阅读说明：本技术 一种汽车大灯镀膜剂及其制备方法 (Automobile headlamp coating agent and preparation method thereof ) 是由 冯敏乐 彭健华 吴勇 于 2021-08-18 设计创作，主要内容包括：本发明涉及涂料技术领域,尤其涉及一种汽车大灯镀膜剂及其制备方法。汽车大灯使用久了容易出现发黄、模糊、开裂的老化现象,更换的话必须要换掉整个汽车大灯总成,包括还能正常使用的原有灯泡和反光杯,造成一定的资源浪费。基于上述问题,本发明提供一种汽车大灯镀膜剂,涂料成分中含有本发明自制的有机-无机杂化聚氨酯丙烯酸酯,采用本发明制备的汽车大灯镀膜剂对汽车大灯喷涂后形成的修复涂层具有较高的硬度、光泽度和耐候性,外观修复效果能达到八九成新的车灯,本发明这种对汽车大灯翻新的修复方式,成本较低,操作简单,符合绿色可持续发展的要求,具有较好的应用前景。(The invention relates to the technical field of coatings, in particular to a coating agent for automobile headlights and a preparation method thereof. The automobile headlamp is used for a long time, the aging phenomena of yellowing, blurring and cracking easily occur, and the whole automobile headlamp assembly must be replaced if the automobile headlamp is replaced, including an original bulb and a reflection cup which can be normally used, so that certain resource waste is caused. Based on the problems, the invention provides the automobile headlamp coating agent, the coating components contain the self-made organic-inorganic hybrid polyurethane acrylate, the repair coating formed after the automobile headlamp is sprayed by the automobile headlamp coating agent prepared by the invention has higher hardness, glossiness and weather resistance, and the appearance repair effect can reach eight nine new automobile lamps.)

1. The automobile headlamp coating agent is characterized by comprising the following components in percentage by mass:

2. the automobile headlamp coating agent according to claim 1, wherein the high-functionality aliphatic polyurethane acrylate is a compound of 9-functionality aliphatic polyurethane acrylate, 12-functionality aliphatic polyurethane acrylate and 15-functionality aliphatic polyurethane acrylate according to a mass ratio of 1:1: 1.

3. The automobile headlamp coating agent according to claim 1, wherein the organic-inorganic hybrid polyurethane acrylate is prepared by the following steps in percentage by mass:

(1) adding 25% of silica sol into a reaction kettle, stirring and heating to 60 ℃, continuously dropping 25% of 3- (methacryloyloxy) propyl trimethoxy silane under the stirring condition, and preserving heat for 1h to obtain modified silica sol;

(2) and (2) adding 10% of pentaerythritol triacrylate and 40% of hexafunctional aliphatic urethane acrylate into a reaction kettle, stirring and heating to 60 ℃, adding the modified silica sol prepared in the step (1) under the stirring condition, and preserving heat for 1h to obtain the organic-inorganic hybrid urethane acrylate.

4. The coating agent for automobile headlights according to claim 3, wherein said hexafunctional aliphatic polyurethane acrylate is Changxing 6145-100.

5. The coating agent for automobile headlights according to claim 1, wherein the polymerization monomer is one or a mixture of two or more of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.

6. The coating composition for automobile headlights according to claim 1, wherein the photoinitiator is one or a mixture of two or more of 1-hydroxy-cyclohexyl-1-phenyl ketone, 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide, benzoyl formate, bis-2, 6-difluoro-3-pyrrole-phenyltitanocene.

7. The automobile headlamp coating agent as claimed in claim 1, wherein the leveling agent is one or a mixture of two or more of acrylate, polyester modified organosiloxane and polyether modified organosiloxane.

8. The coating agent for automobile headlights according to claim 1, wherein the weather-resistant auxiliary agent is one or a mixture of two or more of benzotriazoles mixture, sebacates mixture, and hydroxy triazine derivatives.

9. The coating agent for automobile headlamps as claimed in claim 1, characterized in that the solvent is one or a mixture of two or more of EAC, IBIB, IPA, IBA, n-butanol, dimethyl carbonate, BAC, propylene glycol methyl ether acetate and propylene glycol methyl ether.

