Electroplating-resistant composition, dry film and cured product thereof, and electrode of solar cell

Abstract

Provided are an anti-plating composition and a dry film which have low exposure energy and high sensitivity, and a cured product which is formed therefrom, has excellent plating resistance, high resolution, and is free of lateral erosion and diffusion plating, and an electrode of a solar cell using the same. The electroplating-resistant composition comprises (A) a carboxyl group-containing resin, (B) a photosensitive monomer and (C) a photopolymerization initiator, and the photopolymerization initiator (C) comprises 4, 4 '-diphenyl-1, 3, 4, 5-tetramethyl-1, 3, 5-tetramethyl-1, the invention relates to an oxime ester photopolymerization initiator, which is prepared from 4, 4 '-bis (diethylamino) benzophenone, 2-isopropyl thioxanthone, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl propane-1-one and an oxime ester photopolymerization initiator as shown in a formula (1),

Description

Technical Field

[0001] This invention relates to an anti-plating composition, specifically to an anti-plating composition used in the manufacture of electrodes for solar cells, and its dry film, cured product, and electrodes for solar cells using the same, belonging to the field of anti-plating materials used in solar cell manufacturing. Background Technology

[0002] A solar cell is a semiconductor device that converts solar energy into electrical energy. Under sunlight, a photocurrent is generated inside the solar cell, and electrical energy is output through electrodes. In recent years, solar cell manufacturing technology has continuously improved, production costs have been decreasing, and conversion efficiency has been continuously improving. The application of solar cell power generation has become increasingly widespread and has become an important source of electricity supply.

[0003] Various research and development efforts have been actively undertaken regarding solar cell electrodes and their manufacturing methods, which are core components of solar cells. While low-temperature silver paste technology is commonly used to fabricate solar cell grid lines, it suffers from high costs. To further reduce costs and increase efficiency, electroplating has become a significant research focus for fabricating metal electrodes for solar cells. This method primarily involves partially or completely replacing expensive silver with lower-cost metals such as copper or nickel. When fabricating electrodes using electroplating, the position and size of the metal electrodes need to be defined on the solar cell surface using a patterned mask. Anti-electroplating ink is then used for development, exposure, and washing, followed by electroplating according to the exposed pattern.

[0004] Patent Document 1 provides a photosensitive resin composition and a cured product that exhibits high curability compared to conventional photosensitive resin compositions and inhibits the leaching of components from the cured photosensitive resin composition into the electroplating solution. It addresses the aforementioned issues by combining a specific anthracene compound as a sensitizer with a specific thermosetting resin in the photosensitive resin composition; however, it does not address the exposure energy, photosensitivity, electroplating resistance of the dry film, resolution, or the occurrence of lateral etching.

[0005] Patent document 2 discloses a method for fabricating electrodes for heterojunction solar cells. It uses inexpensive anti-plating ink instead of expensive dry film, and after printing, only UV or heat curing is required before electroplating, making it suitable for mass production. However, it does not address the photosensitivity and resolution of the anti-plating ink.

[0006] Patent document 3 discloses a high-sensitivity photoresist ink for PCBs and its preparation method. By optimizing the proportions and rationally combining raw materials such as high-sensitivity resin, photosensitive resin, epoxy resin, high-sensitivity monomer, and UV high-sensitivity photoinitiator, and using environmentally friendly solvents instead of ordinary solvents, the photosensitive ink is modified from a common type to a high-sensitivity type. This reduces energy consumption, pollution, and improves efficiency. The resulting high-sensitivity photoresist ink exhibits excellent photosensitivity, hardness, heat resistance, and flow properties. However, it does not address the resolution and electroplating resistance of the solder resist ink.

[0007] Patent document 4 discloses a photovoltaic cell solder resist ink and its preparation method. By mixing modified epoxy resin with other raw materials, the resulting photovoltaic cell solder resist ink exhibits good printability, low curing temperature, fast curing speed, and excellent adhesion, solder resistance, and weather resistance after curing. However, it does not address the resolution and electroplating resistance of the solder resist ink.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: CN115128901A

[0011] Patent Document 2: CN109427917A

[0012] Patent Document 3: CN113604103A

[0013] Patent Document 4: CN116396635A Summary of the Invention

[0014] The problem the invention aims to solve

[0015] Traditional anti-plating inks used in the manufacture of solar cell electrodes suffer from poor stability, long exposure times, and excessive lateral etching leading to plating penetration, resulting in a decline in the quality of solar cell electrode manufacturing. This can lead to reduced overall module power, excessive localized heating, and shorten module lifespan; in severe cases, it can even burn out the battery module. Therefore, there is an urgent need to develop an anti-plating ink with low exposure energy and high photosensitivity. Furthermore, the dry film formed from this anti-plating composition should possess excellent electroplating resistance, high resolution, and the advantages of no lateral etching and no plating penetration.

[0016] Solution for solving the problem

[0017] The inventors conducted in-depth research and found that by combining carboxyl-containing resins, photosensitive monomers, and specific photopolymerization initiators, sensitivity can be improved, ink resolution can be enhanced, ink side etching can be reduced to solve the problem of plating penetration, and ultimately the purpose of improving production efficiency and the manufacturing quality of solar cell electrodes can be achieved, thus completing this invention.

[0018] That is, the present invention is as follows.

[0019] [1]. This invention provides an anti-electroplating composition, comprising (A) a carboxyl-containing resin, (B) a photosensitive monomer, and (C) a photopolymerization initiator.

[0020] The photopolymerization initiator (C) comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator shown in formula (1).

