的作用,又提供耐磨性能。(The invention belongs to the technical field of electrophoretic paint preparation, and relates to primer-topcoat integrated electrophoretic paint wear-resistant resin and a preparation method thereof, which mainly comprise the following components in percentage by weight: 10-30% of acrylic resin; 1% -15% of modified epoxy resin; 0.5 to 1 percent of modified rubber; 2% -8% of hard monomer; 2% -8% of N-methylethanolamine; 2% -8% of a solvent; 3-8% of lactic acid; 1-5% of ethylene glycol hexyl ether; 0.05 to 1 percent of polyether siloxane; 50-60% of water, and the invention introduces a reticular acrylic resin main chain on the epoxy structure, which can effectively increase the flexibility and the tensile crack resistance of the paint film; the resin distribution of the molecular weight of the acrylic resin is adjusted, and the edge coverage performance is improved; meanwhile, the modified rubber resin is doped, so that the corrosion resistance is enhanced, and the wear resistance is also provided.)

1. The utility model provides a bottom surface unification electrophoresis lacquer wear-resistant resin which characterized in that: the paint mainly comprises the following components in percentage by weight: 10-30% of acrylic resin; 1% -15% of modified epoxy resin; 0.5 to 1 percent of modified rubber; 2% -8% of hard monomer; 2% -8% of N-methylethanolamine; 2% -8% of a solvent; 3-8% of lactic acid; 1-5% of ethylene glycol hexyl ether; 0.05 to 1 percent of polyether siloxane; 50-60% of water.

2. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 1, wherein: the acrylic resin comprises the following components: 2-8% of glycidyl methacrylate, 1-5% of ethoxylated trimethylolpropane triacrylate, 2-8% of pentaerythritol tetraacrylate, 5-10% of carbitol acrylate and 2-8% of hard monomer; 1 to 5 percent of initiator.

3. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 2, wherein: the hard monomer comprises one or more of styrene, vinyl fluoride, tetrafluoroethylene and butadiene.

4. The super abrasion resistant electrophoretic paint resin according to claim 1, wherein: the initiator is one of tert-butyl peroxybenzoate, azobisisobutyronitrile and benzoyl peroxide.

5. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 1, wherein: the solvent comprises methyl isobutyl ketone, butanone and xylene.

6. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 1, wherein: the modified epoxy resin comprises the following components: 40-60% of epoxy resin; 40-60% of N, N-dimethylformamide, 5-15% of toluene, 2-5% of bisphenol fluorene and 2-5% of 4, 4 difluoro-diphenyl sulfone.

7. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 6, wherein: the modified epoxy resin is prepared by the following steps: (1) adding N, N-dimethylformamide, toluene and anhydrous potassium carbonate into a reactor and refluxing at 145-148 ℃; (2) then bisphenol fluorene and 4, 4 difluoro-diphenyl sulfone are mixed and melted in N, N-dimethyl formamide, and then slowly and uniformly added into a reactor for continuous constant temperature reaction for 5-8h, (3) cooling to room temperature, filtering to remove salt, decompressing and concentrating under acidic condition to obtain white precipitate, filtering, washing and drying to obtain cyclic compound, (4) the cyclic compound and epoxy resin are mixed in a melting mode at 130 ℃ to obtain the modified epoxy resin.

8. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 7, wherein: the mixing ratio of the cyclic compound to the epoxy resin is 1: 4.

9. The primer-topcoat-one-electrophoretic paint abrasion-resistant resin as claimed in claim 1, wherein: the modified rubber comprises amino-terminated liquid nitrile rubber and polyether polyol glycidyl ether.