10. The automobile headlamp coating agent according to any one of claims 1 to 9, which is prepared by the following steps:

under the environment of completely isolating ultraviolet light by using a yellow light lamp, mixing a polymerization monomer, a photoinitiator and a solvent according to the formula amount, stirring at the speed of 200rpm until the mixture is uniformly dispersed, then sequentially adding a high-functional aliphatic polyurethane acrylic resin, an organic-inorganic hybrid polyurethane acrylic resin, a leveling agent and an anti-aging auxiliary agent, and stirring at the speed of 800rpm for 20min until the mixture is uniformly mixed to prepare the automobile headlamp coating agent.

Technical Field

The invention relates to the technical field of coatings, in particular to a coating agent for automobile headlights and a preparation method thereof.

Background

The vehicle headlight serves as an important component for vehicle safety. With increasing safety and costs, headlights for cars are gradually being developed from the first glass covers to the now stiffened PC covers.

The hardness of the PC outer cover is determined by the UV coating sprayed on the surface of the PC outer cover, and after the PC outer cover is used for a certain period of time, the outer cover of the automobile headlamp can generate aging phenomena such as yellowing, blurring and cracking, and the like, thereby having great influence on the safe driving and the appearance of the automobile. Because of the safety consideration, need change the car headlight, must change whole car headlight assembly if change, including original bulb and the reflection of light cup that can also normal use, the cost of change is higher, and causes certain wasting of resources.

Disclosure of Invention

Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: the automobile headlamp is used for a long time, the aging phenomena of yellowing, blurring and cracking easily occur, and the whole automobile headlamp assembly must be replaced if the automobile headlamp is replaced, including an original bulb and a reflection cup which can be normally used, so that certain resource waste is caused.

The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides a coating agent for automobile headlamps, which comprises the following components in percentage by mass:

specifically, the high-functionality aliphatic polyurethane acrylate is a compound consisting of 9-functionality aliphatic polyurethane acrylate, 12-functionality aliphatic polyurethane acrylate and 15-functionality aliphatic polyurethane acrylate according to the mass ratio of 1:1: 1.

Specifically, the organic-inorganic hybrid polyurethane acrylate is prepared by the following steps in percentage by mass:

(1) adding 25% of silica sol into a reaction kettle, stirring and heating to 60 ℃, continuously dropping 25% of 3- (methacryloyloxy) propyl trimethoxy silane under the stirring condition, and preserving heat for 1h to obtain modified silica sol;

(2) and (2) adding 10% of pentaerythritol triacrylate and 40% of hexafunctional aliphatic urethane acrylate into a reaction kettle, stirring and heating to 60 ℃, adding the modified silica sol prepared in the step (1) under the stirring condition, and preserving heat for 1h to obtain the organic-inorganic hybrid urethane acrylate.

Specifically, the hexafunctional aliphatic polyurethane acrylate is Changxing 6145-100.

Specifically, the polymerization monomer is one or a mixture of more than two of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate.

Specifically, the photoinitiator is one or a mixture of more than two of 1-hydroxy-cyclohexyl-1-phenyl ketone, 2, 4, 6 (trimethylbenzoyl) diphenyl phosphine oxide, benzoyl formate and bis-2, 6-difluoro-3 pyrrole-phenyl titanocene.

Specifically, the leveling agent is one or a mixture of more than two of acrylate, polyester modified organic siloxane and polyether modified organic siloxane.

Specifically, the weather-resistant auxiliary agent is one or a mixture of more than two of benzotriazole mixture, sebacate mixture and hydroxy triazine derivative.

Specifically, the solvent is one or a mixture of more than two of EAC, IBIB, IPA, IBA, n-butanol, dimethyl carbonate, BAC, propylene glycol methyl ether acetate and propylene glycol methyl ether.

