阅读说明：本技术 聚酯改性环氧丙烯酸酯树脂及其制备方法和应用 (Polyester modified epoxy acrylate resin and preparation method and application thereof ) 是由 汤玉兰 林敏仪 温嘉敏 梁晓琦 于 2019-10-17 设计创作，主要内容包括：本发明涉及一种聚酯改性环氧丙烯酸酯树脂及其制备方法和应用。该树脂由包括如下重量份的组分制备而成：丙烯酸羟乙酯24-30份；苯酐30-35份；环氧树脂15-20份；二缩三丙二醇二丙烯酸酯15-20份；所述聚酯丙烯酸酯为二官能度聚酯丙烯酸酯,粘度为2000mpa.s/25℃-4000mpa.s/25℃,酸值≤5mgKOH/g。向环氧树脂主链中引入聚酯丙烯酸酯链段后,可以有效改善环氧丙烯酸酯树脂的柔韧性、附着力以及抗黄变性能,改性后的环氧丙烯酸酯树脂符合国家标准、综合性能优异、用途广泛。(The invention relates to a polyester modified epoxy acrylate resin and a preparation method and application thereof. The resin is prepared from the following components in parts by weight: 24-30 parts of hydroxyethyl acrylate; 30-35 parts of phthalic anhydride; 15-20 parts of epoxy resin; 15-20 parts of tripropylene glycol diacrylate; the polyester acrylate is difunctional polyester acrylate, the viscosity is 2000 mpa.s/25-4000 mpa.s/25 ℃, and the acid value is less than or equal to 5 mgKOH/g. After the polyester acrylate chain segment is introduced into the main chain of the epoxy resin, the flexibility, the adhesive force and the yellowing resistance of the epoxy acrylate resin can be effectively improved, and the modified epoxy acrylate resin meets the national standard, has excellent comprehensive performance and wide application.)

1. The polyester modified epoxy acrylate resin is characterized by being prepared from the following components in parts by weight:

the polyester acrylate is difunctional polyester acrylate, the viscosity is 2000 mpa.s/25-4000 mpa.s/25 ℃, and the acid value is less than or equal to 5 mgKOH/g.

2. The polyester-modified epoxy acrylate resin of claim 1, wherein the polyester acrylate is a difunctional polyester acrylate having a viscosity of 2500mpa.s/25 ℃ to 3500mpa.s/25 ℃ and an acid value of 3mgKOH/g to 5 mgKOH/g.

3. The polyester-modified epoxy acrylate resin according to claim 1 or 2, wherein the polyester acrylate is prepared from the following components in parts by weight:

4. the polyester-modified epoxy acrylate resin according to claim 3, wherein the preparation method of the polyester acrylate comprises the following steps:

mixing the hydroxyethyl acrylate b, the phthalic anhydride b and the catalyst b, heating for the first time, and reacting to obtain a mixture A;

when the acid value of the system is 210mgKOH/g-218mgKOH/g, adding the epichlorohydrin and the polymerization inhibitor B into the mixture A, heating for the second time, and reacting to obtain a mixture B;

and when the acid value of the system is less than or equal to 5mgKOH/g, filtering and discharging to obtain the polyester acrylate.

5. The polyester-modified epoxy acrylate resin according to claim 4, wherein the temperature is raised for the first time at 100 ℃ to 110 ℃ for 2h to 3 h.

6. The polyester-modified epoxy acrylate resin according to claim 4 or 5, wherein the temperature is raised for the second time at 110 ℃ to 120 ℃ for 3h to 4 h.

7. A method for preparing the polyester-modified epoxy acrylate resin according to any one of claims 1 to 6, comprising the steps of:

mixing the hydroxyethyl acrylate a, the phthalic anhydride a and the catalyst a to obtain a mixture C;

heating the mixture C to 90-100 ℃, and reacting for 1.5-2 h to obtain a mixture D;

when the acid value of the system is 210mgKOH/g-218mgKOH/g, adding the epoxy resin and a polymerization inhibitor a into the mixture D to obtain a mixture E;

heating the mixture E to 100-110 ℃, and reacting for 3-4h to obtain a mixture F;

and when the acid value of the system is 3mgKOH/g-5mgKOH/g, cooling to 90-100 ℃, and adding the polyester acrylate and the tripropylene glycol diacrylate a into the mixture F to obtain the polyester modified epoxy acrylate resin.

