阅读说明：本技术 一种布线板上绝缘保护层的制备方法 (Preparation method of insulating protective layer on wiring board ) 是由 周雨薇 于 2021-09-01 设计创作，主要内容包括：本发明涉及一种布线板上绝缘保护层的制备方法,属于光敏树脂材料领域,其适于用作积层基板的层间绝缘材料和印刷线路板的绝缘保护膜,应用于微电子领域。该布线板上绝缘保护层的制备方法为先将环氧树脂上的环氧基团与丙烯酸反应制备环氧丙烯酸酯树脂,然后环氧丙烯酸酯树脂上剩余的环氧基团再与酸酐反应制备含有羧基的不饱和树脂,将所得的含有羧基的不饱和树脂、光引发剂、光聚合单体以及环氧固化剂混合均匀后涂覆在覆铜板上,执行曝光、刻蚀、固化等程序得到布线板上绝缘保护层。当使用本发明制备布线板上绝缘保护层时,可以在良好的工作环境下以高生产率和低成本制造防潮可靠性优异的组合多层布线板,是一种很有前途的永久性保护膜材料。(The invention relates to a preparation method of an insulating protective layer on a wiring board, which belongs to the field of photosensitive resin materials, is suitable for being used as an interlayer insulating material of a laminated substrate and an insulating protective film of a printed circuit board and is applied to the field of microelectronics. The preparation method of the insulating protective layer on the wiring board comprises the steps of firstly reacting epoxy groups on epoxy resin with acrylic acid to prepare epoxy acrylate resin, then reacting residual epoxy groups on the epoxy acrylate resin with acid anhydride to prepare unsaturated resin containing carboxyl, uniformly mixing the obtained unsaturated resin containing carboxyl, photoinitiator, photopolymerization monomer and epoxy curing agent, coating the mixture on a copper-clad plate, and carrying out procedures of exposure, etching, curing and the like to obtain the insulating protective layer on the wiring board. When the present invention is used to produce an insulating protective layer on a wiring board, a build-up multilayer wiring board excellent in moisture-proof reliability can be produced at a high productivity and a low cost in a good working environment, and is a promising permanent protective film material.)

1. A method for preparing an insulating protective layer on a wiring board is characterized in that: the preparation method comprises the following steps:

(1) dissolving epoxy resin in butyl acetate, adding acrylic acid, benzyl triethyl ammonium chloride and hydroquinone, and obtaining an epoxy acrylate resin solution at 90-120 ℃ for 3-8 hours, wherein the epoxy resin is one of phenol-novolac epoxy resin, cresol-novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and bisphenol A epoxy resin, and the dosage of the epoxy resin, the butyl acetate, the acrylic acid, the benzyl triethyl ammonium chloride and the hydroquinone is 100 g: 50-200 mL: 10-30 g: 0.1-2 g: 10-100 mg;

(2) adding acid anhydride into the epoxy acrylate resin solution obtained in the step (1), and reacting for 3-8 h at 100-120 ℃ to obtain unsaturated resin containing carboxyl, wherein the acid anhydride is one of anhydrous tetrahydrophthalic acid, hexahydrophthalic anhydride, chloroanal anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, succinic anhydride and itaconic anhydride, and the mass ratio of the acid anhydride to the epoxy acrylate resin solution is 1: 5-20;

(3) stirring 20-40 wt% of the carboxyl-containing unsaturated resin prepared in the step (2), 5-10 wt% of dipentaerythritol hexaacrylate, 2-5 wt% of a photoinitiator, 3-8 wt% of 2-ethyl-4-methylimidazole and 37-70 wt% of butyl acetate at room temperature for 1-3 hours to obtain a photosensitive resin composition, wherein the photoinitiator is one of 2, 2-diethoxyacetophenone, p-dimethylaminopheninone, 2-chlorobenzophenone, benzoin methyl ether, 2-chlorothiophenone, 2-methylthioxanthone and benzoyl peroxide;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 20-100 mu m, pre-curing the photosensitive layer at 40-80 ℃ for 0.5-2 h, selectively performing 200-800 mJ/cm by using a high-pressure mercury lamp according to the circuit requirement of a wiring board by using a corresponding mask plate²Irradiating the substrate with ultraviolet rays for 20-300 s, spraying 0.5-3 wt% of sodium carbonate aqueous solution at 25-50 ℃ for 1-5 min, and finally curing at 120-180 ℃ for 10-60 min to obtain the insulating protective layer on the wiring board.