Specifically, the coating agent for the automobile headlamp is prepared according to the following steps:

under the environment of completely isolating ultraviolet light by using a yellow light lamp, mixing a polymerization monomer, a photoinitiator and a solvent according to the formula amount, stirring at the speed of 200rpm until the mixture is uniformly dispersed, then sequentially adding a high-functional aliphatic polyurethane acrylic resin, an organic-inorganic hybrid polyurethane acrylic resin, a leveling agent and an anti-aging auxiliary agent, and stirring at the speed of 800rpm for 20min until the mixture is uniformly mixed to prepare the automobile headlamp coating agent.

The invention has the beneficial effects that:

(1) after the automobile headlamp coating agent prepared by the invention is adopted to renovate an automobile headlamp, a dried repair coating has higher hardness, glossiness and weather resistance, and the appearance repair effect can reach eight to nine new automobile lamps;

(2) the repairing method for renovating the automobile headlamp has the advantages of low cost and simple operation, meets the requirement of green sustainable development, and has good application prospect.

Detailed Description

The present invention will now be described in further detail with reference to examples.

The high-functional aliphatic urethane acrylate used in the following examples of the present invention was a composition of 9-functional aliphatic urethane acrylate, 12-functional aliphatic urethane acrylate, and 15-functional aliphatic urethane acrylate at a mass ratio of 1:1: 1.

The organic-inorganic hybrid urethane acrylate adopted in the following examples of the invention is prepared by the following steps in percentage by mass:

(1) adding 25% of silica sol into a reaction kettle, stirring and heating to 60 ℃, continuously dropping 25% of 3- (methacryloyloxy) propyl trimethoxy silane under the stirring condition, and preserving heat for 1h to obtain modified silica sol;

(2) and (2) adding 10% of pentaerythritol triacrylate and 40% of hexafunctional aliphatic urethane acrylate into a reaction kettle, stirring and heating to 60 ℃, adding the modified silica sol prepared in the step (1) under the stirring condition, and preserving heat for 1h to obtain the organic-inorganic hybrid urethane acrylate.

The hexafunctional aliphatic polyurethane acrylate used in the following examples of the present invention was Changxing 6145-100.

The polymerization monomer used in the following examples of the present invention is one or a mixture of two or more of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and 2 moles of caprolactone-modified dipentaerythritol hexaacrylate.

The photoinitiator used in the following examples of the present invention is one or a mixture of two or more of 1-hydroxy-cyclohexyl-1-phenyl ketone, 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide, benzoylformate, bis-2, 6-difluoro-3-pyrrole-phenyltitanocene.

The leveling agent used in the following embodiments of the present invention is one or a mixture of two or more of acrylate, polyester-modified organosiloxane, and polyether-modified organosiloxane.

The weather-resistant auxiliary agent adopted in the following embodiments of the invention is one or a mixture of more than two of benzotriazole mixture, sebacate mixture and hydroxy triazine derivative.

The solvent adopted in the following embodiments of the invention is one or a mixture of more than two of EAC, IBIB, IPA, IBA, n-butanol, dimethyl carbonate, BAC, propylene glycol methyl ether acetate and propylene glycol methyl ether.

The coating agent for the automobile headlamp of the embodiment of the invention is prepared by the following steps:

under the environment of completely isolating ultraviolet light by using a yellow light lamp, mixing a polymerization monomer, a photoinitiator and a solvent according to the formula amount, stirring at the speed of 200rpm until the mixture is uniformly dispersed, then sequentially adding a high-functional aliphatic polyurethane acrylic resin, an organic-inorganic hybrid polyurethane acrylic resin, a leveling agent and an anti-aging auxiliary agent, and stirring at the speed of 800rpm for 20min until the mixture is uniformly mixed to prepare the automobile headlamp coating agent.

Example 1

The automobile headlamp coating agent comprises the following components in percentage by mass:

example 2

The automobile headlamp coating agent comprises the following components in percentage by mass:

example 3

The automobile headlamp coating agent comprises the following components in percentage by mass:

example 4

The automobile headlamp coating agent comprises the following components in percentage by mass:

example 5

The automobile headlamp coating agent comprises the following components in percentage by mass:

comparative example 1 is the same as example 1 except that the high-functional aliphatic urethane acrylate used in comparative example 1 is a composition of 9-functional aliphatic urethane acrylate, 12-functional aliphatic urethane acrylate and 15-functional aliphatic urethane acrylate in a mass ratio of 1:2: 1.

