Electroplating-resistant negative photoresist capable of rapidly removing alkali

Abstract

The invention discloses an anti-electroplating negative photoresist capable of fast alkali stripping, and belongs to the technical field of photoresist, the anti-electroplating negative photoresist capable of fast alkali stripping comprises the following components by mass: 60-80 parts of matrix resin, 3-10 parts of a photoinitiator, 7-15 parts of a solvent, 5-10 parts of a reactive diluent, 3-8 parts of a small molecular acid monomer, 0.2-2 parts of a leveling agent and 0.3-2.5 parts of an antifoaming agent; the matrix resin comprises acrylic resin and phenolic epoxy acrylate in a mass ratio of (40-60): (40-60); the micromolecular acid monomer contains carbon-carbon double bonds and carboxyl. The negative photoresist disclosed by the invention has an excellent anti-electroplating effect, can be rapidly degummed by alkali, and is high in resolution ratio.

Description

Technical Field

[0001] The invention relates to the technical field of photoresists, in particular to a negative photoresist which is resistant to electroplating and can be rapidly alkali-stripped. Background Art

[0002] HJT (heterojunction) cells are considered the next generation of mainstream photovoltaic technology due to their high conversion efficiency, low temperature coefficient, and simple process. However, their metallization relies on high-cost silver paste, which leads to high non-silicon costs. The core goal of copper manufacturing processes (including electroplated copper and silver-clad copper technologies) is to reduce costs by replacing silver materials while maintaining cell efficiency and reliability.

[0003] Electroplating copper technology can significantly reduce the non-silicon costs of heterojunction cells by replacing high-cost silver paste with copper electrodes. Copper processing technology has great development prospects in HJT cell applications, and photoresist is a core raw material for this process.

[0004] A major problem with the photoresist currently used in copper processes is that the stripping time is too long. Too long a time will cause strong alkali to corrode the silicon wafer substrate, reducing the light conversion efficiency of the final product.

[0005] In view of this, this application is filed. Summary of the Invention

[0006] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped. The negative photoresist of the present invention has excellent anti-electroplating effect, can be rapidly alkali-stripped, and has high resolution.

[0007] To achieve the above object, the technical solution adopted by the present invention is: A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped, comprising the following components in parts by weight: 60-80 parts of a base resin, 3-10 parts of a photoinitiator, 7-15 parts of a solvent, 5-10 parts of a reactive diluent, 3-8 parts of a small molecule acid monomer, 0.2-2 parts of a leveling agent, and 0.3-2.5 parts of a defoaming agent; The matrix resin comprises an acrylic resin and a novolac epoxy acrylate in a mass ratio of (40-60):(40-60); the acrylic resin has an acid value of 50-150 mgKOH / g and a viscosity of 5000-50000 mPa·s at 25°C; the novolac epoxy acrylate has an acid value of 40-120 mgKOH / g and a viscosity of 10000-100000 mPa·s at 25°C; The small molecule acid monomer contains a carbon-carbon double bond and a carboxyl group.

[0008] The negative photoresist described in the present invention has excellent anti-plating effect, can be quickly alkali-removed, and has high resolution, with a resolution lower than 20μm, can improve light conversion efficiency, and can be well applied to copper process technology.

[0009] The present invention uses acrylic resin and novolac epoxy acrylate with specific acid value and viscosity as matrix resins. The molecular structures of the acrylic resin and novolac epoxy acrylate both contain photosensitive groups (such as double bonds) and alkali-soluble groups (such as carboxyl groups), which can effectively improve photosensitivity, improve molecular structure, and enhance the edge sharpness of the photoresist, significantly improving the resolution of the photoresist, reducing bubbles or defects in the coating process, and effectively reducing the plating phenomenon. At the same time, the acrylic resin and novolac epoxy acrylate form a three-dimensional network cross-linked structure, thereby improving the electroplating resistance, optimizing the acid value of the photoresist, and optimizing the alkali stripping rate.

[0010] The small molecule acid monomer contains a double bond and has photosensitivity, and also carries -COOH, which can react with alkali. It is a key raw material for increasing the film stripping speed. The double bond can participate in the polymerization reaction and enter the main structure of the resin to improve the electroplating resistance; on the other hand, it contains -COOH, which increases the acid value of the cross-linked coating, thereby achieving the effect of rapid alkali stripping.

