A negative photoresist with fast alkali stripping resistance

Abstract

The application discloses a kind of negative photoresist of anti-electroplating fast alkali stripping, belong to photoresist technical field, the negative photoresist of anti-electroplating fast alkali stripping, including the following mass parts components: 60~80 parts base resin, 3~10 parts photo initiator, 7~15 parts solvent, 5~10 parts active diluent, 3~8 parts small molecule acid monomer, 0.2~2 parts leveling agent and 0.3~2.5 parts defoaming agent;The base resin includes mass ratio is (40~60) acrylic resin and phenolic epoxy acrylate (40~60);The small molecule acid monomer contains carbon-carbon double bond and carboxyl.The negative photoresist of the application has excellent anti-electroplating effect, can fast alkali stripping, and resolution is high.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photoresist, and particularly relates to a negative photoresist capable of resisting electroplating and being quickly alkali-stripped. BACKGROUND

[0002] HJT (heterojunction) cells are considered as the next generation mainstream technology of photovoltaics due to high conversion efficiency, low temperature coefficient and simple process. However, the metallization process of the HJT cells relies on high-cost silver paste, resulting in high non-silicon cost. The core goal of the copper process (including electroplated copper and silver-coated copper technology) is to replace silver materials to reduce cost while maintaining cell efficiency and reliability.

[0003] The electroplated copper technology can significantly reduce the non-silicon cost of the heterojunction cell by replacing the high-cost silver paste with a copper electrode. The copper process has a very large development prospect in the application of the HJT cell, and the photoresist is a core raw material of the process.

[0004] A big problem of the photoresist for the copper process is that the stripping time is too long, and the long time will cause strong alkali corrosion of the silicon wafer substrate, resulting in a small final product light conversion efficiency.

[0005] In view of this, the present application is proposed. SUMMARY

[0006] The present application aims to overcome the deficiencies in the prior art and provides a negative photoresist capable of resisting electroplating and being quickly alkali-stripped. The negative photoresist has excellent anti-electroplating effect, can be quickly alkali-stripped, and has high resolution.

[0007] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] A negative photoresist capable of resisting electroplating and being quickly alkali-stripped comprises the following components by mass: 60-80 parts of base resin, 3-10 parts of photoinitiator, 7-15 parts of solvent, 5-10 parts of active 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.

[0009] The base resin comprises acrylic resin and phenolic 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 DEG C; and the phenolic epoxy acrylate has an acid value of 40-120 mgKOH / g and a viscosity of 10000-100000 mPa·s at 25 DEG C.

[0010] The small molecule acid monomer contains a carbon-carbon double bond and a carboxyl group.

[0011] The negative photoresist has excellent anti-electroplating effect, can be quickly alkali-removed, has high resolution, and can improve photoconversion efficiency.

[0012] The acrylic resin and the phenolic epoxy acrylate with specific acid value and viscosity are used as the base resin, the acrylic resin and the phenolic epoxy acrylate both contain photosensitive groups (such as double bonds) and alkali-soluble groups (such as carboxyl groups) in the molecular structure, can effectively improve photosensitivity, improve the molecular structure, and enhance the edge acuity of the photoresist, significantly improve the resolution of the photoresist, reduce bubbles or defects in the coating process, effectively reduce the plating phenomenon, and the acrylic resin and the phenolic epoxy acrylate form a three-dimensional network crosslinked structure, improve the anti-electroplating effect, and optimize the acid value and alkali-removal rate of the photoresist.

[0013] The small-molecule acid monomer contains double bonds and -COOH, has photosensitive activity, and can react with alkali, which is a key raw material for improving the film removal speed, the double bonds can participate in the polymerization reaction and enter the main structure of the resin to improve the anti-electroplating capacity, and the -COOH improves the acid value of the crosslinked coating film, thereby achieving the effect of fast alkali-removal.

[0014] As a preferred embodiment of the application, the anti-electroplating and fast alkali-removal negative photoresist comprises the following components in mass parts: 68-75 parts of base resin, 5-8 parts of photoinitiator, 10-12 parts of solvent, 6-8 parts of active diluent, 4-6 parts of small-molecule acid monomer, 0.5-1 part of leveling agent, and 0.8-1.5 parts of defoaming agent.