[0021]

[0022] [2]. According to the anti-electroplating composition of [1], wherein, by mass ratio, the proportions of the 4,4'-bis(diethylamino)benzophenone, the 2-isopropylthioxanthone, the 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one and the oxime ester-based photopolymerization initiator in the (C) photopolymerization initiator are 0.5-1:1-5:10-30:5-10:0.05-0.75.

[0023] [3]. The anti-plating composition according to [1] or [2], wherein, by mass ratio, the proportions of the 4,4'-bis(diethylamino)benzophenone, the 2-isopropylthioxanthone, the 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one and the oxime ester-based photopolymerization initiator in the (C) photopolymerization initiator are 0.6-0.8:2-4:12-27:6-8:0.08-0.65.

[0024] [4]. The anti-plating composition according to [1] or [2], wherein, by mass ratio, the proportions of the 4,4'-bis(diethylamino)benzophenone, the 2-isopropylthioxanthone, the 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one and the oxime ester-based photopolymerization initiator in the (C) photopolymerization initiator are 0.75:3:15 to 25:7.5:0.1 to 0.5.

[0025] [5]. The anti-plating composition according to [1] or [2], wherein the amount of (C) photopolymerization initiator is 5 to 60 parts by mass relative to 100 parts by mass of the solid component of (A) carboxyl-containing resin.

[0026] [6]. The present invention also provides the use of any one of the anti-plating compositions described in [1] to [5] in the manufacture of electrodes for solar cells.

[0027] [7]. Furthermore, the present invention also provides a dry film, which is obtained by coating an anti-electroplating composition as described in any one of [1] to [5] onto a carrier film and drying it.

[0028] [8]. Furthermore, the present invention also provides a cured product, which is obtained by curing the anti-electroplating composition described in any one of [1] to [5].

[0029] [9]. Furthermore, the present invention also provides a cured product obtained by curing the resin layer of the dry film described in [7].

[0030]

[10] . In addition, the present invention provides an electrode for a solar cell, wherein the solidified material described in [8] or [9] is present.

[0031] The effects of the invention

[0032] According to the present invention, an anti-plating composition and dry film with low exposure energy and high photosensitivity are provided, as well as a cured product formed therefrom having excellent anti-plating properties, high resolution, and no side etching or plating phenomena, and an electrode for a solar cell using the same. Detailed Implementation

[0033] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments.

[0034] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0035] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0036] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0037] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0038] In this specification, (meth)acrylic acid refers to the term collectively known as acrylic acid, methacrylic acid, and mixtures thereof, as well as other similar expressions.

[0039] This invention provides an anti-electroplating composition, characterized in that it comprises (A) a carboxyl-containing resin, (B) a photosensitive monomer, and (C) a photopolymerization initiator.

[0040] The photopolymerization initiator (C) comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator shown in formula (1).

[0041]

[0042] The components of the anti-electroplation composition of the present invention will be described in detail below.

[0043] (A) Carboxyl-containing resin

[0044] As the (A) carboxyl-containing resin, various conventionally known carboxyl-containing resins having carboxyl groups in their molecules can be used. From the perspective of improving photocuring efficiency, the (A) carboxyl-containing resin preferably includes a resin having multiple (meth)acryloyl groups in its molecules, which is cured by polymerization and / or cross-linking upon light irradiation via the olefinic unsaturated double bonds possessed by the (meth)acryloyl groups.

[0045] The (A) carboxyl-containing resin is not particularly limited, and can be, for example, a resin with multiple (meth)acryloyl groups in its molecule obtained by modifying epoxy resin, phenolic resin, polycarbonate resin, polyether resin, polyester resin, polyolefin resin, or polyurethane resin with acrylic acid. From the viewpoint of further improving electroplating resistance, resolution, etc., the double bond equivalent of (A) carboxyl-containing resin is preferably 220 to 410 g / eq, more preferably 250 to 390 g / eq, and even more preferably 270 to 320 g / eq.

[0046] From the viewpoint of achieving the effects of this invention, such as excellent anti-plating performance and high resolution, epoxy-modified acrylic resins are preferred. Typical epoxy-modified acrylic resins include resins obtained by reacting a multifunctional epoxy resin with (meth)acrylic acid to form a diacid anhydride on a hydroxyl group present in the side chain; and resins obtained by further adding compounds having one epoxy group and one or more (meth)acryloyl groups to the resin. Examples of compounds having one epoxy group and one or more (meth)acryloyl groups include glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and 3,4-epoxycyclohexyl methyl methacrylate.

[0047] Multifunctional epoxy resins used for synthesizing epoxy-modified acrylic resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, phenolic varnish type epoxy resins, cresol phenolic varnish type epoxy resins, bisphenol phenolic varnish type epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene phenolic varnish type epoxy resins, triphenylmethane type epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, phosphorus-containing epoxy resins, anthracene type epoxy resins, norbornene type epoxy resins, adamantane type epoxy resins, fluorene type epoxy resins, aminophenol type epoxy resins, aminocresol type epoxy resins, alkylphenol type epoxy resins, etc. These epoxy resins can be used alone or in appropriate combinations of two or more. Among these multifunctional epoxy resins, from the viewpoint of further enhancing the effects of the present invention, phenolic varnish-type epoxy resin and cresolic varnish-type epoxy resin are preferred, and phenolic varnish-type epoxy resin is more preferred.

[0048] Examples of diacid anhydrides used in the synthesis of epoxy-modified acrylic resins include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. These diacid anhydrides can be used alone or in appropriate combinations of two or more. From the viewpoint of further enhancing the effects of the present invention, tetrahydrophthalic anhydride is preferred.

