阅读说明：本技术 一种eb固化铝基板耐磨涂层 (EB solidified aluminum substrate wear-resistant coating ) 是由 赖俊伟 彭健华 吴勇 于 2021-09-17 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EB固化铝基板耐磨涂层。铝基层表面设置的耐酸碱涂层通常不具备较好的耐磨性,在搬运过程中,涂层容易被划伤从而在电路层的蚀刻工艺中失去对铝基层的保护效果。基于上述问题,本发明提供一种EB固化铝基板耐磨涂层,其涂料成分中的改性聚氨酯丙烯酸酯Ⅰ分子结构中引入了聚丁二烯连段,有效提高了固化涂层的韧性、耐磨性和耐刮擦性；改性聚氨酯丙烯酸酯Ⅱ分子结构中引入了三环葵烷结构,可进一步提高涂层的硬度和耐刮擦性。该EB固化铝基板耐磨涂层能有效保障电路层的蚀刻工艺中对铝基层的保护效果。(The invention relates to the technical field of coatings, in particular to an EB (Electron Beam) cured aluminum substrate wear-resistant coating. The acid and alkali resistant coating arranged on the surface of the aluminum base layer generally does not have good wear resistance, and the coating is easily scratched in the carrying process, so that the protection effect on the aluminum base layer is lost in the etching process of the circuit layer. Based on the problems, the invention provides the EB cured aluminum substrate wear-resistant coating, wherein polybutadiene connecting segments are introduced into the molecular structure of the modified polyurethane acrylate I in the coating components, so that the toughness, the wear resistance and the scratch resistance of the cured coating are effectively improved; the modified polyurethane acrylate II molecular structure introduces a tricyclodecane structure, so that the hardness and scratch resistance of the coating can be further improved. The EB curing aluminum substrate wear-resistant coating can effectively guarantee the protection effect on an aluminum base layer in the etching process of a circuit layer.)

1. An EB (Electron beam) cured aluminum substrate wear-resistant coating is characterized by comprising the following components in parts by weight:

15-25 parts of modified polyurethane acrylate I

15-25 parts of modified polyurethane acrylate II

15-25 parts of urethane acrylate

10-20 parts of active monomer

30-60 parts of diamond micro powder

1-5 parts of wear-resistant auxiliary agent

0.1-0.5 part of dispersant.

2. The EB-cured aluminum substrate wear-resistant coating according to claim 1, wherein the modified polyurethane acrylate I is prepared by the following steps:

adding 30.2g of IPDI, 0.04g of catalyst DBTDL and 70mL of THF into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding 30.4g of PETA into the flask under the protection of nitrogen, stirring for reaction after the dropwise addition is completed, monitoring the reaction through FTIR measurement, adding 0.005g of hydroquinone into the reaction system, dropwise adding HTPB, continuing the reaction at 70 ℃ until the isocyanate absorption peak of IPDI disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the colorless high-viscosity liquid modified polyurethane acrylate I.

3. The EB-cured aluminum substrate wear-resistant coating according to claim 1, wherein the modified polyurethane acrylate II is prepared by the following steps:

(1) adding 28.2g of DCPDA, 0.05g of catalyst 1173 and 70mL of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding 10.4g of mercaptoethanol into the flask under the protection of nitrogen, irradiating the mercaptoethanol with a 365nm wavelength LED lamp while stirring, monitoring the reaction through FTIR measurement, eliminating the double bond absorption peak in the reactant, and removing the solvent by rotary evaporation to obtain a product a;

(2) adding 0.005g of hydroquinone into a reaction system, dripping PETA into the reaction system, continuing the reaction at 70 ℃ until the isocyanate absorption peak of the IPDI disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the colorless viscous liquid modified polyurethane acrylate II.

4. The EB cured aluminum substrate abrasion resistant coating of claim 1 in which the urethane acrylate aliphatic urethane acrylate and/or aromatic urethane acrylate.

5. The EB-cured aluminum substrate wear-resistant coating according to claim 1, wherein the reactive monomer is one or a combination of two or more of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-ethylene glycol diacrylate and tripropylene glycol diacrylate.

