阅读说明：本技术 一种紫外光固化亮光白树脂及其制备方法 (Ultraviolet light curing bright white resin and preparation method thereof ) 是由 邹庆鹏 谢灯咨 于 2020-11-24 设计创作，主要内容包括：本发明提供了一种紫外光固化亮光白树脂,按重量份数,包括以下组分：羟基丙烯酸酯50～60份,酸酐20～30份,抗氧剂0～0.2份,阻聚剂0～0.1份,环氧树脂15～30份,催化剂0～0.8份,不饱和聚酯0～8份。这种紫外光固化亮光白树脂,其使用羟基丙烯酸酯和环氧树脂作为主体反应物,合成可紫外光固化的亮光白树脂,通过引入大量多官的羟基丙烯酸酯使得树脂具有高的双键密度,固化后具有高硬度、高光泽；环氧树脂采用1-4丁二醇二缩水甘油醚,将其优异的耐黄变性能带入分子中,使合成的树脂具有优异的亮白性能。本发明还提供了上述紫外光固化亮光白树脂的制备方法。(The invention provides an ultraviolet curing bright white resin which comprises the following components in parts by weight: 50-60 parts of hydroxyl acrylate, 20-30 parts of anhydride, 0-0.2 part of antioxidant, 0-0.1 part of polymerization inhibitor, 15-30 parts of epoxy resin, 0-0.8 part of catalyst and 0-8 parts of unsaturated polyester. The ultraviolet light curing bright white resin is synthesized by using hydroxyl acrylate and epoxy resin as main reactants, and has high double bond density and high hardness and high gloss after being cured by introducing a large amount of polyfunctional hydroxyl acrylate; the epoxy resin adopts 1-4 butanediol diglycidyl ether, and brings the excellent yellowing resistance into molecules, so that the synthesized resin has excellent bright white performance. The invention also provides a preparation method of the ultraviolet curing bright white resin.)

1. The ultraviolet curing bright white resin is characterized by comprising the following components in parts by weight:

2. the UV-curable brilliant white resin according to claim 1, wherein the hydroxy acrylate is at least one of pentaerythritol triacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.

3. The UV-curable brilliant white resin according to claim 1, wherein the acid anhydride is at least one of hexahydrophthalic anhydride or succinic anhydride.

4. The UV-curable brilliant white resin according to claim 1, wherein the antioxidant is at least one of hypophosphorous acid, 2, 6-di-tert-butylphenol or phenol.

5. The UV-curable brilliant white resin according to claim 1, wherein the polymerization inhibitor is at least one of p-hydroxyanisole or hydroquinone.

6. The UV-curable brilliant white resin according to claim 1, wherein the epoxy resin is 1, 4-butanediol diglycidyl ether.

7. The UV-curable brilliant white resin according to claim 1, wherein the catalyst is at least one of triphenylphosphine, triethylamine or benzyltriethylammonium chloride.

8. A method for preparing the UV-curable brilliant white resin according to any one of claims 1 to 7, characterized in that it is prepared by the following steps:

s1, sequentially adding hydroxyl acrylate, acid anhydride, an antioxidant and a polymerization inhibitor into a reaction kettle in parts by weight, heating to 40-50 ℃, and stirring until the hydroxyl acrylate, the acid anhydride, the antioxidant and the polymerization inhibitor are dissolved;

s2, heating to 100 ℃, and preserving heat for 1-2 h;

s3, cooling to 90 ℃, adding epoxy resin, a catalyst and unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

s4, heating to 108-110 ℃ and preserving heat;

s5, measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Technical Field

The invention relates to the technical field of paint production, in particular to ultraviolet curing bright white resin and a preparation method thereof.

Background

The ultraviolet curing is a process of initiating the polymerization and crosslinking of resin containing active functional groups into insoluble and infusible solid coating films by converting a photoinitiator in a liquid UV material into free radicals or cations under the medium-short wave irradiation of ultraviolet light. The ultraviolet curing technology is widely applied to the fields of coatings, printing ink, adhesives and the like because of the advantages of high efficiency, economy, energy conservation, wide applicability and environmental friendliness.

In the field of coatings, white base paints require not only the resin to have bright white properties, but also high hardness, high gloss, yellowing resistance, and bright white transparency.

Chinese patent with publication number CN103059717A discloses a high leveling property ultraviolet curing coating composition for curtain coating, which comprises the following components in parts by weight: 4-30 parts of low-viscosity acrylate resin, 70-96 parts of monomer, 3-8 parts of photoinitiator, 140-350 parts of solvent and 0.01-1 part of flatting agent. Preferably: 4-20 parts of low-viscosity acrylate resin, 80-96 parts of monomer, 4-6 parts of photoinitiator, 100-250 parts of solvent and 0.05-0.5 part of flatting agent. The viscosity and the adding amount of the resin are controlled, so that the viscosity can be effectively reduced, and the leveling property of the coating is improved. However, the coating composition prepared in the patent still has to be verified in the aspect of bright white performance.