[0049] Therefore, from the viewpoint of further enhancing the effects of the present invention, epoxy-modified acrylic resins obtained by reacting phenolic varnish-type epoxy resins or cresolic varnish-type epoxy resins with (meth)acrylic acid to add tetrahydrophthalic anhydride to the hydroxyl groups present in the side chains are further preferred. Especially from the viewpoint of excellent electroplating resistance, high resolution, and absence of side etching and plating penetration, epoxy-modified acrylic resins obtained by reacting cresolic varnish-type epoxy resins with acrylic acid to add tetrahydrophthalic anhydride to the hydroxyl groups present in the side chains are particularly preferred. From the same viewpoint, epoxy-modified acrylic resins obtained by further adding glycidyl (meth)acrylate to these epoxy-modified acrylic resins are also preferred.

[0050] As for the carboxyl-containing resin mentioned in (A) above, both commercially available and synthetic products can be used. Examples of commercially available products include the GF series manufactured by Guangzhou Starley Electronic Materials Co., Ltd., such as GF-105, GF-159, and GF-148. Specific examples of synthetic products include the compounds listed below:

[0051] (1) A carboxyl-containing resin is formed by reacting a multifunctional epoxy resin with (meth)acrylic acid to add dicarboxylic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the hydroxyl groups present in the side chain.

[0052] (2) A multifunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a 2-functional epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid to form a carboxyl-containing resin by adding a dicarboxylic acid anhydride to the generated hydroxyl group.

[0053] (3) A compound with multiple phenolic hydroxyl groups in one molecule is reacted with ethylene oxide, propylene oxide and other epoxides to obtain a reaction product. The reaction product is then reacted with a monocarboxylic acid containing an unsaturated group. The resulting reaction product is then reacted with a polyacid anhydride to obtain a carboxyl-containing resin.

[0054] (4) A compound with multiple phenolic hydroxyl groups in one molecule is reacted with cyclic carbonate compounds such as ethylene carbonate and propylene carbonate to obtain a reaction product. The reaction product is then reacted with a monocarboxylic acid containing an unsaturated group. The resulting reaction product is then reacted with a polyacid anhydride to obtain a carboxyl-containing resin.

[0055] (5) A carboxyl-containing resin formed by further adding (meth)acrylate, α-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl methacrylate and other compounds having one epoxy group and one or more (meth)acryloyl groups to the carboxyl-containing resins described in (1) to (4) above.

[0056] From the viewpoint of anti-electroplating performance and resolution, (A) the acid value of the carboxyl-containing resin is 5 to 120 mg KOH / g, preferably 10 to 110 mg KOH / g, and more preferably 20 to 100 mg KOH / g.

[0057] (A) The weight-average molecular weight of the carboxyl-containing resin varies depending on the resin skeleton, and is generally preferably 5,000 to 150,000. By having a weight-average molecular weight of 5,000 or more, the coating strength can be improved. Furthermore, by having a weight-average molecular weight of 150,000 or less, anti-plating properties, resolution, etc., can be improved. More preferably, it is 6,000 to 120,000, and even more preferably, it is 7,000 to 100,000.

[0058] (A) The amount of carboxyl-containing resin in the anti-electroplating composition is preferably 30 to 90% by mass, calculated as solids. Setting it to 30% by mass or more improves coatability, film strength, resolution, etc. Furthermore, setting it to 90% by mass or less improves anti-electroplating properties. More preferably, it is 40 to 80% by mass; even more preferably, it is 50 to 70% by mass; and most preferably, it is 55 to 65% by mass.

[0059] These (A) carboxyl-containing resins are not limited to the substances listed above; one type or two or more types may be used in combination.

[0060] (B) Photosensitive monomers

[0061] The anti-plating composition of the present invention further comprises a photosensitive monomer, which is a compound having multiple (meth)acryloyl groups in its molecule. The photosensitive monomer undergoes photocuring or cross-linking by irradiation with active energy rays, making the anti-plating composition of the present invention insoluble in alkaline aqueous solutions, or contributing to the insolubility of the resin composition of the present invention in alkaline aqueous solutions. As (B) the photosensitive monomer, a compound having multiple (meth)acryloyl groups in its molecule is preferred.

[0062] Examples of such photosensitive monomers (B) include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and hexanediol; polyacrylates of polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, and triethyl isocyanurate, or their ethylene oxide adducts or propylene oxide adducts; polyacrylates of phenoxyacrylates, bisphenol A diacrylates, and their ethylene oxide adducts or propylene oxide adducts; polyacrylates of glycidyl ethers such as glyceryl diglycidyl ether, glyceryl triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; melamine acrylates; and / or various methacrylates corresponding to the above acrylates.

[0063] Furthermore, examples include: epoxy acrylate resins obtained by reacting multifunctional epoxy resins such as cresol phenolic varnish-type epoxy resins with acrylic acid (such epoxy acrylate resins do not include substances belonging to the above-mentioned (A) epoxy-modified acrylic resins); and epoxy acrylate compounds obtained by further reacting the hydroxyl groups of such epoxy acrylate resins with semi-carbamate compounds (obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate).

[0064] These (B) photosensitive monomers can be used alone or in mixtures of two or more. From the viewpoint of maximizing the effects of the present invention, acrylic monomers containing two or more functional groups are preferred. Furthermore, from the viewpoint of improving resolution and anti-plating properties, acrylic monomers containing three or more functional groups are more preferred, and acrylic monomers containing four or more functional groups are even more preferred.

[0065] (B) The molecular weight of the photosensitive monomer is preferably 200 to 3000, more preferably 250 to 2000, and even more preferably 300 to 1000. When the molecular weight is 200 or higher, the resolution is good. On the other hand, when the molecular weight is 3000 or lower, the developability is good.