Technical Field

The invention relates to a preparation method of an insulating protective layer on a wiring board, which belongs to the field of photosensitive resin materials, is suitable for being used as an interlayer insulating material of a laminated substrate and an insulating protective film of a printed circuit board and is applied to the field of microelectronics.

Background

In recent years, new demands have been made for further miniaturization and higher functionality of electronic devices, computers, and the like, and there has been a demand for using components of higher density in accordance therewith. For example, in order to increase the wiring density per unit volume in a printed wiring board, miniaturization of circuits and formation of multilayer wiring boards have been promoted, and ultrahigh-density substrates called stacked multilayer substrates have been proposed and put into practical use. In the multilayer wiring board, a laminate of a printed wiring board and a conductive layer and an insulating layer of an insulating layer, or a laminate of an insulating layer and a conductive layer which are alternately laminated, is pressed. The stacked multilayer substrate is characterized in that interlayer conduction is performed through internal via holes instead of via holes conventionally used for interlayer conduction of multilayer substrates, and as a method of providing internal via holes in an insulating layer, there are two methods, mainly a laser method and a photosensitive resin method, respectively, at present. Among them, the laser method has been reported more, but the laser method has a low through hole drilling speed, a low productivity, and a new need for a dedicated facility, resulting in a high cost.

Compared with the laser method, the photosensitive resin method uses a photosensitive resin, also generally referred to as a subtractive method, in which ultraviolet rays are irradiated on a desired mask pattern, the mask pattern is developed to form connection openings (through holes), the resin surface is roughened with a chromic acid mixed solution to enhance adhesion with copper plating, and then copper plating is performed to form a conductive layer, a lot of through holes can be manufactured, and conventional printed wiring board manufacturing equipment can be used as it is, thus having advantages of higher productivity and lower cost. As a conventional method for manufacturing a multilayer wiring board, a photosensitive resin is coated on a printed wiring board formed of a circuit, and as a photosensitive resin used in the method, a type of photosensitive resin developed using an organic solvent or an aqueous developer has been studied; however, the former has a problem of deterioration of working environment, the latter has a problem of insufficient moisture-proof reliability of the resin itself, and the actual use time cannot exceed ten minutes. Accordingly, the present invention provides a method for producing an insulating protective layer on a wiring board, with which a build-up multilayer wiring board having high productivity and low cost and having sufficient moisture-proof reliability under good conditions can be produced.

Disclosure of Invention

The invention aims to solve the problems that the existing laser method has low drilling speed of through holes, low productivity and high cost due to the new requirement of special facilities, and the photosensitive resin used by the photosensitive resin method has the defects of deteriorated working environment, insufficient moisture-proof reliability of the resin, overlong actual use time and the like. The preparation method specifically comprises the steps of firstly reacting epoxy groups on epoxy resin with acrylic acid to prepare epoxy acrylate resin, then reacting residual epoxy groups on the epoxy acrylate resin with acid anhydride to prepare unsaturated resin containing carboxyl, uniformly mixing the obtained unsaturated resin containing carboxyl, photoinitiator, photopolymerization monomer and epoxy curing agent, coating the mixture on a copper-clad plate, and carrying out procedures of exposure, etching, curing and the like to obtain the insulating protective layer on the wiring board.