[0015] As a preferred embodiment of the application, the small-molecule acid monomer comprises at least one of itaconic acid, acrylic acid, methacrylic acid, 1,6-heptadiene-4-carboxylic acid, and methyl-1,6-heptadiene-4-carboxylic acid.

[0016] As a preferred embodiment of the application, the acid value of the acrylic resin is 50-70 mgKOH / g, and the viscosity at 25℃ is 25000-40000 mPa·s.

[0017] As a preferred embodiment of the application, the acid value of the phenolic epoxy acrylate is 50-110 mgKOH / g, and the viscosity at 25℃ is 30000-90000 mPa·s.

[0018] As a preferred embodiment of the present application, the photoinitiator includes at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, benzophenone and bis 2,6-difluoro-3-pyrrole phenyl titanium.

[0019] As a preferred embodiment of the present application, the photoinitiator includes 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1: (1.5~2.5): (0.8~1.2).

[0020] As a preferred embodiment of the present application, the solvent includes at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isoflurone, N-methyl pyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, alcohol ester twelve and DBE solvent.

[0021] As a preferred embodiment of the present application, the active diluent includes at least one of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol triacrylate.

[0022] As a preferred embodiment of the present application, the defoaming agent includes a non-fluorine non-silicon defoaming agent, the defoaming agent includes at least one of an acrylate defoaming agent, a mineral oil defoaming agent, the defoaming agent includes at least one of defoaming agent BYK-1794 (BYK), defoaming agent BYK-055 (BYK), defoaming agent LAP-20 (Japan Kiri), a fluorine silicon surface additive usually has a relatively low surface tension, causing the stripping solution to be difficult to wet the photoresist surface, inhibiting the progress of stripping, and the use of a non-fluorine non-silicon defoaming agent can further improve the stripping effect.

[0023] As a preferred embodiment of the present application, the leveling agent includes an acrylate leveling agent, and the use of an acrylate leveling agent can improve the surface tension of the photoresist coating film, make the stripping solution better wet the surface, and improve the stripping speed.

[0024] As a preferred embodiment of the present application, the leveling agent includes at least one of leveling agent LHP-95 (Japan Kiri), leveling agent BYK390 (BYK), and leveling agent L-3580 (Foshan Yuehehua).

[0025] Wherein, the application is not limited to the preparation method of the anti-electroplating fast alkali-removable negative photoresist, and those skilled in the art can prepare the anti-electroplating fast alkali-removable negative photoresist according to the conventional method in the art, for example, mixing the raw materials uniformly to obtain the anti-electroplating fast alkali-removable negative photoresist.

[0026] The negative photoresist has excellent anti-electroplating effect, can be quickly removed by alkali, has high resolution, the resolution is lower than 20 μm, can improve the photoconversion efficiency, and can be well applied to the copper process technology. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The resolution pattern of the negative photoresist of Example 1. DETAILED DESCRIPTION

[0028] To make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme of the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0029] In the present application, the technical features described in an open manner include both the closed technical scheme consisting of the listed features and the open technical scheme containing the listed features.

[0030] In the present application, if no special description is provided, the numerical range is regarded as continuous and includes the minimum value and the maximum value of the range and each value between the minimum value and the maximum value. Further, when a range is referred to an integer, each integer between the minimum value and the maximum value of the range is included. In addition, when multiple ranges are provided to describe a feature or a characteristic, the ranges can be combined. In other words, unless otherwise specified, all the ranges disclosed herein should be understood as including any and all sub-ranges falling within the range.

[0031] In the present application, the specific dispersion and stirring treatment method is not particularly limited.

[0032] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present application are commercially available raw materials and instruments, and the components and raw materials used in each parallel experiment are the same.

[0033] The sources of raw materials of the examples and comparative examples are as follows:

[0034] Acrylic resin-1: acid value 60 mgKOH / g, viscosity at 25℃ 30000 mPa-s, from Guangzhou Linchuan Company, brand LC-891.

[0035] Acrylic resin-2: acid value 70 mgKOH / g, viscosity at 25℃ 25000 mPa-s, from Showa Highpolymer, brand BSR-12.

[0036] Acrylic resin-3: acid value 50 mgKOH / g, viscosity at 25℃ 40000 mPa-s, from Guangzhou Yinxin Company, brand 2261.

[0037] Acrylic resin-4: acid value 24 mgKOH / g, viscosity at 25℃ 1250 mPa-s, from Hanchwa, brand Soluryl-80T.