[0066] Relative to 100 parts by weight of the solid component of (A) carboxyl-containing resin, a blending amount of (B) photosensitive monomer in the range of 5 to 40 parts by weight is suitable. If the blending amount of (B) photosensitive monomer exceeds 40 parts by weight, the content of (A) carboxyl-containing resin becomes relatively low, resulting in reduced photocurability and developability during exposure, making it difficult to obtain satisfactory electroplating resistance. If the aforementioned blending amount is less than 5 parts by weight, it is difficult to improve photocurability, difficult to form patterns through alkaline development after irradiation with active energy rays, and poor electroplating resistance. From the viewpoint of further enhancing the effects of the present invention, 8 to 35 parts by weight is more preferred, 10 to 32 parts by weight is more preferably preferred, and 20 to 30 parts by weight is most preferred.

[0067] As the aforementioned photosensitive monomer (B), commercially available products can be used, such as MT-3501A, MT-3501G (manufactured by Zhangjiagang Dongya Di'ai Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), and A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). These photosensitive monomers (B) are not limited to the substances listed above; one type can be used, or two or more types can be used in combination.

[0068] (C) Photopolymerization initiator

[0069] The anti-electroplating composition of the present invention further comprises a photopolymerization initiator. From the perspective of enabling the anti-electroplating composition to have excellent electroplating resistance, no plating penetration, and high resolution, the photopolymerization initiator preferably comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester photopolymerization initiator shown in formula (1) as essential components.

[0070]

[0071] Through in-depth research, the inventors of this invention have discovered that by simultaneously using the aforementioned specific (C) photopolymerization initiator, and by ensuring that the proportions of the aforementioned 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator shown in formula (1) are within a specific range, the anti-electroplating composition of this invention has low exposure energy and high photosensitivity. The resulting cured films all exhibit excellent electroplating resistance, high resolution, and no side etching or plating penetration.

[0072] By using the above-mentioned five specific photopolymerization initiators in combination, the anti-plating composition of the present invention can still fully cure and form a film even under short exposure times or low exposure intensities, and even with a film thickness of about 10 μm, it is not prone to cracking. This prevents plating seepage during electroplating, exhibiting excellent anti-plating performance and also possessing excellent resolution. Surprisingly, as shown in the embodiments and comparative examples of the present invention, without the use of any of the photopolymerization initiators, the electroplating resistance and photosensitivity are affected, and side etching leading to leakage may occur.

[0073] The specific combination of the above-mentioned 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one and the oxime ester photopolymerization initiator shown in formula (1) in the anti-plating composition of the present invention provides the anti-plating composition with excellent photosensitivity, and the cured film obtained therefrom exhibits excellent copper plating resistance, no plating penetration, and high resolution. From a high-level perspective, it is preferable that the proportions of the above-mentioned 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator shown in formula (1) satisfy the following relationship: preferably 4,4'-bis(diethylamino)benzophenone: 2-isopropylthioxanthone: 2,4,6-trimethylbenzoyldiphenylphosphine oxide Phosphine: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one: oxime ester photopolymerization initiator of formula (1) above = 0.5~1:1~5:10~30:5~10:0.05~0.75; more preferably 4,4'-bis(diethylamino)benzophenone: 2-isopropylthioxanthone: 2,4,6-trimethylbenzoyldiphenylphosphine oxide: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one: oxime ester photopolymerization initiator of formula (1) above = 0.5~1:1~5:10~30:5~10:0.05~0.75; The oxime ester photopolymerization initiator = 0.6-0.8: 2-4: 12-27: 6-8: 0.08-0.65; more preferably 4,4'-bis(diethylamino)benzophenone: 2-isopropylthioxanthone: 2,4,6-trimethylbenzoyldiphenylphosphine oxide: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one: the oxime ester photopolymerization initiator shown in formula (1) above = 0.75: 3: 15-25: 7.5: 0.1-0.5.

[0074] As the photopolymerization initiator of (C) above, commercially available products can be used, such as EAB manufactured by BASF AG, Germany, for 4,4'-bis(diethylamino)benzophenone; ITX manufactured by Hubei Gurun Technology Co., Ltd., for 2-isopropylthioxanthone; TPO manufactured by IGMRESINS BV, for 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Omnirad 907 (#907) manufactured by IGMRESINS BV, for 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one; and TOE-04-A3 manufactured by Nippon Chemical Industries, Ltd., for the oxime ester photopolymerization initiator shown in formula (1).

[0075]

[0076] Furthermore, relative to 100 parts by mass of the solid component of (A) carboxyl-containing resin, the amount of (C) photopolymerization initiator is 5 to 60 parts by mass. Setting it to 5 parts by mass or more improves the copper plating resistance of the cured film, etc. Additionally, setting it to 60 parts by mass or less reduces the likelihood of haloing, resulting in good resolution and sensitivity. More preferably, it is 10 to 50 parts by mass; even more preferably, 20 to 40 parts by mass; and most preferably, 26 to 37 parts by mass.

[0077] Without affecting the purpose of the present invention, the anti-electroplating composition of the present invention may also contain other photopolymerization initiators besides (C) photopolymerization initiator. As other photopolymerization initiators, any photopolymerization initiator commonly used in anti-electroplating compositions other than the above-mentioned 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one and the oxime ester photopolymerization initiator shown in formula (1) above is acceptable and there are no particular limitations.