Comparative example 2 is the same as example 1 except that the high-functional aliphatic urethane acrylate used in comparative example 2 is a composition of 9-functional aliphatic urethane acrylate, 12-functional aliphatic urethane acrylate and 15-functional aliphatic urethane acrylate in a mass ratio of 1:1: 2.

Comparative example 3 is the same as example 1 except that the high-functional aliphatic urethane acrylate used in comparative example 3 is a compound of 9-functional aliphatic urethane acrylate, 12-functional aliphatic urethane acrylate and 15-functional aliphatic urethane acrylate in a mass ratio of 2:1: 1.

Comparative example 4 the same as example 1 except that comparative example 4 used the hexafunctional aliphatic urethane acrylate in the preparation of the organic-inorganic hybrid urethane acrylate was sartomer CN 9010.

Comparative example 5 is the same as example 1 except that comparative example 5 uses a hexafunctional aliphatic urethane acrylate as Changxing 6146-100 in the preparation of the organic-inorganic hybrid urethane acrylate.

Comparative example 6 the same as example 1 except that comparative example 6 used a hexafunctional organic-inorganic hybrid monomer model number 601Q-35 instead of the self-made organic-inorganic hybrid urethane acrylate of the present invention.

And fully polishing the automobile headlamp with cracked surface layer by using 2000-mesh sand paper, wiping the surface by using alcohol to remove oil stains on the surface, spraying the coating agents prepared in the examples 1-5 and the comparative examples 1-5 on the surface of the polished automobile headlamp, leveling the surface at room temperature, and curing the coating agents under the irradiation of an ultraviolet lamp with the power of 40W to form a repair coating.

And (3) performance testing:

adhesion, hardness, gloss, hot and cold cycle resistance, and weather resistance tests were performed on the repair coatings formed in examples 1-5 and comparative examples 1-6:

1. adhesion force: the adhesion was measured according to ASTM D3359-2002 "adhesive tape method".

2. Hardness: the test is carried out according to GB/T6739-2006 determination of paint film hardness by the pencil method for color paint and varnish.

3. Gloss: the test was carried out using a gloss meter, the test angle being 60 degrees.

4. Cold and heat cycle resistance: cold-hot cycle testing machine, conditions: 80 ℃ x 3h → room temperature x 1h → 30 ℃ x 3h → room temperature x 1h is one cycle, and the test conditions are 6 cycles.

5. Weather resistance (xenon lamp accelerated aging test machine): the method is carried out according to the time set by the base material classification, after the time set is reached, the surface is cleaned by soapy water, then the surface is placed for 2 hours at room temperature, and the appearance, the adhesive force, the color, the luster and the like are inspected.

The test conditions are as follows:

a. average irradiance: 550W/m²；

b. Temperature of the working chamber: the air temperature is 45 ℃ plus or minus 2 ℃, and the blackboard temperature is 65 ℃ plus or minus 2 ℃;

c. relative humidity: 60% -80%;

d. artificially raining for 18 minutes in light every 120 minutes, and using pure water (the conductivity is less than 2 mu s/cm) as a water source;

e. the conditions are repeated until a specified total time.

And (4) qualified standard: the delta E (color difference) is less than or equal to 3.0, the gloss retention rate is more than or equal to 80 percent, the adhesive force is more than or equal to 4B, and the phenomena of whitening, cracking, foaming and the like do not occur on the board surface.

6. And (3) wear resistance test: a sample plate with the specification of 10cm multiplied by 10cm is manufactured and placed on a Taber 5135 rotary abrasion-resistant testing machine for testing, and the testing conditions are as follows: the load is 500G, a CS-10F grinding wheel is used for rotating 100 times, the gloss before and after the comparison test is carried out, and the gloss retention rate is more than or equal to 80 percent, so that the product is qualified.

The specific test results are shown in table 1:

TABLE 1

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.