8. A UV roll coated white primer, characterized in that the UV roll coated white primer comprises the polyester modified epoxy acrylate resin according to any one of claims 1 to 6.

9. The UV roller coating white primer according to claim 8, which is prepared from the following components in parts by weight:

10. the UV roll coated white primer according to claim 9, characterized in that the solvent is xylene.

11. The UV roller coating white primer according to claim 9 or 10, wherein the auxiliary agent H is one or a combination of several selected from the group consisting of an antifoaming agent, an anti-settling agent, a lubricating dispersant, fumed silica, heavy calcium carbonate, talc and a photoinitiator.

12. A method of making a UV roll coated white primer according to any one of claims 8 to 11 comprising the steps of:

and dispersing the polyester modified epoxy acrylate resin, tripropylene glycol diacrylate, an auxiliary agent H and a solvent to obtain the UV roller coating white primer.

Technical Field

The invention relates to the field of coatings, in particular to polyester modified epoxy acrylate resin and a preparation method and application thereof.

Background

Ultraviolet (UV) and Electron Beam (EB) curing radiation curing technologies are advanced technologies for surface treatment of materials emerging in the sixties of the twentieth century. The ultraviolet curing coating is a novel coating which utilizes ultraviolet light to initiate the rapid cross-linking polymerization of liquid materials in the coating and is instantly cured into solid at normal temperature, has the characteristics of high efficiency, environmental protection, energy conservation and high quality, and is widely applied to the fields of paper, wood, plastics, metal, leather, textiles, stone, glass, ceramics and the like. The UV woodware paint is the UV paint which is the first to realize commercial use and is the UV product with the largest use amount at present.

The epoxy acrylate capable of being cured by ultraviolet light is an environment-friendly prepolymer which is widely used, and has the advantages of strong adhesive force, good chemical corrosion resistance, high coating hardness and high curing speed. However, the existing epoxy acrylate has more residual acrylate groups in a film layer after photocuring, is unfavorable for aging resistance and yellowing resistance, and has high brittleness and insufficient flexibility of a cured film.

Disclosure of Invention

Therefore, the polyester modified epoxy acrylate resin which has good flexibility, strong adhesive force, high hardness and good yellowing resistance is needed to be provided.

The technical scheme is as follows:

the polyester modified epoxy acrylate resin is prepared from the following components in parts by weight:

the polyester acrylate is difunctional polyester acrylate, the viscosity is 2000 mpa.s/25-4000 mpa.s/25 ℃, and the acid value is less than or equal to 5 mgKOH/g.

The invention also provides a preparation method of the polyester modified epoxy acrylate resin, which comprises the following steps:

mixing the hydroxyethyl acrylate a, the phthalic anhydride a and the catalyst a to obtain a mixture C;

heating the mixture C to 90-100 ℃, and reacting for 1.5-2 h to obtain a mixture D;

when the acid value of the system is 210mgKOH/g-218mgKOH/g, adding the epoxy resin and a polymerization inhibitor a into the mixture D to obtain a mixture E;

heating the mixture E to 100-110 ℃, and reacting for 3-4h to obtain a mixture F;

and when the acid value of the system is 3mgKOH/g-5mgKOH/g, cooling to 90-100 ℃, and adding the polyester acrylate and the tripropylene glycol diacrylate a into the mixture F to obtain the polyester modified epoxy acrylate resin.

The invention also provides a UV roller coating white primer, which comprises the polyester modified epoxy acrylate resin.

The UV roller coating white primer is prepared from the following components in parts by weight:

the invention also provides a preparation method of the UV roller coating white primer, which comprises the following steps:

and dispersing the polyester modified epoxy acrylate resin, tripropylene glycol diacrylate b, an auxiliary agent H and a solvent to obtain the UV roller coating white primer.

Has the advantages that: the chemical activity of the epoxy group can effectively improve the hardness of the curing agent after film formation, the polyester acrylate molecule contains C-C double bond and ester group, a bifunctional polyester acrylate chain segment with the viscosity of 2000 mpa.s/25-4000 mpa.s/25 ℃, the acid value of less than or equal to 5mgKOH/g and the solid content of more than or equal to 95 percent is introduced into the main chain of the epoxy resin, the epoxy acrylate resin can be endowed with excellent flexibility, the reaction of the hydroxyethyl acrylate and the phthalic anhydride has polarity, electromagnetic bond force is generated between adjacent interfaces of the molecules, the structure is compact, and the hardness is high; the components are matched with each other, so that the hardness, flexibility, adhesive force, viscosity and yellowing resistance of the epoxy acrylate resin can be effectively improved.