[0078] Other photopolymerization initiators include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin ethers such as methyl benzoin, ethyl benzoin, benzoin derivatives such as benzoin dimethyl ketal, 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-( 2,4,5-triarylimidazol dimers, such as (o-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazolium dimer, and 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolium dimer; acridine derivatives such as 9-phenylacridinium and 1,7-bis(9,9'-acridyl)heptane; N-phenylglycine; N-phenylglycine derivatives; and coumarin compounds.

[0079] Other commercially available photopolymerization initiators include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (#369) and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (#819), manufactured by BASF AG. These other photopolymerization initiators can be used alone or in mixtures of two or more.

[0080] Other ingredients

[0081] In addition to the above-mentioned (A) carboxyl-containing resin, (B) photosensitive monomer, and (C) photopolymerization initiator, the anti-electroplating composition of the present invention may also contain other ingredients.

[0082] Furthermore, the anti-electroplation composition of the present invention may also contain organic solvents, which are used in the preparation of the composition and viscosity adjustment.

[0083] Organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, they include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolves, methyl cellosolves, butyl cellosolves, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ethers, naphtha, hydrogenated naphtha, and solvent naphtha. This (H) organic solvent can be used alone or in mixtures of two or more. Commercially available examples of organic solvents include carbitol acetate (CA), manufactured by Jiangsu Tianyin Chemical Co., Ltd.

[0084] The anti-electroplating composition of the present invention may contain inorganic fillers, but from the viewpoint of facilitating film removal by alkaline washing, it is preferable to exclude inorganic fillers. Furthermore, the anti-electroplating composition of the present invention exhibits excellent anti-electroplating properties even without inorganic fillers. Typical inorganic fillers are inorganic powders, such as titanium dioxide, silicon dioxide, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0085] The anti-electroplating composition of the present invention may contain a colorant, and commonly used organic colorants may be used. It should be noted that the colorant contained in the anti-electroplating composition of the present invention preferably does not include substances that are inorganic fillers. Examples of colorants include perylene-based, phthalocyanine-based, anthraquinone-based, monoazo-based, diazo-based, azo lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, quinacridone-based, isoindolinone-based, and anthraquinone-based.

[0086] This colorant can be used alone or in mixtures of two or more. Commercially available colorants include FASTOGEN (registered trademark) FA5380 blue pigment manufactured by DIC Corporation, and LP-81(HA)-1 green pigment paste 7007-UV(YST) (registered trademark) manufactured by Index Pigment Technology Co., Ltd.

[0087] As a colorant, different colors can be selected according to the specific lateral etching requirements. For example, when lateral etching close to zero is required, a blue colorant can be used in the anti-plating composition of the present invention to make the cross-section of the ink opening close to a rectangular cross-section. When slight lateral etching is required and the cross-section of the ink opening is a trapezoidal shape, a green colorant can be used in the anti-plating composition of the present invention.

[0088] Furthermore, the anti-electroplating composition of the present invention may also be formulated with, as needed, polymerization inhibitors, thermosetting catalysts, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, antioxidants, volatility agents, anti-aging agents, antibacterial / antifungal agents, defoamers, leveling agents, anti-sagging agents, thickeners, adhesion promoters, thixotropic promoters, photoinitiators, sensitizers, photoalkalizing agents, thermoplastic resins, elastomers, organic fillers, release agents, surface treatment agents, dispersants, dispersing aids, surface modifiers, stabilizers, phosphors, cellulose resins, and other commonly known additives.

[0089] Melamine is preferably added. As an antioxidant, it improves the adhesion between the substrate and the cured film of the thermosetting composition by inhibiting the oxidation of the conductor (copper) on the substrate. As a thermosetting catalyst, it can improve the acid and alkali resistance, metal plating resistance, adhesion, and hardness of the cured film formed by the anti-plating composition. Commercially available melamine products include MELAMINE manufactured by Guangzhou Jiachun Electronics Co., Ltd.

[0090] Commercially available additives used as additives in the anti-electroplating composition of the present invention include, for example, silicone defoamer KS-66 manufactured by Shin-Etsu Chemical Industry Co., Ltd., polymeric defoamer BYK-057 manufactured by BYK-CHEMIE GmbH, wetting and dispersing agent BYK-145 manufactured by BYK-CHEMIE GmbH, defoaming and leveling agent BYK-354 manufactured by BYK-CHEMIE GmbH, fumed silica AEROSIL#974 manufactured by EPOCHCORPORATION as a thickener, and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt ANTIGEL-688 manufactured by Tianjin Mosen Technology Co., Ltd. as a polymerization inhibitor.

[0091] Dry film, cured material, and electrodes for solar cells

[0092] The anti-electroplating composition of the present invention can also be made into a dry film, the dry film comprising a carrier film (support) and a layer formed on the carrier film by the above-described anti-electroplating composition.

[0093] During dry film formation, the anti-electroplating composition of the present invention is diluted with the aforementioned organic solvent and adjusted to an appropriate viscosity. It is then coated onto a carrier film with a uniform thickness using a corner roller coater, doctor blade coater, lip coater, bar coater, extrusion coater, reverse coater, transfer roller coater, gravure coater, or spray coater. Typically, it is dried at a temperature of 50–130°C for 1–30 minutes to form a resin layer as a dried coating. There are no particular limitations on the resin layer; a thickness of 10–150 μm, preferably 20–60 μm, based on the dried film thickness, is generally suitable.

[0094] Plastic films are used as the carrier film, preferably polyester films such as polyethylene terephthalate, polyimide films, polyamide-imide films, polypropylene films, and polystyrene films. There are no particular restrictions on the thickness of the carrier film, and a range of 10–150 μm is generally suitable.