10. The preparation method of the primer-topcoat electrophoretic paint wear-resistant resin is characterized by comprising the following steps of: the preparation method comprises the following preparation steps:

s1: adding 1-15% of modified epoxy resin into 2-8% of methyl isobutyl ketone, and heating to 115-130 ℃ for dissolution;

s2: 2-8% of glycidyl methacrylate, 1-5% of ethoxylated trimethylolpropane triacrylate, 2-8% of pentaerythritol tetraacrylate, 5-10% of carbitol acrylate and 2-8% of hard monomer at the temperature of 120-130 ℃; 1-5% of initiator is mixed, the mixture obtained in the step S1 is dripped into the mixture at constant speed within 3-4h, and the mixture is reacted for 2h at constant temperature of 125-;

s3: reducing the temperature of the step S2 to 100 ℃, adding N-methylethanolamine, raising the temperature to 120-;

s4: cooling the reaction to 90 ℃, dropwise adding 0.5-1% of modified rubber, 0.05-1% of polyether siloxane, 1-5% of ethylene glycol hexyl ether, 2-7% of IPDI curing agent and 2-7% of HDI curing agent, and stirring for reacting for 1 h;

s5: cooling to 70 ℃, adding 3-8% of lactic acid and 50-60% of water, stirring for reacting for 1h, and cooling to room temperature to obtain the primer-topcoat electrophoretic paint wear-resistant resin.

Technical Field

The invention belongs to the technical field of electrophoretic paint preparation, and particularly relates to primer-topcoat integrated electrophoretic paint wear-resistant resin and a preparation method thereof.

Background

The electrophoretic coating is a novel coating with low pollution, energy conservation, resource conservation, protection and corrosion resistance, has the characteristics of smooth coating, good water resistance and chemical resistance and the like, is easy to realize the mechanization and automation of the coating industry, is suitable for coating workpieces with edges, corners and holes, and is widely applied to coating hardware such as automobiles, automatic vehicles, electromechanics, household appliances and the like.

The invention patent with application publication number CN11169281A discloses a bottom-surface-in-one cathode electrophoretic paint and a preparation method thereof, wherein the components comprise ED-1, color paste, ED-3, emulsion and acrylic resin, and by the components, when in actual use, the conventional cathode electrophoretic paint can be used as a surface independent paint film with salt fog resistance and weather resistance both over 500h, and does not need to be sprayed with finish paint or powder, so that economic benefit and time benefit are brought to construction of a user, the wear-resisting strength of the electrophoretic paint is not high, and meanwhile, as the resin formed in the patent is of a linear structure, the resin substance of the linear structure is low in strength, low in flexibility and easy to break.

Disclosure of Invention

The invention aims to provide a primer-topcoat electrophoretic paint wear-resistant resin and a preparation method thereof, which can effectively increase the flexibility and the tensile crack resistance of a paint film; the resin distribution of the molecular weight of the acrylic resin is adjusted, and the edge coverage performance is improved; meanwhile, the modified rubber resin is doped, so that the corrosion resistance is enhanced, and the wear resistance is also provided.

The technical purpose of the invention is realized by the following technical scheme: the utility model provides a bottom surface unification electrophoresis lacquer wear-resistant resin which characterized in that: the paint mainly comprises the following components in percentage by weight: 10-30% of acrylic resin; 1% -15% of modified epoxy resin; 0.5 to 1 percent of modified rubber; 2% -8% of hard monomer; 2% -8% of N-methylethanolamine; 2% -8% of a solvent; 3-8% of lactic acid; 1-5% of ethylene glycol hexyl ether; 0.05 to 1 percent of polyether siloxane; 50-60% of water.

The invention is further provided with: the acrylic resin comprises the following components: 2-8% of glycidyl methacrylate, 1-5% of ethoxylated trimethylolpropane triacrylate, 2-8% of pentaerythritol tetraacrylate, 5-10% of carbitol acrylate and 2-8% of hard monomer; 1 to 5 percent of initiator.

The invention is further provided with: the hard monomer comprises one or more of styrene, vinyl fluoride, tetrafluoroethylene and butadiene.

The invention is further provided with: the initiator is one of tert-butyl peroxybenzoate, azobisisobutyronitrile and benzoyl peroxide.

The invention is further provided with: the solvent comprises methyl isobutyl ketone, butanone and xylene.

The invention is further provided with: the modified epoxy resin comprises the following components: 40-60% of epoxy resin; 40-60% of N, N-dimethylformamide, 5-15% of toluene, 2-5% of bisphenol fluorene and 2-5% of 4, 4 difluoro-diphenyl sulfone; .