[0011] As a preferred embodiment of the present invention, the negative photoresist that is resistant to electroplating and can be quickly alkali-stripped comprises the following components in parts by mass: 68 to 75 parts of a base resin, 5 to 8 parts of a photoinitiator, 10 to 12 parts of a solvent, 6 to 8 parts of a reactive diluent, 4 to 6 parts of a small molecule acid monomer, 0.5 to 1 part of a leveling agent, and 0.8 to 1.5 parts of a defoaming agent.

[0012] As a preferred embodiment of the present invention, the small molecule acid monomer includes at least one of itaconic acid, acrylic acid, methacrylic acid, 1,6-heptadiene-4-carboxylic acid, and methyl-1,6-heptadiene-4-carboxylic acid.

[0013] As a preferred embodiment of the present invention, the acrylic resin has an acid value of 50-70 mgKOH / g and a viscosity of 25,000-40,000 mPa·s at 25°C.

[0014] As a preferred embodiment of the present invention, the acid value of the novolac epoxy acrylate is 50-110 mgKOH / g, and the viscosity at 25° C. is 30,000-90,000 mPa·s.

[0015] As a preferred embodiment of the present invention, the photoinitiator includes at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, dibenzophenone and bis-2,6-difluoro-3-pyrrolphenyl titanocene.

[0016] As a preferred embodiment of the present invention, the photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:(1.5~2.5):(0.8~1.2).

[0017] As a preferred embodiment of the present invention, the solvent includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isophorone, N-methyl pyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, alcohol ester dodecahydrate and DBE solvent.

[0018] As a preferred embodiment of the present invention, the reactive diluent includes at least one of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol triacrylate.

[0019] As a preferred embodiment of the present invention, the defoaming agent includes a non-fluorine and non-silicone defoaming agent, the defoaming agent includes at least one of an acrylate defoaming agent and a mineral oil defoaming agent, the defoaming agent includes at least one of defoaming agent BYK-1794 (BYK), defoaming agent BYK-055 (BYK), and defoaming agent LAP-20 (Kushu Corporation, Japan). Fluorine and silicon surface additives usually have a relatively low surface tension, which makes it difficult for the stripping liquid to wet the photoresist surface, thereby inhibiting the stripping process. The use of non-fluorine and non-silicone defoaming agents can further improve the stripping effect.

[0020] As a preferred embodiment of the present invention, the leveling agent includes an acrylic leveling agent. The use of an acrylic leveling agent can increase the surface tension of the photoresist coating, allowing the stripping liquid to better wet the surface and increase the stripping speed.

[0021] As a preferred embodiment of the present invention, the leveling agent includes at least one of leveling agent LHP-95 (produced by Kusunoki Co., Ltd., Japan), leveling agent BYK390 (produced by BYK), and leveling agent L-3580 (produced by Yuehehua, Foshan).

[0022] Among them, the present invention is not limited to the preparation method of the negative photoresist that is resistant to electroplating and can be quickly alkali-stripped. Those skilled in the art can prepare it into a negative photoresist that is resistant to electroplating and can be quickly alkali-stripped according to conventional methods in the field. For example, the negative photoresist that is resistant to electroplating and can be quickly alkali-stripped can be obtained by mixing all the raw materials evenly.

[0023] The beneficial effects of the present invention are: the negative photoresist described in the present invention has excellent anti-plating effect, can be quickly alkali-removed, and has high resolution, the resolution is lower than 20μm, can improve light conversion efficiency, and can be well applied to copper process technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a resolution diagram of the negative photoresist of Example 1. DETAILED DESCRIPTION

[0025] To make the purpose, technical solutions, and advantages of the embodiments of this application more clear, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0026] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0027] In this application, when referring to numerical ranges, unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0028] In the present application, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0029] Unless otherwise specified, the components, raw materials or instruments used in the embodiments and comparative examples of the present invention are all commercially available raw materials or instruments, and the components and raw materials used in each parallel experiment are all of the same kind.

[0030] The sources of raw materials for the embodiments and comparative examples are as follows: Acrylic resin-1: acid value is 60 mgKOH / g, viscosity at 25°C is 30000 mPa·s, sourced from Guangzhou Linchuan Company, brand LC-891.