[0095] At this point, after the resin layer is formed on the carrier film, in order to prevent dust from adhering to the surface of the resin layer, it is preferable to further laminate a peelable cover film on the surface of the resin layer. As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, or surface-treated paper can be used, provided that the adhesive force between the resin layer and the cover film is less than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

[0096] As a method for manufacturing solar cell electrodes using the anti-electroplating composition of the present invention or its dry film, known manufacturing methods can be employed.

[0097] For example, the anti-plating composition of the present invention can be adjusted to a viscosity suitable for a coating method as needed, and applied to the surface of a solar cell with a pyramidal textured surface by methods such as screen printing, curtain coating, spraying, or roller coating. The solvent contained in the composition is then evaporated and dried at a temperature of, for example, 60–100°C, to form a coating film. Alternatively, the dry film of the present invention can be laminated onto the surface of a solar cell with a pyramidal textured surface, and a carrier film can be peeled off, thereby forming a layer formed by the anti-plating composition on the surface of the solar cell. Then, exposure is selectively performed by irradiation with active energy rays through a photomask with a predetermined exposure pattern. The unexposed areas are developed at a temperature of, for example, around 30°C, with a developer such as a 1–2% Na₂CO₃ or K₂CO₃ solution for, for example, 60–90 seconds, to form an anti-plating mask with a predetermined exposure pattern. Electroplating is then performed on the surface of the solar cell with the anti-plating mask, thereby forming a metal layer as an electrode on the surface of the solar cell at the pattern gaps. Then, the anti-electroplating mask is removed by washing with NaOH or KOH solution at a temperature of, for example, 40 to 70°C. After that, a PVD welding layer is deposited and sintered to obtain a solar cell module with electrodes.

[0098] Example

[0099] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0100] It should be noted that, unless otherwise specified, "parts" and "%" below refer to quality standards.

[0101] By mixing the components shown in Tables 1 and 2 at their indicated mixing ratios (mass basis), the anti-plating compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were obtained.

[0102] [Table 1]

[0103]

[0104] [Table 2]

[0105]

[0106] Remark:

[0107] *1: (A) Carboxyl-containing resin, such as the acrylic modified resin prepared in Example 1 below, with a solid content of 64% and an acid value of 83 mgKOH / g.

[0108] *2: (B) Photosensitive monomer, MT3501G, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (100% solids), manufactured by Zhangjiagang Dongya Di'ai Chemical Co., Ltd.

[0109] *3: (C) Photopolymerization initiator, EAB, 4,4'-bis(diethylamino)benzophenone, manufactured by BASF, Germany

[0110]

[0111] *4: (C) Photopolymerization initiator, ITX, 2-isopropylthioxanthone, manufactured by Hubei Gurun Technology Co., Ltd.

[0112]

[0113] *5: (C) Photopolymerization initiator, TPO, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by IGM Resins B.V.

[0114]

[0115] *6: (C) Photopolymerization initiator, Omnirad 907 (#907), 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, manufactured by IGM Resins BV.

[0116]

[0117] *7: (C) Photopolymerization initiator, TOE-04-A3, manufactured by Nippon Chemical Industries, Ltd.

[0118]

[0119] *8: Polymerization inhibitor, ANTIGEL-688, tris(N-nitroso-N-phenylhydroxylamine) aluminum salt, manufactured by Tianjin Mosen Technology Co., Ltd.

[0120] *9: Blue pigment, FASTOGEN (registered trademark) FA5380, manufactured by DIC.

[0121] *10: Silicone-based defoamer, KS-66, manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0122] *11: Wetting and dispersing agent, BYK-145, manufactured by BYK-CHEMIE GmbH

[0123] *12: Defoaming and leveling agent, BYK-354, manufactured by BYK-CHEMIE GmbH.

[0124] *13: Melamine, manufactured by Guangzhou Jiachun Electronics Co., Ltd.

[0125] *14: Thickener, AEROSIL#974, fumed silica, manufactured by EPOCH CORPORATION

[0126] *15: Solvent, CA, carbitol acetate, manufactured by Jiangsu Tianyin Chemical Co., Ltd.

[0127] "Unmeasurable": The formation of a "positive trapezoid" (i.e., the cross-section of the cured film forms a positive trapezoid that is narrower at the top and wider at the bottom) indicates insufficient etching and the film cannot be used for electroplating.

[0128] Synthesis example 1

[0129] To 650 parts of diethylene glycol monoethyl ether acetate, 1070 parts of o-cresol phenolic varnish-type epoxy resin (manufactured by DIC Corporation, EPICLONN-695, softening point 95℃, epoxy equivalent 214, average number of functional groups 7.6) (glycidyl group (total aromatic rings): 5.0 mol), 360 parts of acrylic acid (5.0 mol), and 1.5 parts of hydroquinone were added. The mixture was heated to 100℃ and stirred until homogeneous. Next, 4.3 parts of triphenylphosphine were added, and the mixture was heated to 110℃. After reacting for 2 hours, 1.6 parts of triphenylphosphine were added, and the temperature was raised to 120℃ for a further 12 hours of reaction. To the resulting reaction solution, 525 parts of aromatic hydrocarbon (SOLVESSO 150) and 608 parts of tetrahydrophthalic anhydride (4.0 mol) were added, and the mixture was reacted at 110℃ for 4 hours. Further, 142.0 parts (1.0 mol) of glycidyl methacrylate were added to the obtained reaction solution, and the reaction was carried out at 115°C for 4 hours to obtain a solution of epoxy-modified acrylic resin of cresol phenolic varnish type with a solid content of 83 mg KOH / g and a solid content of 64%.

[0130] The anti-electroplation compositions obtained in Examples 1-9 and Comparative Examples 1-5 were evaluated for performance as follows.