[0038] Phenolic epoxy acrylate-1: acid value 60 mgKOH / g, viscosity at 25℃ 90000 mPa-s, from Japan Chemical Company, brand KR-1000.

[0039] Phenolic epoxy acrylate-2: acid value 110 mgKOH / g, viscosity at 25℃ 30000 mPa-s, from Japan Chemical Company, brand PCR-2014HW.

[0040] Phenolic epoxy acrylate-3: acid value 50 mgKOH / g, viscosity at 25℃ 50000 mPa-s, from Japan Chemical Company, brand CCR-4959HW.

[0041] Solvent: diethylene glycol ethyl ether acetate.

[0042] Active diluent-1: 1,6-hexanediol diacrylate.

[0043] Active diluent-2: tripropylene glycol diacrylate.

[0044] Defoamer-1: BYK-1794 (BYK Company).

[0045] Defoamer-2: defoamer BYK-055 (BYK Company).

[0046] Leveling agent-1: leveling agent LHP-95 (Japan Kiri Company).

[0047] Leveling agent-2: leveling agent BYK390 (BYK Company).

[0048] Small molecule acid monomer-1: itaconic acid.

[0049] Small molecule acid monomer-2: methacrylic acid.

[0050] The following examples are provided to facilitate an understanding of the present application. The examples are provided without admitting that the scope of the claims is limited by the examples.

[0051] Example 1

[0052] A negative photoresist with anti-electroplating and fast alkali stripping, comprising the following components by mass fraction: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, 0.8 parts of defoaming agent-1.

[0053] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0054] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0055] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping is as follows: the base resin, photoinitiator, solvent-1, active diluent-1, small molecule acid monomer-1, leveling agent-1 and defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping.

[0056] Example 2

[0057] The difference between Example 2 and Example 1 is that the amount of each raw material is different, and the others are the same.

[0058] A negative photoresist with anti-electroplating and fast alkali stripping, comprising the following components by mass fraction: 75 parts of base resin, 8 parts of photoinitiator, 12 parts of solvent-1, 8 parts of active diluent-1, 6 parts of small molecule acid monomer-1, 1 part of leveling agent-1, 1.5 parts of defoaming agent-1.

[0059] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0060] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0061] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping is as follows: the base resin, photoinitiator, solvent-1, active diluent-1, small molecule acid monomer-1, leveling agent-1 and defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping.

[0062] Example 3

[0063] Example 3 differs from Example 1 in that the amounts of the respective raw materials are different, and the others are the same.

[0064] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising the following components in mass parts: 60 parts of base resin, 3 parts of photoinitiator, 7 parts of solvent-1, 5 parts of active diluent-1, 3 parts of small molecule acid monomer-1, 0.2 parts of leveling agent-1, and 0.3 parts of defoaming agent-1.

[0065] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0066] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0067] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1 and the defoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0068] Example 4

[0069] Example 4 differs from Example 1 in that the amounts of the respective raw materials are different, and the others are the same.

[0070] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising the following components in mass parts: 80 parts of base resin, 10 parts of photoinitiator, 15 parts of solvent-1, 10 parts of active diluent-1, 8 parts of small molecule acid monomer-1, 2 parts of leveling agent-1, and 2.5 parts of defoaming agent-1.

[0071] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0072] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0073] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1 and the defoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0074] Example 5

[0075] Example 5 differs from example 1 in that the selection of raw materials is different, and the others are the same.

[0076] A negative photoresist resistant to electroplating and fast alkali stripping, comprising the following components by mass fraction: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-2, 6 parts of active diluent-2, 4 parts of small molecule acid monomer-2, 0.5 parts of leveling agent-2, and 0.8 parts of defoaming agent-2.

[0077] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0078] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0079] The preparation method of the negative photoresist resistant to electroplating and fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-2, the active diluent-2, the small molecule acid monomer-2, the leveling agent-2 and the defoaming agent-2 are uniformly mixed to obtain the negative photoresist resistant to electroplating and fast alkali stripping.

[0080] Example 6

[0081] Example 6 differs from example 1 in that the mass ratio of acrylic resin-1 and phenolic epoxy acrylate-1 is different, and the others are the same.

[0082] A negative photoresist resistant to electroplating and fast alkali stripping, comprising the following components by mass fraction: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0083] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 60:40.