6. The EB cured aluminum substrate wear resistant coating of claim 1 in which the diamond micropowder has a particle size of 1 to 5 μm.

7. The EB cured aluminum substrate wear resistant coating of claim 1 in which the wear adjuvant is a silicone anti-scratch agent.

8. The EB cured aluminum substrate wear resistant coating of claim 1 in which the dispersant is a polymeric dispersant.

9. The EB cured aluminum substrate wear resistant coating according to any one of claims 1 to 7 prepared by the steps of:

(1) under the condition of keeping out of the sun, mixing, heating and uniformly stirring the polyurethane acrylic resin, the modified polyurethane acrylate I, the modified polyurethane acrylate II and the active monomer according to the formula ratio, adding the wear-resistant auxiliary agent and uniformly stirring when the heating temperature reaches 50-60 ℃, and adding the dispersing agent and the diamond micropowder and uniformly stirring when the heating temperature reaches 65-70 ℃ to obtain the EB (Electron Beam) cured aluminum substrate wear-resistant coating;

(2) and (2) coating the EB curing aluminum substrate wear-resistant coating obtained in the step (1) on the surface of an aluminum substrate, curing the coating under EB curing equipment, and obtaining the EB curing aluminum substrate wear-resistant coating after the curing is finished.

Technical Field

The invention relates to the technical field of coatings, in particular to an EB (Electron Beam) cured aluminum substrate wear-resistant coating.

Background

The aluminum-based copper clad laminate is a metal-based copper clad laminate with a good heat dissipation function, is one of aluminum-based printed circuit board raw materials, and is widely applied to LED lighting products. Generally, an aluminum-based single panel is composed of three layers, namely a circuit layer (copper foil), an insulating layer and an aluminum base layer.

The circuit layer is manufactured by etching a copper plate to form a printed circuit to realize the assembly and connection of devices, the main process is grinding a plate, pasting a film, exposing, developing, etching and stripping, and the etching process is usually carried out in a corrosive acidic or alkaline environment. The aluminum in the aluminum base layer is a metal with strong activity and can easily react with acidic or alkaline solution used in the etching and film stripping processes.

In order to prevent the surface of the aluminum base layer from being corroded, the Chinese utility model patent CN 210042387U is provided with an acid and alkali resistant coating on the surface of the aluminum base plate, and the surface of the aluminum base layer of the aluminum base plate can be effectively prevented from being corroded by the method. However, the acid and alkali resistant coating does not have good wear resistance, and the coating is easily scratched in the process of carrying, so that the protection effect on the aluminum base layer is lost in the etching process of the circuit layer.

Disclosure of Invention

Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: the acid and alkali resistant coating arranged on the surface of the aluminum base layer generally does not have good wear resistance, and the coating is easily scratched in the carrying process, so that the protection effect on the aluminum base layer is lost in the etching process of the circuit layer.

The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides an EB (Electron beam) cured aluminum substrate wear-resistant coating which comprises the following components in parts by weight:

specifically, the modified polyurethane acrylate I is prepared according to the following steps:

adding 30.2g of IPDI (isophorone diisocyanate), 0.04g of catalyst DBTDL (dibutyltin dilaurate) and 70ml of THF (tetrahydrofuran) into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding 30.4g of PETA (pentaerythritol triacrylate) into the flask under the protection of nitrogen, stirring the mixture after the dropwise adding is completed, monitoring the reaction by FTIR (infrared Fourier transform infrared spectroscopy), adding 0.005g of hydroquinone into the reaction system, dropwise adding HTPB (hydroxyl-terminated polybutadiene), continuing the reaction at 70 ℃ until the isocyanate absorption peak of IPDI disappears on the FTIR spectrum, finishing the reaction, and finally removing the solvent by rotary evaporation to obtain the colorless high-viscosity liquid modified polyurethane acrylate I.