[0131] Evaluation methods and benchmarks

[0132] (1) Measurement of film thickness

[0133] The anti-electroplating compositions of the above embodiments and comparative examples were coated onto the entire surface of a solar cell, pre-baked at 80°C for 20 minutes, and then placed at 20°C for 10 minutes. The film thickness was approximately 10 μm. A DI exposure machine (SCREEN Ledia6) was used with a 405 nm light source at 100% output power and 400 mJ / cm². 2 The film was patterned using an exposure level of 1% sodium carbonate aqueous solution at 30°C and developed for 60 seconds at a spray pressure of 2 kg. The film thickness was then measured using an optical microscope, and the measured film thicknesses are recorded in Tables 1 and 2.

[0134] (2) 405nm exposure sensitivity

[0135] After polishing the copper-free substrate with a jet scrubber, washing and drying were performed. The anti-plating compositions described in Tables 1 and 2 were then applied via screen printing and dried in a hot air circulating drying oven at 80°C for 30 minutes. After drying, the substrate was exposed to a step tablet (Kodak No. 2) at a wavelength of 405 nm. The photosensitivity was evaluated by the number of segments remaining on the step tablet after development using a 1 wt% sodium carbonate aqueous solution at 30°C for 60 seconds at a spray pressure of 0.2 MPa.

[0136] (3) Evaluation of resolution

[0137] The anti-electroplating compositions of the above examples and comparative examples were coated onto the entire surface of a solar cell, dried at 80°C for 15 minutes, and cooled to room temperature to form a resin layer with a thickness of 10 μm. For the upper surface (exposed surface) of the dried composition, a DI exposure machine (SCREEN Ledia6) was used, with exposure patterns designed with line / spacing of 10 μm / 10 μm, 20 μm / 20 μm, 30 μm / 30 μm, 40 μm / 40 μm, 50 μm / 50 μm, 60 μm / 60 μm, 70 μm / 70 μm, 80 μm / 80 μm, 90 μm / 90 μm, 100 μm / 100 μm, and 200 μm / 200 μm, using a 405 nm light source with 100% output power and 400 mJ / cm². 2 Exposure was performed using a 1% sodium carbonate aqueous solution at 30°C, and development was carried out for 60 seconds at a spray pressure of 2 kg to obtain the evaluation substrate.

[0138] The opening grooves after development were observed using a microscope, and the width of the grooves was measured as an evaluation of the resolution. The results obtained from the evaluation according to the following criteria are recorded in Table 1 and Table 2, respectively.

[0139] The measured trench width is >30μm×

[0140] The measured trench width was 20–30 μm.

[0141] The measured trench width was <20 μm.

[0142] (4) Evaluation of lateral erosion

[0143] The anti-electroplating compositions of the above embodiments and comparative examples were coated onto the entire surface of a solar cell, pre-baked at 80°C for 20 minutes, and then placed at 20°C for 10 minutes. The film thickness was approximately 10 μm. A DI exposure machine (SCREEN Ledia6) was used with a 405 nm light source at 100% output power and 400 mJ / cm². 2 Pattern exposure was performed using a 1% (w / w) sodium carbonate aqueous solution at 30°C, with development for 60 seconds at a spray pressure of 2 kg. Lateral etching was then measured using an optical microscope, and the results, along with those obtained from evaluation according to the following criteria, are recorded in Tables 1 and 2, respectively.

[0144] Lateral erosion > 2μm ×

[0145] Lateral erosion = 2 μm △

[0146] Lateral erosion < 2 μm ○

[0147] The "unmeasurable" result forming a "positive trapezoid" (i.e., the cross-section of the cured film forms a positive trapezoid that is narrower at the top and wider at the bottom) indicates insufficient etching and renders the film unsuitable for electroplating.

[0148] (5) Evaluation of resistance to copper plating

[0149] The anti-electroplating compositions of the above examples and comparative examples were coated onto the entire surface of a solar cell, dried at 80°C for 20 minutes, and cooled to room temperature to form a resin layer with a thickness of 10 μm. For the upper surface (exposed surface) of the dried composition, a DI exposure machine (SCREEN Ledia6) was used with a 405 nm light source at 100% output power and 400 mJ / cm². 2 The exposure amount was used for pattern exposure, and the substrate was developed for 60 seconds using a 1% sodium carbonate aqueous solution at 30°C and a spray pressure of 2 kg to obtain the evaluation substrate.

[0150] The evaluation substrate obtained above is used in a copper plating process to evaluate its resistance to copper plating.

[0151] In the copper electroplating process, the electroplating solution is prepared as follows: copper sulfate (CuSiO4·5H2O) 200g / L, sulfuric acid (H2SO4) 80g / L, chloride ions (Cl... - 70 mg / L of solvent, 13 ml / L of inhibitor, 30 ml / L of brightener, and 20 ml / L of leveling agent. Electroplating operating conditions: temperature 20–25℃, current density 5 A / dm³. 2 The stirring intensity is strong, and the copper plating thickness is 10μm.

[0152] The evaluation items are: 1) whether there is peeling of the anti-plating composition on the surface of the cell after copper plating, and whether there is short circuit due to crossover of the copper grid lines; 2) after copper plating, a 3M tape stress pull-out test is performed to see if the copper grid lines peel off.

[0153] The evaluation criteria are as follows:

[0154] After copper plating, there was no peeling of the anti-plating composition on the surface of the battery cell, no cross-short circuits of the copper grid lines, and no peeling of the copper grid lines during the 3M tape stress pull-out test.

[0155] After copper plating, there was no peeling of the anti-plating composition on the surface of the battery cell, and no short circuit due to copper grid lines crossing. However, during the 3M tape stress pull-out test, the copper grid lines peeled off.