[0084] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

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

[0086] Example 7

[0087] Example 7 differs from example 1 in that the selection of acrylic resin and phenolic epoxy acrylate is different, and others are the same.

[0088] A negative photoresist with anti-electroplating and fast alkali stripping resistance comprises the following components by mass fraction: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0089] The base resin comprises acrylic resin-2 and phenolic epoxy acrylate-2 in a mass ratio of 40:60.

[0090] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0091] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping resistance is as follows: the base resin, photoinitiator, solvent-1, active diluent-1, small molecule acid monomer-1, leveling agent-1 and defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping resistance.

[0092] Example 8

[0093] Example 8 differs from example 1 in that the selection of acrylic resin and phenolic epoxy acrylate is different, and others are the same.

[0094] A negative photoresist with anti-electroplating and fast alkali stripping resistance comprises the following components by mass fraction: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0095] The base resin comprises acrylic resin-3 and phenolic epoxy acrylate-3 in a mass ratio of 40:60.

[0096] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0097] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping resistance is as follows: the base resin, photoinitiator, solvent-1, active diluent-1, small molecule acid monomer-1, leveling agent-1 and defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping resistance.

[0098] Example 9

[0099] Example 9 differs from example 1 in that the selection of the photoinitiator is different, and the others are the same.

[0100] A negative photoresist resistant to electroplating and fast alkali stripping, comprising the following components in mass parts: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0101] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0102] The photoinitiator comprises 2-isopropylthioxanthone and 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone in a mass ratio of 1:2.

[0103] The preparation method of the negative photoresist resistant to electroplating and fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1, and the defoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and fast alkali stripping.

[0104] Example 10

[0105] Example 10 differs from example 1 in that the selection of the photoinitiator is different, and the others are the same.

[0106] A negative photoresist resistant to electroplating and fast alkali stripping, comprising the following components in mass parts: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0107] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0108] The photoinitiator comprises 2-isopropylthioxanthone and 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone in a mass ratio of 1:2.

[0109] The preparation method of the negative photoresist resistant to electroplating and fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1, and the defoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and fast alkali stripping.

[0110] Example 11

[0111] Example 11 differs from example 1 in that the selection of the photoinitiator is different, and the others are the same.

[0112] A negative photoresist with anti-electroplating and fast alkali stripping, comprising the following components by mass fraction: 68 parts of base resin, 5 parts of photo initiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0113] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0114] The photo initiator comprises 2-phenyl benz-2-dimethylamine-1-(4-morpholinyl benzyl phenyl) butanone and phenyl bis(2,4,6-trimethyl benzoyl) phosphine oxide in a mass ratio of 2:1.

[0115] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping is as follows: the base resin, the photo initiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1, and the defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping.

[0116] Example 12

[0117] Example 12 is different from example 1 in that the selection of the photo initiator is different, and the others are the same.

[0118] A negative photoresist with anti-electroplating and fast alkali stripping, comprising the following components by mass fraction: 68 parts of base resin, 5 parts of photo initiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule acid monomer-1, 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0119] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0120] The photo initiator comprises benzophenone, bis 2,6-difluoro-3-pyrrole phenyl titanium and phenyl bis(2,4,6-trimethyl benzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0121] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping is as follows: the base resin, the photo initiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1, and the defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping.

[0122] Comparative example 1

[0123] Comparative example 1 is different from example 1 in that the amount of each raw material is different, and the others are the same.

[0124] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising the following components by mass fraction: 50 parts of a base resin, 1 part of a photoinitiator, 5 parts of a solvent-1, 2 parts of an active diluent-1, 2 parts of a small molecule acid monomer-1, 0.1 part of a leveling agent-1, and 0.2 part of an antifoaming agent-1.

[0125] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0126] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0127] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1 and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0128] Comparative Example 2

[0129] Comparative Example 2 is different from Example 1 in that the amounts of the raw materials are different, and other aspects are the same.

[0130] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising the following components by mass fraction: 90 parts of a base resin, 15 parts of a photoinitiator, 20 parts of a solvent-1, 15 parts of an active diluent-1, 12 parts of a small molecule acid monomer-1, 3 parts of a leveling agent-1, and 3 parts of an antifoaming agent-1.