The preparation method of the insulating protective layer on the wiring board is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) dissolving epoxy resin in butyl acetate, adding acrylic acid, benzyl triethyl ammonium chloride and hydroquinone, and obtaining an epoxy acrylate resin solution at 90-120 ℃ for 3-8 hours, wherein the epoxy resin is one of phenol-novolac epoxy resin, cresol-novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and bisphenol A epoxy resin, and the dosage of the epoxy resin, the butyl acetate, the acrylic acid, the benzyl triethyl ammonium chloride and the hydroquinone is 100 g: 50-200 mL: 10-30 g: 0.1-2 g: 10-100 mg;

(2) adding acid anhydride into the epoxy acrylate resin solution obtained in the step (1), and reacting for 3-8 h at 100-120 ℃ to obtain unsaturated resin containing carboxyl, wherein the acid anhydride is one of anhydrous tetrahydrophthalic acid, hexahydrophthalic anhydride, chloroanal anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, succinic anhydride and itaconic anhydride, and the mass ratio of the acid anhydride to the epoxy acrylate resin solution is 1: 5-20;

(3) stirring 20-40 wt% of the carboxyl-containing unsaturated resin prepared in the step (2), 5-10 wt% of dipentaerythritol hexaacrylate, 2-5 wt% of a photoinitiator, 3-8 wt% of 2-ethyl-4-methylimidazole and 37-70 wt% of butyl acetate at room temperature for 1-3 hours to obtain a photosensitive resin composition, wherein the photoinitiator is one of 2, 2-diethoxyacetophenone, p-dimethylaminopheninone, 2-chlorobenzophenone, benzoin methyl ether, 2-chlorothiophenone, 2-methylthioxanthone and benzoyl peroxide;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 20-100 mu m, pre-curing the photosensitive layer at 40-80 ℃ for 0.5-2 h, selectively performing 200-800 mJ/cm by using a high-pressure mercury lamp according to the circuit requirement of a wiring board by using a corresponding mask plate²Irradiating the substrate with ultraviolet rays for 20-300 s, spraying 0.5-3 wt% of sodium carbonate aqueous solution at 25-50 ℃ for 1-5 min, and finally curing at 120-180 ℃ for 10-60 min to obtain the insulating protective layer on the wiring board.

The invention has the beneficial effects that: since the unsaturated resin having a carboxyl group of the present invention can be photopolymerized with a photopolymerizable monomer, a firm and stable protective layer can be formed, which is suitable for producing an alkali-developable photosensitive resin composition. The insulating protective layer on a wiring board prepared by the present invention is a photosensitive resin composition which can be developed using an alkaline aqueous solution having little adverse effect on the human body and has excellent moisture-proof reliability, heat resistance, resolution, chemical resistance, acid resistance, alkali resistance. Therefore, when the present invention is used to produce an insulating protective layer on a wiring board, a build-up multilayer wiring board excellent in moisture-proof reliability can be produced at a high productivity and a low cost in a good working environment, and is a promising permanent protective film material.

Drawings

FIG. 1 is a structural formula of an epoxy acrylate resin prepared in example 1 of the present invention

FIG. 2 is a structural formula of a carboxyl group-containing unsaturated resin prepared in example 1 of the present invention

Detailed Description

The present invention is further described in the following description of the specific embodiments, but the present invention is not limited thereto, and those skilled in the art can make various modifications or alterations based on the basic idea of the present invention without departing from the scope of the present invention.

Example 1

(1) Dissolving 100g of bisphenol A epoxy resin in 100mL of butyl acetate, adding 25g of acrylic acid, 0.5g of benzyltriethylammonium chloride and 50mg of hydroquinone, and carrying out reaction at 120 ℃ for 4h to obtain an epoxy acrylate resin solution, wherein the structural formula of the epoxy acrylate resin solution is shown in figure 1;

(2) adding 25g of succinic anhydride into 200g of the epoxy acrylate resin solution obtained in the step (1), and reacting at 120 ℃ for 4h to obtain unsaturated resin containing carboxyl, wherein the structural formula of the unsaturated resin is shown in figure 2;