[0031] Acrylic resin-2: acid value is 70 mgKOH / g, viscosity at 25°C is 25000 mPa·s, sourced from Showa High Molecular, brand BSR-12.

[0032] Acrylic resin-3: acid value is 50 mgKOH / g, viscosity at 25°C is 40000 mPa·s, sourced from Guangzhou Yingxin Company, brand 2261.

[0033] Acrylic resin-4: acid value is 24 mgKOH / g, viscosity is 1250 mPa·s at 25°C, sourced from Hanwha, brand name Soluryl‑80T.

[0034] Novolac epoxy acrylate-1: the acid value is 60 mgKOH / g, the viscosity at 25°C is 90,000 mPa·s, and it is sourced from Nippon Kayaku Co., Ltd. with the brand name KR-1000.

[0035] Novolac epoxy acrylate-2: The acid value is 110 mgKOH / g, the viscosity at 25°C is 30,000 mPa·s, and it is sourced from Nippon Kayaku Co., Ltd. with the brand name PCR-2014HW.

[0036] Novolac epoxy acrylate-3: The acid value is 50 mgKOH / g, the viscosity at 25°C is 50,000 mPa·s, and it is sourced from Nippon Kayaku Co., Ltd. with the brand name CCR-4959HW.

[0037] Solvent: Diethylene glycol ethyl ether acetate.

[0038] Reactive diluent-1: 1,6-hexanediol diacrylate.

[0039] Reactive diluent-2: tripropylene glycol diacrylate.

[0040] Defoaming agent-1: BYK-1794 (BYK).

[0041] Defoamer-2: Defoamer BYK-055 (BYK).

[0042] Leveling agent-1: Leveling agent LHP-95 (Kushu Co., Ltd., Japan).

[0043] Leveling agent-2: Leveling agent BYK390 (BYK).

[0044] Small molecule acid monomer-1: itaconic acid.

[0045] Small molecule acid monomer-2: methacrylic acid.

[0046] The following examples are provided to facilitate understanding of the present invention. These examples are not provided to limit the scope of the claims.

[0047] Example 1 A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0048] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0049] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0050] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0051] Example 2 The difference between Example 2 and Example 1 is that the amounts of the raw materials are different, and the other aspects are the same.

[0052] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 75 parts of a base resin, 8 parts of a photoinitiator, 12 parts of a solvent-1, 8 parts of a reactive diluent-1, 6 parts of a small molecule acid monomer-1, 1 part of a leveling agent-1, and 1.5 parts of a defoaming agent-1.

[0053] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0054] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0055] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0056] Example 3 The difference between Example 3 and Example 1 is that the amounts of the raw materials are different, and the other aspects are the same.

[0057] A negative photoresist that is resistant to electroplating and can be quickly alkali-stripped comprises the following components in parts by mass: 60 parts of a base resin, 3 parts of a photoinitiator, 7 parts of a solvent, 5 parts of a reactive diluent, 3 parts of a small molecule acid monomer, 0.2 parts of a leveling agent, and 0.3 parts of a defoaming agent.

[0058] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0059] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0060] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0061] Example 4 The difference between Example 4 and Example 1 is that the amounts of the raw materials are different, and everything else is the same.

[0062] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 80 parts of a base resin, 10 parts of a photoinitiator, 15 parts of a solvent-1, 10 parts of a reactive diluent-1, 8 parts of a small molecule acid monomer-1, 2 parts of a leveling agent-1, and 2.5 parts of a defoaming agent-1.

[0063] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0064] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0065] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0066] Example 5 The difference between Example 5 and Example 1 is that the selection of raw materials is different, and everything else is the same.

[0067] A negative photoresist that is resistant to electroplating and can be quickly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-2, 6 parts of a reactive diluent-2, 4 parts of a small molecule acid monomer-2, 0.5 parts of a leveling agent-2, and 0.8 parts of a defoaming agent-2.

[0068] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0069] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0070] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-2, a reactive diluent-2, a small molecule acid monomer-2, a leveling agent-2, and a defoaming agent-2 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0071] Example 6 The difference between Example 6 and Example 1 is that the mass ratio of acrylic resin-1 and novolac epoxy acrylate-1 is different, and the other parts are the same.