Therefore, how to provide a resin which can be cured by ultraviolet light and has bright white performance is a technical problem to be solved by those skilled in the art.

Disclosure of Invention

In order to solve the above problems in the prior art, the present invention provides an ultraviolet light curing brilliant white resin, which uses hydroxyl acrylate and epoxy resin as main reactants to synthesize an ultraviolet light curable brilliant white resin, wherein the resin has high double bond density by introducing a large amount of polyfunctional hydroxyl acrylate, and has high hardness and high gloss after curing; the epoxy resin adopts 1-4 butanediol diglycidyl ether, and brings the excellent yellowing resistance into molecules, so that the synthesized resin has excellent bright white performance. The invention also provides a preparation method of the ultraviolet curing bright white resin.

In order to achieve the purpose, the invention provides the following technical scheme:

the ultraviolet curing bright white resin comprises the following components in parts by weight:

according to a further description as an embodiment of the present invention, the hydroxy acrylate is at least one of pentaerythritol triacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate.

As a further description of the technical solution of the present invention, the acid anhydride is at least one of hexahydrophthalic anhydride or succinic anhydride.

As further description of the technical scheme of the invention, the antioxidant is at least one of hypophosphorous acid, 2, 6-di-tert-butylphenol or phenol.

As a further description of the technical scheme of the invention, the polymerization inhibitor is at least one of p-hydroxyanisole or hydroquinone.

As further described in the technical scheme of the invention, the epoxy resin is 1, 4-butanediol diglycidyl ether, the epoxy resin brings excellent yellowing resistance into molecules, and the synthesized resin has excellent bright white performance.

As further description of the technical scheme of the invention, the catalyst is at least one of triphenylphosphine, triethylamine or benzyltriethylammonium chloride.

The invention also provides a preparation method of the ultraviolet curing bright white resin, which comprises the following steps:

s1, sequentially adding hydroxyl acrylate, acid anhydride, an antioxidant and a polymerization inhibitor into a reaction kettle in parts by weight, heating to 40-50 ℃, and stirring until the hydroxyl acrylate, the acid anhydride, the antioxidant and the polymerization inhibitor are dissolved;

s2, heating to 100 ℃, and preserving heat for 1-2 h;

s3, cooling to 90 ℃, adding epoxy resin, a catalyst and unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

s4, heating to 108-110 ℃ and preserving heat;

s5, measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Based on the technical scheme, the invention has the following technical effects:

(1) the ultraviolet light curing bright white resin provided by the invention uses hydroxyl acrylate and epoxy resin as main reactants to synthesize the ultraviolet light curing bright white resin, and the resin has high double bond density by introducing a large amount of polyfunctional hydroxyl acrylate and has high hardness and high gloss after curing; the epoxy resin adopts 1-4 butanediol diglycidyl ether, and brings the excellent yellowing resistance into molecules, so that the synthesized resin has excellent bright white performance.

(2) The preparation method of the ultraviolet curing bright white resin provided by the invention is simple to operate, and the ultraviolet curing bright white resin containing unsaturated double bonds with better comprehensive performance can be prepared by optimizing components and adopting a temperature programming process.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. The invention provides a preferred embodiment. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Example 1

The ultraviolet curing bright white resin comprises the following components in parts by weight:

the hydroxy acrylate is at least one of pentaerythritol triacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.

The acid anhydride is at least one of hexahydrophthalic anhydride or succinic anhydride.

The antioxidant is at least one of hypophosphorous acid, 2, 6-di-tert-butylphenol or phenol.

The polymerization inhibitor is at least one of p-hydroxyanisole or hydroquinone.

The epoxy resin is 1, 4-butanediol diglycidyl ether, the epoxy resin brings excellent yellowing resistance into molecules, and the synthesized resin has excellent bright white performance.

The catalyst is at least one of triphenylphosphine, triethylamine or benzyltriethylammonium chloride.