(3) stirring 30 wt% of the carboxyl group-containing unsaturated resin prepared in the above step (2), 10 wt% of dipentaerythritol hexaacrylate, 4 wt% of photoinitiator 2, 2-diethoxyacetophenone, 6 wt% of 2-ethyl-4-methylimidazole and 50 wt% of butyl acetate at room temperature for 1 hour to obtain a photosensitive resin composition;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 40 mu m, pre-curing the photosensitive layer at 60 ℃ for 1h, selectively performing 500mJ/cm by using a high-pressure mercury lamp according to the circuit requirements of a wiring board by using a corresponding mask²Then spraying 2 wt% sodium carbonate aqueous solution at 30 deg.C for 3min, and finally curing at 150 deg.C for 40min to obtain the insulating protective layer on the wiring board.

Example 2

(1) Dissolving 100g of bisphenol A epoxy resin in 100mL of butyl acetate, adding 10g of acrylic acid, 0.5g of benzyltriethylammonium chloride and 50mg of hydroquinone into the solution, and carrying out reaction at 120 ℃ for 4 hours to obtain an epoxy acrylate resin solution;

(2) adding 25g of succinic anhydride to 200g of the epoxy acrylate resin solution obtained in the step (1), and reacting at 120 ℃ for 4h to obtain unsaturated resin containing carboxyl;

(3) stirring 30 wt% of the carboxyl group-containing unsaturated resin prepared in the above step (2), 10 wt% of dipentaerythritol hexaacrylate, 4 wt% of photoinitiator 2, 2-diethoxyacetophenone, 6 wt% of 2-ethyl-4-methylimidazole and 50 wt% of butyl acetate at room temperature for 1 hour to obtain a photosensitive resin composition;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 40 mu m, andprecuring at 60 deg.C for 1h, selectively performing 500mJ/cm by using high-pressure mercury lamp according to the circuit requirement of wiring board and corresponding mask²Then spraying 2 wt% sodium carbonate aqueous solution at 30 deg.C for 3min, and finally curing at 150 deg.C for 40min to obtain the insulating protective layer on the wiring board.

Embodiment 3

(1) Dissolving 100g of bisphenol F epoxy resin in 100mL of butyl acetate, adding 25g of acrylic acid, 0.5g of benzyltriethylammonium chloride and 50mg of hydroquinone into the solution, and carrying out reaction at 120 ℃ for 4 hours to obtain an epoxy acrylate resin solution;

(2) adding 25g of succinic anhydride to 200g of the epoxy acrylate resin solution obtained in the step (1), and reacting at 120 ℃ for 4h to obtain unsaturated resin containing carboxyl;

(3) stirring 30 wt% of the carboxyl group-containing unsaturated resin prepared in the above step (2), 10 wt% of dipentaerythritol hexaacrylate, 4 wt% of photoinitiator 2, 2-diethoxyacetophenone, 6 wt% of 2-ethyl-4-methylimidazole and 50 wt% of butyl acetate at room temperature for 1 hour to obtain a photosensitive resin composition;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 40 mu m, pre-curing the photosensitive layer at 60 ℃ for 1h, selectively performing 500mJ/cm by using a high-pressure mercury lamp according to the circuit requirements of a wiring board by using a corresponding mask²Then spraying 2 wt% sodium carbonate aqueous solution at 30 deg.C for 3min, and finally curing at 150 deg.C for 40min to obtain the insulating protective layer on the wiring board.