[0072] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0073] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 60:40.

[0074] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0075] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0076] Example 7 The difference between Example 7 and Example 1 is that the selection of acrylic resin and novolac epoxy acrylate is different, and all other aspects are the same.

[0077] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0078] The matrix resin includes acrylic resin-2 and novolac epoxy acrylate-2 in a mass ratio of 40:60.

[0079] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0080] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0081] Example 8 The difference between Example 8 and Example 1 is that the selection of acrylic resin and novolac epoxy acrylate is different, and all other aspects are the same.

[0082] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0083] The matrix resin includes acrylic resin-3 and novolac epoxy acrylate-3 in a mass ratio of 40:60.

[0084] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0085] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0086] Example 9 The difference between Example 9 and Example 1 is that the selection of photoinitiator is different, and everything else is the same.

[0087] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0088] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0089] The photoinitiator includes 2-isopropylthioxanthone and 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone in a mass ratio of 1:2.

[0090] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0091] Example 10 The difference between Example 10 and Example 1 is that the selection of photoinitiator is different, and everything else is the same.

[0092] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0093] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0094] The photoinitiator comprises 2-isopropylthioxanthone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:1.

[0095] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0096] Example 11 The difference between Example 11 and Example 1 is that the selection of photoinitiator is different, and everything else is the same.

[0097] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0098] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0099] The photoinitiator comprises 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 2:1.

[0100] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0101] Example 12 The difference between Example 12 and Example 1 is that the selection of photoinitiator is different, and everything else is the same.

[0102] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0103] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0104] The photoinitiator comprises benzophenone, bis-2,6-difluoro-3-pyrrolephenyl titanocene and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0105] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0106] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the amounts of the raw materials are different, and the other aspects are the same.

[0107] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 50 parts of a base resin, 1 part of a photoinitiator, 5 parts of a solvent-1, 2 parts of a reactive diluent-1, 2 parts of a small molecule acid monomer-1, 0.1 parts of a leveling agent-1, and 0.2 parts of a defoaming agent-1.

[0108] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0109] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0110] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0111] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the amounts of the raw materials are different, and the other aspects are the same.

[0112] A negative photoresist that is resistant to electroplating and can be quickly alkali-stripped comprises the following components in parts by mass: 90 parts of a base resin, 15 parts of a photoinitiator, 20 parts of a solvent-1, 15 parts of a reactive diluent-1, 12 parts of a small molecule acid monomer-1, 3 parts of a leveling agent-1, and 3 parts of a defoaming agent-1.

[0113] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0114] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0115] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0116] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the base resin is different, and the other aspects are the same.

[0117] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0118] The base resin includes acrylic resin-1.

[0119] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0120] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0121] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the base resin is different, and the other aspects are the same.

[0122] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0123] The base resin includes novolac epoxy acrylate-1.

[0124] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0125] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0126] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the base resin is different, and the other aspects are the same.

[0127] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0128] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 20:80.

[0129] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0130] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0131] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the base resin is different, and the other aspects are the same.

[0132] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0133] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 80:20.

[0134] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0135] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0136] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is that the base resin is different, and the other aspects are the same.

[0137] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0138] The matrix resin includes acrylic resin-4 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0139] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0140] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule acid monomer-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0141] Comparative Example 8 The difference between Comparative Example 8 and Example 1 is that no small molecule acid monomer is added in Comparative Example 8, and all other conditions are the same.

[0142] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0143] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0144] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0145] The preparation method of the electroplating-resistant and rapidly alkali-strippable negative photoresist is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain the electroplating-resistant and rapidly alkali-strippable negative photoresist.

[0146] Comparative Example 9 The difference between Comparative Example 9 and Example 1 is that Comparative Example 9 uses small molecule phenol (p-hydroxyanisole) to replace the small molecule acid monomer, and all other conditions are the same.

[0147] A negative photoresist that is resistant to electroplating and can be rapidly alkali-stripped comprises the following components in parts by mass: 68 parts of a base resin, 5 parts of a photoinitiator, 10 parts of a solvent-1, 6 parts of a reactive diluent-1, 4 parts of a small molecule phenol (p-hydroxyanisole), 0.5 parts of a leveling agent-1, and 0.8 parts of a defoaming agent-1.