Specifically, the modified polyurethane acrylate II is prepared according to the following steps:

(1) adding 28.2g of DCPDA (tricyclodecane dimethanol diacrylate), 0.05g of catalyst 1173 and 70ml of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding 10.4g of mercaptoethanol into the flask under the protection of nitrogen, irradiating the mercaptoethanol with an LED lamp with the wavelength of 365nm while stirring, monitoring the reaction through FTIR measurement, eliminating a double bond absorption peak in reactants, and removing the solvent by rotary evaporation to obtain a product a;

(2) adding 0.005g of hydroquinone into a reaction system, dripping PETA into the reaction system, continuing the reaction at 70 ℃ until the isocyanate absorption peak of the IPDI disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the colorless viscous liquid modified polyurethane acrylate II, wherein the reaction is shown as follows:

specifically, the polyurethane acrylate is aliphatic polyurethane acrylate and/or aromatic polyurethane acrylate.

Specifically, the active monomer is one or a composition of more than two of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-ethylene glycol diacrylate and tripropylene glycol diacrylate.

Specifically, the particle size of the diamond micro powder is 1-5 μm.

Specifically, the wear-resistant auxiliary agent is an organosilicon anti-scratch agent.

Specifically, the dispersant is a polymeric dispersant.

Specifically, the EB cured aluminum substrate wear-resistant coating is prepared according to the following steps:

(1) under the condition of keeping out of the sun, mixing, heating and uniformly stirring the polyurethane acrylic resin, the modified polyurethane acrylate I, the modified polyurethane acrylate II and the active monomer according to the formula ratio, adding the wear-resistant auxiliary agent and uniformly stirring when the heating temperature reaches 50-60 ℃, and adding the dispersing agent and the diamond micropowder and uniformly stirring when the heating temperature reaches 65-70 ℃ to obtain the EB (Electron Beam) cured aluminum substrate wear-resistant coating;

(2) and (2) coating the EB curing aluminum substrate wear-resistant coating obtained in the step (1) on the surface of an aluminum substrate, curing the coating under EB curing equipment, and obtaining the EB curing aluminum substrate wear-resistant coating after the curing is finished.

The invention has the beneficial effects that:

(1) polybutadiene connecting segments are introduced into the molecular structure of the modified polyurethane acrylate I in the coating system, so that the toughness, the wear resistance and the scratch resistance of the cured coating are effectively improved;

(2) the modified polyurethane acrylate II molecular structure in the coating system of the invention introduces a tricyclodecane structure, which can further improve the hardness and scratch resistance of the coating;

(3) the DCPDA is directly added into a coating system to participate in resin polymerization reaction, and can also improve the hardness and the scratch resistance of the coating to a certain extent, but the DCPDA is a bifunctional monomer, has insufficient reactivity and limited crosslinking degree, is added into the coating system after being polyfunctionalized to participate in polymerization reaction, not only improves the reactivity of the DCPDA, but also effectively improves the crosslinking density of the resin system, and is very favorable for improving the hardness, the wear resistance and the scratch resistance of the coating.

Detailed Description

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

The hydroxyl-terminated polybutadiene used in the following examples of the present invention had a number average molecular weight of 3000.

The modified polyurethane acrylate I in the following embodiment of the invention is prepared according to the following steps:

adding 30.2g of IPDI, 0.04g of catalyst DBTDL and 70mL of THF into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 70 ℃, dropwise adding 30.4g of PETA into the flask under the protection of nitrogen, stirring for reaction after the dropwise addition is completed, monitoring the reaction through FTIR measurement, adding 0.005g of hydroquinone into the reaction system, dropwise adding HTPB, continuing the reaction at 70 ℃ until the isocyanate absorption peak of IPDI disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the colorless high-viscosity liquid modified polyurethane acrylate I.