Detailed Description

The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The polyester modified epoxy acrylate resin is prepared from the following components in parts by weight:

the polyester acrylate is difunctional polyester acrylate, the viscosity is 2000 mpa.s/25-4000 mpa.s/25 ℃, and the acid value is less than or equal to 5 mgKOH/g.

The chemical activity of the epoxy group can effectively improve the hardness of the curing agent after film formation, the polyester acrylate molecule contains C-C double bond and ester group, and a difunctional polyester acrylate chain segment with the viscosity of 2000 mpa.s/25-4000 mpa.s/25 ℃ and the acid value of less than or equal to 5mgKOH/g is introduced into the main chain of the epoxy resin, so that the epoxy acrylate resin can be endowed with excellent flexibility; the reaction of the hydroxyethyl acrylate and the phthalic anhydride has polarity, electromagnetic bond force is generated between adjacent interfaces of molecules, the structure is compact, and the hardness is high; the components are matched with each other, so that the hardness, flexibility, adhesive force, viscosity and yellowing resistance of the epoxy acrylate resin can be effectively improved.

In the invention, the raw materials for preparing the polyester modified epoxy acrylate resin comprise 24-30 parts by weight of hydroxyethyl acrylate a, preferably 28-30 parts by weight of hydroxyethyl acrylate, and the hydroxyethyl acrylate a is acrylic acid-hydroxyethyl acrylate from Jiangsu silver swallow chemical industry Co.

In the invention, the raw materials for preparing the polyester modified epoxy acrylate resin also comprise 30-35 parts by weight of phthalic anhydride a, wherein the reaction of the hydroxyethyl acrylate and the phthalic anhydride has polarity, and electromagnetic bond force is generated between adjacent molecular interfaces, and the phthalic anhydride a is purchased from anhydrous phthalic anhydride purchased from Aijing GmbH of Korea.

In the invention, the raw materials for preparing the polyester modified epoxy acrylate resin also comprise 15-20 parts by weight of epoxy resin, preferably 15-18 parts by weight of epoxy resin, wherein the epoxy resin is purchased from Jiangsu nong Yang, the model is YN1828, the epoxy equivalent is 185-188, and the hydrolysis chlorine is less than or equal to 200 PPM; or purchased from Touchun Nolnogu chemical engineering, model E-44, epoxy equivalent of 185-188 and hydrolytic chlorine of less than or equal to 200 PPM.

In the present invention, the raw materials for preparing the polyester-modified epoxy acrylate resin further comprise 15 to 20 parts by weight of tripropylene glycol diacrylate a, which is commercially available from tripropylene glycol diacrylate (benzene-free TPGDA) of shanghai cyanide speciality chemical company, ltd, and can be used as a reactive diluent to significantly reduce the viscosity of a resin system.

In the invention, the raw material of the polyester modified epoxy acrylate resin also comprises 0.8-1 part by weight of catalyst a, wherein the catalyst a is N, N-dibutylamine. The manufacturer of the N, N-dibutylamine is not particularly limited in this regard.

In the invention, the raw materials of the polyester modified epoxy acrylate resin also comprise 0.1-0.3 part by weight of polymerization inhibitor a, and the polymerization inhibitor a is p-hydroxyanisole, so that the surface polymerization inhibition effect of oxygen on free radical polymerization is effectively prevented. The manufacturer of the p-hydroxyanisole is not particularly limited in this regard.

In the invention, the raw material of the polyester modified epoxy acrylate resin also comprises 15-25 parts by weight of polyester acrylate, preferably 15-20 parts by weight of polyester acrylate; the polyester acrylate is difunctional polyester acrylate, the viscosity is 2000 mpa.s/25-4000 mpa.s/25 ℃, the acid value is less than or equal to 5mgKOH/g, preferably, the viscosity of the polyester acrylate is 2500 mpa.s/25-3500 mpa.s/25 ℃, and the acid value is 3mgKOH/g-5 mgKOH/g.