The invention is further provided with: the modified epoxy resin is prepared by the following steps: (1) adding N, N-dimethylformamide, toluene and anhydrous potassium carbonate into a reactor, and refluxing at 145-148 ℃; (2) then bisphenol fluorene and 4, 4 difluoro-diphenyl sulfone are mixed and melted in N, N-dimethyl formamide, and then slowly and uniformly added into a reactor for continuous constant temperature reaction for 5-8h, (3) cooling to room temperature, filtering to remove salt, decompressing and concentrating under acidic condition to obtain white precipitate, filtering, washing and drying to obtain cyclic compound, (4) the cyclic compound and epoxy resin are mixed in a melting mode at 130 ℃ to obtain the modified epoxy resin.

The invention is further provided with: the mixing ratio of the cyclic compound to the epoxy resin is 1: 4.

The invention is further provided with: the modified rubber comprises amino-terminated liquid nitrile rubber and polyether polyol glycidyl ether.

The preparation method of the primer-topcoat electrophoretic paint wear-resistant resin is characterized by comprising the following steps of: the preparation method comprises the following preparation steps:

s1: adding the modified epoxy resin into methyl isobutyl ketone, and heating to 115-130 ℃ for dissolution;

s2: 2-8% of glycidyl methacrylate, 1-5% of ethoxylated trimethylolpropane triacrylate, 2-8% of pentaerythritol tetraacrylate, 5-10% of carbitol acrylate and 2-8% of hard monomer at the temperature of 120-130 ℃; 1-5% of initiator is mixed, the mixture obtained in the step S1 is dripped into the mixture at constant speed within 3-4h, and the mixture is reacted for 2h at constant temperature of 125-;

s3: reducing the temperature of the step S2 to 100 ℃, adding N-methylethanolamine, raising the temperature to 120-;

s4: cooling the reaction to 90 ℃, dropwise adding 0.5-1% of modified rubber, 0.05-1% of polyether siloxane, 1-5% of ethylene glycol hexyl ether, 2-7% of IPDI curing agent and 2-7% of HDI curing agent, and stirring for reacting for 1 h;

s5: cooling to 70 ℃, adding 3-8% of lactic acid and 50-60% of water, stirring for reacting for 1h, and cooling to room temperature to obtain the primer-topcoat electrophoretic paint wear-resistant resin.

The invention has the beneficial effects that: .

1. According to the invention, the reticular acrylic resin main chain is introduced into the epoxy structure, so that the flexibility and the tensile crack resistance of a paint film can be effectively increased; the resin distribution of the molecular weight of the acrylic resin is adjusted, and the edge coverage performance is improved; meanwhile, the modified rubber resin is doped, so that the effect of enhancing corrosion resistance is achieved, and the wear resistance is improved.

2. According to the invention, the epoxy resin is modified, the epoxy resin modified by the cyclic compound containing the rigid structure can play the effects of toughening, reinforcement and heat resistance, the synthesized cyclic compound not only has good solubility in some polar protic solvents, but also shows excellent solubility in polar aprotic solvents, and the structure contains a large number of rigid groups, so that the strength of the resin can be improved, and meanwhile, due to the large cyclic structure, the chain winding among resins in a previous structure can be avoided, the intermolecular interaction Li is reduced, and the solubility is increased.

3. According to the invention, the amino-terminated liquid nitrile rubber and the initiator interact to generate oxidative polymerization, then the terminal amino group in the amino-terminated liquid nitrile rubber reacts with the epoxy group in the polyether polyol glycidyl ether to form the modified rubber resin, and the modified rubber resin is hybridized with the epoxy modified acrylic resin, so that the strength and the wear resistance of the electrophoretic paint resin can be greatly improved, the formed electrophoretic paint has certain toughness, and the impact resistance and the wear resistance of the electrophoretic paint are improved.