[0131] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0132] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0133] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small molecule acid monomer-1, the leveling agent-1 and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0134] Comparative Example 3

[0135] Comparative Example 3 is different from Example 1 in that the base resin is different, and other aspects are the same.

[0136] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising 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 an active diluent-1, 4 parts of a small-molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of an antifoaming agent-1.

[0137] The base resin comprises an acrylic resin-1.

[0138] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethyl benzoyl) phosphine oxide at a mass ratio of 1:2:1.

[0139] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small-molecule acid monomer-1, the leveling agent-1 and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0140] Comparative Example 4

[0141] Comparative Example 4 is different from Example 1 in that the base resin is different, and other aspects are the same.

[0142] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising 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 an active diluent-1, 4 parts of a small-molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of an antifoaming agent-1.

[0143] The base resin comprises a phenolic epoxy acrylate-1.

[0144] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone and phenyl bis(2,4,6-trimethyl benzoyl) phosphine oxide at a mass ratio of 1:2:1.

[0145] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small-molecule acid monomer-1, the leveling agent-1 and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0146] Comparative Example 5

[0147] Comparative Example 5 is different from Example 1 in that the base resin is different, and other aspects are the same.

[0148] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising 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 an active diluent-1, 4 parts of a small-molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of an antifoaming agent-1.

[0149] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 at a mass ratio of 20:80.

[0150] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone, and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide at a mass ratio of 1:2:1.

[0151] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small-molecule acid monomer-1, the leveling agent-1, and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0152] Comparative Example 6

[0153] Comparative Example 6 is different from Example 1 in that the base resin is different, and other aspects are the same.

[0154] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising 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 an active diluent-1, 4 parts of a small-molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of an antifoaming agent-1.

[0155] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 at a mass ratio of 80:20.

[0156] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone, and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide at a mass ratio of 1:2:1.

[0157] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small-molecule acid monomer-1, the leveling agent-1, and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0158] Comparative Example 7

[0159] Comparative Example 7 is different from Example 1 in that the base resin is different, and other aspects are the same.

[0160] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising 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 an active diluent-1, 4 parts of a small-molecule acid monomer-1, 0.5 parts of a leveling agent-1, and 0.8 parts of an antifoaming agent-1.

[0161] The base resin comprises acrylic resin-4 and phenolic epoxy acrylate-1 at a mass ratio of 40:60.

[0162] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone, and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide at a mass ratio of 1:2:1.

[0163] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the small-molecule acid monomer-1, the leveling agent-1, and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0164] Comparative Example 8

[0165] Comparative Example 8 is different from Example 1 in that no small-molecule acid monomer is added in Comparative Example 8, and the other conditions are the same.

[0166] A negative photoresist resistant to electroplating and capable of fast alkali stripping, comprising 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 an active diluent-1, 0.5 parts of a leveling agent-1, and 0.8 parts of an antifoaming agent-1.

[0167] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 at a mass ratio of 40:60.

[0168] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl phenyl) butanone, and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide at a mass ratio of 1:2:1.

[0169] The preparation method of the negative photoresist resistant to electroplating and capable of fast alkali stripping is as follows: the base resin, the photoinitiator, the solvent-1, the active diluent-1, the leveling agent-1, and the antifoaming agent-1 are uniformly mixed to obtain the negative photoresist resistant to electroplating and capable of fast alkali stripping.

[0170] Comparative Example 9

[0171] Comparative Example 9 is different from Example 1 in that a small-molecule phenol (p-hydroxyanisole) is used to replace the small-molecule acid monomer in Comparative Example 9, and the other conditions are the same.

[0172] A negative photoresist with anti-electroplating and fast alkali stripping, comprising the following components by mass fraction: 68 parts of base resin, 5 parts of photoinitiator, 10 parts of solvent-1, 6 parts of active diluent-1, 4 parts of small molecule phenol (p-hydroxyanisole), 0.5 parts of leveling agent-1, and 0.8 parts of defoaming agent-1.

[0173] The base resin comprises acrylic resin-1 and phenolic epoxy acrylate-1 in a mass ratio of 40:60.

[0174] The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzylphenyl) butanone, and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:2:1.

[0175] The preparation method of the negative photoresist with anti-electroplating and fast alkali stripping is as follows: the base resin, photoinitiator, solvent-1, active diluent-1, small molecule phenol (p-hydroxyanisole), leveling agent-1, and defoaming agent-1 are uniformly mixed to obtain the negative photoresist with anti-electroplating and fast alkali stripping.