The modified polyurethane acrylate II in the following embodiment of the invention is carried out according to the following steps:

(1) adding 28.2g of DCPDA, 0.05g of catalyst 1173 and 70mL of toluene into a three-hole round-bottom flask, then raising the temperature of the round-bottom flask to 50 ℃, dropwise adding 10.4g of mercaptoethanol into the flask under the protection of nitrogen, irradiating the mercaptoethanol with a 365nm wavelength LED lamp while stirring, monitoring the reaction through FTIR measurement, eliminating the double bond absorption peak in the reactant, and removing the solvent by rotary evaporation to obtain a product a;

(2) adding 0.005g of hydroquinone into a reaction system, dripping PETA into the reaction system, continuing the reaction at 70 ℃ until the isocyanate absorption peak of the IPDI disappears on an FTIR spectrum, finishing the reaction, and finally removing the solvent through rotary evaporation to obtain the colorless viscous liquid modified polyurethane acrylate II.

The urethane acrylates of the following examples of the present invention are Yangxing 6145-100 or Yangxing 6146-100.

The reactive monomer in the following examples of the present invention is one or a combination of two or more of pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-ethylene glycol diacrylate and tripropylene glycol diacrylate.

The diamond fine powder in the following examples of the present invention had a particle size of 1 to 5 μm.

The wear-resistant auxiliary agent in the following embodiment of the invention is an organosilicon anti-scratch agent, and is shown in a chart L-1133.

The dispersant in the following examples of the present invention is a polymeric dispersant.

The EB cured aluminum substrate wear-resistant coating in the following embodiment of the invention is prepared according to the following steps:

(1) under the condition of keeping out of the sun, mixing, heating and uniformly stirring the polyurethane acrylic resin, the modified polyurethane acrylate I, the modified polyurethane acrylate II and the active monomer according to the formula ratio, adding the wear-resistant auxiliary agent and uniformly stirring when the heating temperature reaches 50-60 ℃, and adding the dispersing agent and the diamond micropowder and uniformly stirring when the heating temperature reaches 65-70 ℃ to obtain the EB (Electron Beam) cured aluminum substrate wear-resistant coating;

(2) and (2) coating the EB curing aluminum substrate wear-resistant coating obtained in the step (1) on the surface of an aluminum substrate, curing the coating under EB curing equipment, wherein EB curing energy is 150-200keV, the dosage of EB curing agent is 20-50kGy, and curing to form a film under irradiation, thus obtaining the EB curing aluminum substrate wear-resistant coating after curing.

Example 1

The EB cured aluminum substrate wear-resistant coating comprises the following components in parts by weight:

example 2

The EB cured aluminum substrate wear-resistant coating comprises the following components in parts by weight:

example 3

The EB cured aluminum substrate wear-resistant coating comprises the following components in parts by weight:

example 4

The EB cured aluminum substrate wear-resistant coating comprises the following components in parts by weight:

example 5

The EB cured aluminum substrate wear-resistant coating comprises the following components in parts by weight:

comparative example 1 the same as example 1 except that the modified urethane acrylate II was not added in comparative example 1.

Comparative example 2 the same as example 1 except that in comparative example 2, the modified urethane acrylate II was entirely replaced with DCPDA.

Comparative example 3 the same as example 1 except that in comparative example 3, the modified urethane acrylate II was entirely replaced with the modified urethane acrylate I.

And (3) performance testing:

the coatings obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to the relevant performance tests, the specific test types being as follows:

hardness: the test was carried out according to standard GB/T6739-2006.

Scratch resistance: testing was performed according to standard BSEN 16094-2012.

Wear resistance: the test was carried out according to standard GB/T1768-2006, 100 r.

Adhesion force: the tests were carried out according to the standard GB/T9286-1998.

The specific test results are shown in table 1.

TABLE 1

Test item	Hardness of	Scratch resistance (grade)	Abrasion resistance (g/100r)	Adhesion force
					Example 1	3H	1	0.020	Level 0
Example 2	4H	1	0.015	Level 0
					Example 3	3H	1	0.025	Level 0
Example 4	3H	1	0.024	Level 0
					Example 5	4H	1	0.021	Level 0
Comparative example 1	H	3	0.053	Level 0
					Comparative example 2	2H	2	0.038	Level 0
Comparative example 3	2H	2	0.029	Level 0

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.