4. According to the invention, the ratio of the acrylic resin to the epoxy resin is controlled, and the influence of the viscosity and the neutralization degree of the resin on the product is fully evaluated, tested and researched, so that the problem of emulsion stability of the modified epoxy acrylic resin is effectively solved. Meanwhile, the proper amino-terminated synthetic rubber resin is selected for modification and then is acidified into cationic resin, and the proper doping proportion is tested, so that the wear resistance of the resin is improved.

5. The invention adopts the amine-enclosed HDI crosslinking agent without benzene ring and the methyl ethyl ketoxime-enclosed IPDI crosslinking agent composite system to carry out curing reaction, adopts the composite curing agent with proper proportion to adjust the content of soft and hard segments in the electrophoretic paint resin, obviously enhances the intermolecular hydrogen bond acting force due to the existence of the reaction product urea bond, improves the cohesion of the electrophoretic paint, and shows that the hardness of the electrophoretic paint is improved.

Detailed Description

The technical solutions in the examples will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.

Example 1

A preparation method of primer-topcoat integrated electrophoretic paint wear-resistant resin comprises the following steps:

s1: adding 3 percent of epoxy resin into 2 percent of methyl isobutyl ketone, and heating to 115-130 ℃ for dissolution;

s2: at the temperature of 120 ℃ and 130 ℃, 2 percent of glycidyl methacrylate, 2 percent of ethoxylated trimethylolpropane triacrylate, 4 percent of pentaerythritol tetraacrylate, 5 percent of carbitol acrylate and 4 percent of styrene are mixed; 1-5% of initiator is mixed, the mixture obtained in the step S1 is dripped into the mixture at constant speed within 3-4h, and the mixture is reacted for 2h at constant temperature of 125-;

s3: reducing the temperature of the step S2 to 100 ℃, adding 3 percent N-methylethanolamine, raising the temperature to 120-125 ℃, and keeping the temperature for 2 h;

s4: cooling the reaction to 90 ℃, dropwise adding 0.2% of polyether siloxane, 3% of ethylene glycol hexyl ether, 2% of IPDI curing agent and 4% of HDI curing agent, and stirring for reaction for 1 h;

s5: cooling to 70 ℃, adding 3-8% of lactic acid and 50-60% of water, stirring for reacting for 1h, and cooling to room temperature to obtain the primer-topcoat electrophoretic paint wear-resistant resin.

Example 2

A preparation method of primer-topcoat integrated electrophoretic paint wear-resistant resin comprises the following steps:

s1: adding 8% of modified epoxy resin into 4% of methyl isobutyl ketone, and heating to 115-130 ℃ for dissolution;

s2: at the temperature of 120-130 ℃, 3 percent of glycidyl methacrylate, 3 percent of ethoxylated trimethylolpropane triacrylate, 4 percent of pentaerythritol tetraacrylate, 5 percent of carbitol acrylate and 5 percent of vinyl fluoride are mixed; mixing the initiator by 3 percent, uniformly dropping the initiator into the mixture obtained in the step S1, finishing dropping within 3-4h, and reacting at constant temperature of 125-;

s3: reducing the temperature of the step S2 to 100 ℃, adding 4 percent N-methylethanolamine, raising the temperature to 120-;

s4: cooling the reaction to 90 ℃, dropwise adding 0.4% of polyether siloxane, 4% of ethylene glycol hexyl ether, 2% of IPDI curing agent and 4% of HDI curing agent, and stirring for reaction for 1 h;

s5: cooling to 70 ℃, adding 4% of lactic acid and 50-60% of water, stirring for reacting for 1h, and cooling to room temperature to obtain the primer-topcoat electrophoretic paint wear-resistant resin.