[0176] Test example

[0177] Photoresist use process (test process)

[0178] 1. Printing and coating: using a 200-350 mesh steel screen printing, uniformly coating the photoresist on the substrate, controlling the photoresist printing thickness to be 12 μm, and pre-baking: the baking condition is air oven 90℃ / 10min.

[0179] 2. Exposure: using a non-contact exposure machine with a 365um light source, the exposure energy is 30-100mj / cm 2 .

[0180] 3. Development: using 1% sodium carbonate solution for development, the temperature is 30℃, the spraying pressure is 0.1MPa, and the development time is 50 seconds;

[0181] 4. Electroplating: electroplating condition: 5% sulfuric acid, 50℃, current 0.15A, 30 minutes.

[0182] Performance test:

[0183] 1. Resolution: using a 500 times microscope to observe and measure, observing and measuring the line width, wherein the line width of example 1 is as Figure 1 shown, and recording the line distribution (whether there are gaps, broken lines, and line not straight, and residual / short circuit phenomenon).

[0184] 2. Stripping time: at 45℃, the photoresist film is stripped in 5% sodium hydroxide solution, and the time when the stripping is completely dry is recorded (more than 45s is unqualified).

[0185] 3. Anti-electroplating: no discoloration, no peeling, no defect, no penetration and no leakage (electroplating conditions: 5% sulfuric acid, 50°C, current 0.15A, 30 minutes).

[0186] Table 1

[0187]

[0188] As can be seen from Table 1, the negative photoresist has excellent anti-electroplating effect, can be quickly alkali stripped, and has a resolution less than 20 μm.

[0189] It should be noted that the above examples are only used to illustrate the technical solutions of the present application, and are not intended to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application.

Claims

1. A negative photoresist which is resistant to electroplating and can be quickly alkali-stripped, characterized in that, The composition comprises the following components by mass: 60-80 parts of a base resin, 3-10 parts of a photoinitiator, 7-15 parts of a solvent, 5-10 parts of an active 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 an antifoaming agent; The base resin comprises an acrylic resin and a phenolic 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; and the phenolic 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 rapid alkali-strippable negative photoresist according to claim 1, wherein The small-molecule acid monomer comprises 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 rapid alkali-strippable negative photoresist of claim 1, wherein The acrylic resin has an acid value of 50-70 mgKOH / g and a viscosity of 25000-40000 mPa·s at 25°C.

4. The rapid alkali-strippable negative photoresist of claim 1, wherein The phenolic epoxy acrylate has an acid value of 50-110 mgKOH / g and a viscosity of 30000-90000 mPa·s at 25°C.

5. The rapid alkali-strippable negative photoresist of claim 1, wherein The photoinitiator comprises at least one of 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, benzophenone, and bis 2,6-difluoro-3-pyrrole phenyl titaniumocene.

6. The rapid alkali-strippable negative photoresist of claim 1, wherein, The photoinitiator comprises 2-isopropylthioxanthone, 2-phenylbenz-2-dimethylamine-1-(4-morpholinobenzyl) butanone, and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide in a mass ratio of 1:(1.5-2.5):(0.8-1.2).

7. The rapid alkali-strippable negative photoresist of claim 1, wherein The solvent comprises at least one of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, isofuroleone, N-methyl pyrrolidone, propylene glycol methyl ether acetate, dipropylene glycol methyl ether, turpentine, alcohol ester twelve, and DBE solvent.

8. The rapid alkali-strippable negative photoresist of claim 1, wherein, The active diluent comprises at least one of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol triacrylate.

9. The rapid alkali-strippable negative photoresist of claim 1, wherein The antifoaming agent comprises a non-fluorine non-silicon antifoaming agent.

10. The negative photoresist according to claim 9, wherein The antifoaming agent comprises at least one of an acrylate antifoaming agent and a mineral oil antifoaming agent.

11. The rapid alkali-strippable negative photoresist of claim 9, wherein The antifoaming agent comprises at least one of antifoaming agent BYK-1794, antifoaming agent BYK-055, and antifoaming agent LAP-20.

12. The rapid alkali-strippable negative photoresist of claim 1, wherein The leveling agent comprises an acrylate leveling agent.

Images