The preparation method of the ultraviolet curing bright white resin comprises the following steps:

s1, sequentially adding hydroxyl acrylate, acid anhydride, an antioxidant and a polymerization inhibitor into a reaction kettle in parts by weight, heating to 40-50 ℃, and stirring until the hydroxyl acrylate, the acid anhydride, the antioxidant and the polymerization inhibitor are dissolved;

s2, heating to 100 ℃, and preserving heat for 1-2 h;

s3, cooling to 90 ℃, adding epoxy resin, a catalyst and unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

s4, heating to 108-110 ℃ and preserving heat;

s5, measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Example 2

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): adding 525g of pentaerythritol triacrylate, 39g of hydroxyethyl acrylate, 200g of hexahydrophthalic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle in sequence, heating to 40-50 ℃, and stirring until the mixture is dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 182g of 1, 4-butanediol diglycidyl ether, 4g of triphenylphosphine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

The self-produced unsaturated polyester is high-fullness and yellowing-resistant unsaturated polyester resin.

Example 3

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): sequentially adding 300g of pentaerythritol triacrylate, 200g of hydroxypropyl acrylate, 43.7g of hydroxypropyl acrylate, 200g of succinic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle, heating to 40-50 ℃, and stirring until the components are dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 176g of 1, 4-butanediol diglycidyl ether, 4g of triphenylphosphine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Example 4

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): adding 525g of pentaerythritol triacrylate, 43.7g of hydroxyethyl methacrylate, 200g of hexahydrophthalic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle in sequence, heating to 40-50 ℃, and stirring until the mixture is dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 182g of 1, 4-butanediol diglycidyl ether, 3.5g of triethylamine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Example 5

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): adding 520g of pentaerythritol triacrylate, 48.4g of hydroxypropyl methacrylate, 200g of hexahydrophthalic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle in sequence, heating to 40-50 ℃, and stirring until the mixture is dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 182g of 1, 4-butanediol diglycidyl ether, 4g of triphenylphosphine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Example 6

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): adding 525g of pentaerythritol triacrylate, 39g of hydroxyethyl acrylate, 130g of succinic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle in sequence, heating to 40-50 ℃, and stirring until the components are dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 182g of 1, 4-butanediol diglycidyl ether, 4g of triphenylphosphine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Example 7

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): adding 525g of pentaerythritol triacrylate, 43.7g of hydroxypropyl acrylate, 130g of succinic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle in sequence, heating to 40-50 ℃, and stirring until the mixture is dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 182g of 1, 4-butanediol diglycidyl ether, 4g of triphenylphosphine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Example 8

An ultraviolet light-curable brilliant white resin is prepared according to the following steps:

step 1): adding 525g of pentaerythritol triacrylate, 43.7g of hydroxypropyl methacrylate, 130g of succinic anhydride, 0.5g of 2, 6-di-tert-butylphenol and 0.6g of p-hydroxyphenyl ether into a reaction kettle in sequence, heating to 40-50 ℃, and stirring until the mixture is dissolved;

step 2): heating to 100 ℃ and preserving heat for 1-2 h;

step 3): cooling to 90 ℃, adding 176g of 1, 4-butanediol diglycidyl ether, 4g of triphenylphosphine and 46g of self-produced unsaturated polyester, slowly heating to 95 ℃, and keeping the temperature for 1 h;

step 4): heating to 108-110 ℃ and preserving heat;

step 5): and (4) measuring the acid value, and cooling and discharging when the Av is less than or equal to 4 mgKOH/g.

Comparative example 1

Conventional uv curable resins.

The uv-curable brilliant white resins of examples 2 to 8, and the conventional uv-curable resin of comparative example 1 were examined. The test results are shown in Table 1.

Table 1 performance test table of uv-curable brilliant white resins of examples 2 to 8 and conventional uv-curable resin of comparative example 1

Detecting items	Appearance of coating film	Yellowing resistance	Gloss of	Adhesion force	Hardness of
						Example 2	Full of light and bright as mirror	+++	103	0	2H
Example 3	Full of light and bright as mirror	+++	102	0	2H
						Example 4	Full of light and bright as mirror	+++	100	0	2H
Example 5	Full of light and bright as mirror	+++	100	0	2H
						Example 6	Full of light and bright as mirror	+++	102	0	2H
Example 7	Full of light and bright as mirror	+++	104	0	2H
						Example 8	Full of light and bright as mirror	+++	99	0	2H
Comparative example 1	Smooth and full of	++	95	1	H

As can be seen from the test results in table 1, the uv curable brilliant white resins provided in examples 2 to 8, which are synthesized using hydroxy acrylate and epoxy resin as main reactants, have high double bond density by introducing a large amount of multifunctional hydroxy acrylate, and have high hardness and high gloss after curing; the epoxy resin adopts 1-4 butanediol diglycidyl ether, and brings the excellent yellowing resistance into molecules, so that the synthesized resin has excellent bright white performance, and in addition, the resin also has good adhesive force and performance.

The foregoing is merely exemplary and illustrative of the structures of the present invention, which are described in some detail and detail, and are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications are possible without departing from the inventive concept, and such obvious alternatives fall within the scope of the invention.