Example 4

(1) Dissolving 100g of bisphenol A epoxy resin in 100mL of butyl acetate, adding 25g of acrylic acid, 0.5g of benzyltriethylammonium chloride and 50mg of hydroquinone into the solution, and carrying out reaction at 120 ℃ for 4 hours to obtain an epoxy acrylate resin solution;

(2) adding 10g of succinic anhydride to 200g of the epoxy acrylate resin solution obtained in the step (1), and reacting at 120 ℃ for 4h to obtain unsaturated resin containing carboxyl;

(3) stirring 30 wt% of the carboxyl group-containing unsaturated resin prepared in the above step (2), 10 wt% of dipentaerythritol hexaacrylate, 4 wt% of photoinitiator 2, 2-diethoxyacetophenone, 6 wt% of 2-ethyl-4-methylimidazole and 50 wt% of butyl acetate at room temperature for 1 hour to obtain a photosensitive resin composition;

coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 40 mu m, pre-curing the photosensitive layer at 60 ℃ for 1h, selectively performing 500mJ/cm by using a high-pressure mercury lamp according to the circuit requirements of a wiring board by using a corresponding mask²Then spraying 2 wt% sodium carbonate aqueous solution at 30 deg.C for 3min, and finally curing at 150 deg.C for 40min to obtain the insulating protective layer on the wiring board.

Example 5

(1) Dissolving 100g of bisphenol A epoxy resin in 100mL of butyl acetate, adding 25g of acrylic acid, 0.5g of benzyltriethylammonium chloride and 50mg of hydroquinone, and carrying out reaction at 120 ℃ for 4h to obtain an epoxy acrylate resin solution, wherein the structural formula of the epoxy acrylate resin solution is shown in figure 1;

(2) adding 25g of succinic anhydride into 200g of the epoxy acrylate resin solution obtained in the step (1), and reacting at 120 ℃ for 4h to obtain unsaturated resin containing carboxyl, wherein the structural formula of the unsaturated resin is shown in figure 2;

(3) stirring 40 wt% of the carboxyl group-containing unsaturated resin prepared in the above step (2), 10 wt% of dipentaerythritol hexaacrylate, 4 wt% of photoinitiator 2, 2-diethoxyacetophenone, 6 wt% of 2-ethyl-4-methylimidazole and 60 wt% of butyl acetate at room temperature for 1 hour to obtain a photosensitive resin composition;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 40 mu m, pre-curing the photosensitive layer at 60 ℃ for 1h, selectively performing 500mJ/cm by using a high-pressure mercury lamp according to the circuit requirements of a wiring board by using a corresponding mask²Then spraying 2 wt% sodium carbonate aqueous solution at 30 deg.C for 3min, and finally curing at 150 deg.C for 40min to obtain the insulating protective layer on the wiring board.

Example 6

(1) Dissolving 100g of bisphenol A epoxy resin in 100mL of butyl acetate, adding 25g of acrylic acid, 0.5g of benzyltriethylammonium chloride and 50mg of hydroquinone, and carrying out reaction at 120 ℃ for 4h to obtain an epoxy acrylate resin solution, wherein the structural formula of the epoxy acrylate resin solution is shown in figure 1;

(2) adding 25g of succinic anhydride into 200g of the epoxy acrylate resin solution obtained in the step (1), and reacting at 120 ℃ for 4h to obtain unsaturated resin containing carboxyl, wherein the structural formula of the unsaturated resin is shown in figure 2;

(3) stirring 30 wt% of the carboxyl group-containing unsaturated resin prepared in the above step (2), 10 wt% of dipentaerythritol hexaacrylate, 4 wt% of photoinitiator benzoin methyl ether, 6 wt% of 2-ethyl-4-methylimidazole and 60 wt% of butyl acetate at room temperature for 1 hour to obtain a photosensitive resin composition;

(4) coating the composition obtained in the step (3) on a copper-clad plate to form a photosensitive layer with the thickness of 40 mu m, pre-curing the photosensitive layer at 60 ℃ for 1h, selectively performing 500mJ/cm by using a high-pressure mercury lamp according to the circuit requirements of a wiring board by using a corresponding mask²Then spraying 2 wt% sodium carbonate aqueous solution at 30 deg.C for 3min, and finally curing at 150 deg.C for 40min to obtain the insulating protective layer on the wiring board.