Example 3

A preparation method of primer-topcoat integrated electrophoretic paint wear-resistant resin comprises the following steps:

s1: adding 5% of modified epoxy resin into 6% of methyl isobutyl ketone, and heating to 115-130 ℃ for dissolution;

s2: at the temperature of 120 ℃ and 130 ℃, 6 percent of glycidyl methacrylate, 4 percent of ethoxylated trimethylolpropane triacrylate, 6 percent of pentaerythritol tetraacrylate, 6 percent of carbitol acrylate and 6 percent of tetrafluoroethylene are mixed; 4 percent of initiator is mixed, the mixture obtained in the step S1 is dripped into the mixture at constant speed within 3-4h, and the mixture is reacted for 2h at constant temperature of 125-;

s3: reducing the temperature of the step S2 to 100 ℃, adding 6 percent N-methylethanolamine, raising the temperature to 120-;

s4: cooling the reaction to 90 ℃, dropwise adding 0.8% of modified rubber, 0.4% of polyether siloxane, 4% of ethylene glycol hexyl ether, 6% of IPDI curing agent and 2% of HDI curing agent, and stirring for reacting for 1 h;

s5: cooling to 70 ℃, adding 6% of lactic acid and 50-60% of water, stirring for reacting for 1h, and cooling to room temperature to obtain the primer-topcoat electrophoretic paint wear-resistant resin.

Example 4

A preparation method of primer-topcoat integrated electrophoretic paint wear-resistant resin comprises the following steps:

s1: adding 14% of modified epoxy resin into 8% of methyl isobutyl ketone, and heating to 115-130 ℃ for dissolution;

s2: at the temperature of 120 ℃ and 130 ℃, 8 percent of glycidyl methacrylate, 5 percent of ethoxylated trimethylolpropane triacrylate, 8 percent of pentaerythritol tetraacrylate, 10 percent of carbitol acrylate and 2 to 8 percent of butadiene are added; 1-5% of initiator is mixed, the mixture obtained in the step S1 is dripped into the mixture at constant speed within 3-4h, and the mixture is reacted for 2h at constant temperature of 125-;

s3: reducing the temperature of the step S2 to 100 ℃, adding 8 percent N-methylethanolamine, raising the temperature to 120-125 ℃, and keeping the temperature for 2 h;

s4: cooling the reaction to 90 ℃, dropwise adding 1% of modified rubber, 1% of polyether siloxane, 5% of ethylene glycol hexyl ether, 2% of IPDI curing agent and 7% of HDI curing agent, and stirring for reacting for 1 h;

s5: cooling to 70 ℃, adding 8% of lactic acid and 50-60% of water, stirring for reacting for 1h, and cooling to room temperature to obtain the primer-topcoat electrophoretic paint wear-resistant resin.

Determining the storage stability according to the national standard GB 6753.3-86; the adhesion of the electrophoretic coating of the cathode is measured according to GB/T9286-1998 test for marking the paint film of the colored paint and the varnish; carrying out impact resistance measurement on the cathode electrophoretic coating according to GB/T1732-93 paint film impact resistance measurement method; the weather resistance of the electrophoretic coating is determined by referring to the calibration standard of an ultraviolet aging test box for JJF (non-ferrous metal) 0002-; performing wear resistance test on the electrophoretic coating by referring to GB/T1768 and 2006 method for measuring wear resistance of colored paint and varnish by a rotating rubber grinding wheel method; the neutral salt spray test was performed according to GB/T1771-2007, and the test results are shown in Table 1:

TABLE 1 examination of the properties of the electrodeposition paint coatings prepared from the resins of examples 1 to 4

The electrophoretic paints formed by the resins in examples 1-4 can be seen that the performance of each electrophoretic paint coating is better, the storage stability and the mechanical stability are higher, compared with example 2 in example 1, the modified epoxy resin is adopted in example 2, the cyclic compound modified epoxy resin containing a rigid structure can play a role in toughening, reinforcing and corrosion resistance, compared with example 2 in examples 3-4, the modified rubber is added in examples 3-4, and the modified rubber resin is adopted, so that the effect of enhancing corrosion resistance is achieved, and the wear resistance is also provided. Therefore, the ground-in-one electrophoretic paint resin formed in the application document can effectively increase the flexibility and the tensile crack resistance of a paint film; the resin distribution of the molecular weight of the acrylic resin is adjusted, and the edge coverage performance is improved; meanwhile, the modified rubber resin is doped, so that the corrosion resistance is enhanced, and the wear resistance is also provided.