[0148] The matrix resin includes acrylic resin-1 and novolac epoxy acrylate-1 in a mass ratio of 40:60.

[0149] The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:2:1.

[0150] The preparation method of the negative photoresist that is resistant to electroplating and can be quickly alkali-stripped is as follows: a base resin, a photoinitiator, a solvent-1, a reactive diluent-1, a small molecule phenol (p-hydroxyanisole), a leveling agent-1, and a defoaming agent-1 are uniformly mixed to obtain a negative photoresist that is resistant to electroplating and can be quickly alkali-stripped.

[0151] Test Case Photoresist usage process (testing process) 1. Printing and coating: Use 200-350 mesh steel screen printing, and evenly coat the photoresist on the substrate. Control the photoresist printing thickness at 12μm. Pre-baking: The baking condition is a forced air oven at 90℃ / 10min.

[0152] 2. Exposure: Use a non-contact exposure machine with a 365um light source and an exposure energy of 30-100mj / cm 2 .

[0153] 3. Development: Use 1% sodium carbonate solution for development, temperature 30°C, spray pressure 0.1MPa, and development time 50 seconds; 4. Electroplating: Electroplating conditions: 5% sulfuric acid, 50°C, current 0.15A, 30 minutes.

[0154] Performance testing: 1. Resolution: Observe and measure the line width using a 500x microscope. The line width of Example 1 is as follows: Figure 1 As shown, record the line distribution (whether there are gaps, broken lines, crooked lines, residuals / short circuits).

[0155] 2. Stripping time: At 45°C, strip the photoresist film in 5% sodium hydroxide solution and record the time it takes to completely strip the film (greater than 45s is unqualified).

[0156] 3. Electroplating resistance: no discoloration, no peeling, no defects, no seepage, no missing plating (electroplating conditions: 5% sulfuric acid, 50℃, current 0.15A, 30 minutes).

[0157] Table 1 As can be seen from Table 1, the negative photoresist of the present invention has excellent anti-plating effect, can be quickly alkali-stripped, and has a resolution lower than 20 μm.

[0158] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A negative photoresist that is resistant to electroplating and can be quickly alkali-stripped, characterized in that: The invention comprises the following components in parts by weight: 60-80 parts of base resin, 3-10 parts of photoinitiator, 7-15 parts of solvent, 5-10 parts of reactive diluent, 3-8 parts of small molecule acid monomer, 0.2-2 parts of leveling agent and 0.3-2.5 parts of defoaming agent; The matrix resin comprises an acrylic resin and a novolac epoxy acrylate in a mass ratio of (40-60):(40-60); the acrylic resin has an acid value of 50-150 mgKOH / g and a viscosity of 5000-50000 mPa·s at 25°C; the novolac epoxy acrylate has an acid value of 40-120 mgKOH / g and a viscosity of 10000-100000 mPa·s at 25°C; The small molecule acid monomer contains a carbon-carbon double bond and a carboxyl group.

2. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The small molecule acid monomer includes at least one of itaconic acid, acrylic acid, methacrylic acid, 1,6-heptadiene-4-carboxylic acid and methyl-1,6-heptadiene-4-carboxylic acid.

3. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The acrylic resin has an acid value of 50-70 mgKOH / g and a viscosity of 25,000-40,000 mPa·s at 25° C.

4. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The novolac epoxy acrylate has an acid value of 50-110 mgKOH / g and a viscosity of 30,000-90,000 mPa·s at 25° C.

5. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The photoinitiator includes at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, benzophenone and bis-2,6-difluoro-3-pyrrolphenyl titanocene.

6. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide in a mass ratio of 1:(1.5-2.5):(0.8-1.2).

7. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The solvent includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isophorone, N-methyl pyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, alcohol ester dodecyl and DBE solvent.

8. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The reactive diluent includes at least one of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol triacrylate.

9. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The defoamer includes a non-fluorine and non-silicone defoamer, the defoamer includes at least one of an acrylate defoamer and a mineral oil defoamer, and the defoamer includes at least one of defoamer BYK-1794, defoamer BYK-055, and defoamer LAP-20.

10. The negative photoresist with rapid alkali stripping and anti-plating properties according to claim 1, characterized in that: The leveling agent includes an acrylic leveling agent.

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