In some preferred embodiments, the polyester acrylate has a solids content of 95% or more.

The polyester acrylate is a self-produced polyester acrylate of Jia Bao Li chemical group Limited company.

The polyester acrylate is prepared from the following components in parts by weight:

the types and manufacturers of the hydroxyethyl acrylate b, the phthalic anhydride b, the catalyst b and the polymerization inhibitor b can be the same as those of the hydroxyethyl acrylate a, the phthalic anhydride a, the catalyst a and the polymerization inhibitor a, and are not described again.

In the invention, the raw material for preparing the polyester acrylate comprises 20-30 parts by weight of epoxy chloropropane, wherein the epoxy chloropropane is obtained from epichlorohydrin of Qilu chemical Co., Ltd.

The preparation method of the polyester acrylate comprises the following steps:

mixing the hydroxyethyl acrylate b, the phthalic anhydride b and the catalyst b, heating for the first time, and reacting to obtain a mixture A;

when the acid value of the system is 210mgKOH/g-218mgKOH/g, adding the epichlorohydrin and the polymerization inhibitor B into the mixture A, heating for the second time, and reacting to obtain a mixture B;

and when the acid value of the system is less than or equal to 5mgKOH/g, filtering and discharging to obtain the polyester acrylate.

Preferably, the temperature is raised for the first time at 100-110 ℃, and the reaction time is 2-3 h.

Preferably, the temperature is raised for the second time, the temperature is 110-120 ℃, and the reaction time is 3-4 h.

The invention also provides a preparation method of the polyester modified epoxy acrylate resin, which comprises the following steps:

mixing the hydroxyethyl acrylate a, the phthalic anhydride a and the catalyst a to obtain a mixture C;

heating the mixture C to 90-100 ℃, and reacting for 1.5-2 h to obtain a mixture D;

when the acid value of the system is 210mgKOH/g-218mgKOH/g, adding the epoxy resin and a polymerization inhibitor a into the mixture D to obtain a mixture E;

heating the mixture E to 100-110 ℃, and reacting for 3-4h to obtain a mixture F;

and when the acid value of the system is 3mgKOH/g-5mgKOH/g, cooling to 90-100 ℃, and adding the polyester acrylate and the tripropylene glycol diacrylate a into the mixture F to obtain the polyester modified epoxy acrylate resin.

The invention also provides a UV roller coating white primer, which comprises the polyester modified epoxy acrylate resin.

The UV roller coating white primer is prepared from the following components in parts by weight:

the raw materials for preparing the UV roller coating white primer comprise 25-40 parts by weight of the polyester modified epoxy acrylate resin, and can meet the performances of high gloss, high humidity, high adhesion and the like required by the white primer.

The raw material for preparing the UV roller coating white primer also comprises 10-15 parts by weight of tripropylene glycol diacrylate b which is used as a reactive diluent and can obviously reduce the viscosity of a resin system, and the tripropylene glycol diacrylate is commercially available from tripropylene glycol diacrylate (benzene-free TPGDA) of Shanghai Cyani speciality chemical Co.

The raw materials for preparing the UV roller coating white primer also comprise 20-25 parts by weight of titanium dioxide, and the titanium dioxide manufacturers have no special limitation to the invention.

The raw materials for preparing the UV roller coating white primer also comprise a certain amount of an auxiliary agent H and a solvent, wherein the auxiliary agent H is one or a combination of more of a defoaming agent, an anti-settling slurry, a lubricating dispersant, fumed silica, heavy calcium carbonate, talcum powder and a photoinitiator, and the solvent is xylene.

The defoaming agent is polysiloxane-polyether copolymer.

The anti-settling slurry is a dispersed mixture of fumed silica and xylene.

The lubricating dispersant is a solvent type high molecular weight wetting dispersant.

The particle size of the talcum powder is 2500 meshes.

The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.

The invention also provides a preparation method of the UV roller coating white primer, which comprises the following steps:

and dispersing the polyester modified epoxy acrylate resin, tripropylene glycol diacrylate b, an auxiliary agent H and a solvent to obtain the UV roller coating white primer.

For further understanding of the present invention, the polyester modified epoxy acrylate resin and its application provided by the present invention will be specifically described below with reference to examples.

Unless otherwise specified, all starting materials below are commercial technical grade materials.