[0156] After copper plating, the surface of the solar cell may exhibit peeling of the anti-plating composition or short circuits caused by copper grid wire crossings.

[0157] The results of the aforementioned evaluation tests are shown in Tables 1 and 2 above.

[0158] As can be seen from the results in Tables 1 and 2, the anti-plating composition of the present invention has low exposure energy and high photosensitivity. Furthermore, the dry film formed by the anti-plating composition has excellent copper plating resistance, high resolution, and no side etching or plating penetration.

[0159] On the other hand, compared to Example 1, Comparative Example 1, which did not use EAB as a photopolymerization initiator, did not show significant adverse effects on properties such as photosensitivity, resolution, and copper plating resistance. However, in the side etching evaluation, it became a "positive trapezoid" (i.e., the cross-section of the cured film formed a positive trapezoid that was narrower at the top and wider at the bottom), making it impossible to measure. This indicates that insufficient etching occurred, and it cannot be used for electroplating. Compared to Example 1, Comparative Example 2, which did not use ITX as a photopolymerization initiator, did not show significant adverse effects on resolution and side etching evaluation, but its photosensitivity decreased by 2 orders, and its copper plating resistance was poor. Compared to Example 1, Comparative Example 2, which did not use T... Comparative Example 3 (PO) did not show a significant adverse effect on resolution, but its photosensitivity decreased by one order, side etching was severe, and its copper plating resistance deteriorated. Compared to Example 1, Comparative Example 4 (not used) did not show a significant adverse effect on resolution, but its photosensitivity decreased by one order, its side etching was severe, and its copper plating resistance deteriorated. Compared to Example 1, Comparative Example 5 (not using TOE-04-A3) did not show a significant adverse effect on resolution and side etching evaluation, but its photosensitivity decreased significantly (by three orders), and its copper plating resistance deteriorated, which may lead to plating penetration. Overall, while the comparative examples and examples had similar resolutions, the comparative examples exhibited more severe side etching, which may affect the shape of the grid circuit and thus the accuracy of the wire circuit. Furthermore, the other comparative examples (except for Comparative Example 1) had poor copper plating resistance, and the cured film may crack during electroplating, leading to plating penetration. This reduces the electrode quality of the prepared solar cell and affects its lifespan.

[0160] Furthermore, in the photosensitivity evaluation results of Examples 1-9, the wavelength energy of 365 mJ / cm was selected as the highest. 2 The exposure levels and photosensitivity evaluation results were all 0, but at a low wavelength energy of 405 mJ / cm², the results were 0. 2 When exposed to a certain exposure level, superior photosensitivity evaluation results were obtained. This result indicates that the anti-plating composition of the present invention requires low exposure energy and exhibits excellent photosensitivity evaluation at 405 mJ / cm². 2The exposure energy is high, resulting in excellent photosensitivity. Furthermore, the results of Examples 1-9 show that when the proportions of EAB, ITX, TPO, #907, and TOE-04-A3 as photopolymerization initiators satisfy a specific relationship (EAB:ITX:TPO:#907:TOE-04-A3 = 0.75:3:15-25:7.5:0.1-0.5), an anti-plating composition with low exposure energy and high photosensitivity can be obtained. The dry film formed from this composition exhibits excellent copper plating resistance, high resolution, and no side etching or plating penetration.

[0161] These results demonstrate that the anti-electroplating composition of the present invention has low exposure energy and high photosensitivity, making it particularly suitable for use as an ink for electroplating solar cells. Furthermore, the dry film formed therefrom exhibits excellent electroplating resistance, high resolution, and is free from side etching and plating penetration, making it especially suitable for solar cells.

[0162] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0163] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. An anti-electroplating composition, characterized in that, It contains (A) a carboxyl-containing resin, (B) a photosensitive monomer, and (C) a photopolymerization initiator. The photopolymerization initiator (C) comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator shown in formula (1).

2. The anti-electroplating composition according to claim 1, characterized in that, By mass ratio, the proportions of the 4,4'-bis(diethylamino)benzophenone, the 2-isopropylthioxanthone, the 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator in the (C) photopolymerization initiator are 0.5–1:1–5:10–30:5–10:0.05–0.

75.

3. The anti-electroplating composition according to claim 1 or 2, characterized in that, By mass ratio, the proportions of the 4,4'-bis(diethylamino)benzophenone, the 2-isopropylthioxanthone, the 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator in the (C) photopolymerization initiator are 0.6–0.8: 2–4: 12–27: 6–8: 0.08–0.

65.

4. The anti-electroplating composition according to claim 1 or 2, characterized in that, By mass ratio, the proportions of the 4,4'-bis(diethylamino)benzophenone, the 2-isopropylthioxanthone, the 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and the oxime ester-based photopolymerization initiator in the (C) photopolymerization initiator are 0.75:3:15-25:7.5:0.1-0.

5.

5. The anti-electroplating composition according to claim 1 or 2, characterized in that, The amount of (C) photopolymerization initiator is 5 to 60 parts by mass relative to 100 parts by mass of solid components of (A) carboxyl-containing resin.

6. The use of the anti-plating composition according to any one of claims 1 to 5 in the manufacture of electrodes for solar cells.

7. A dry film, characterized in that, It is obtained by coating the anti-electroplating composition according to any one of claims 1 to 5 onto a carrier film and drying it.

8. A cured product, characterized in that, It is obtained by curing the anti-electroplating composition according to any one of claims 1 to 5.

9. A cured product, characterized in that, It is obtained by curing the resin layer of the dry film as described in claim 7.

10. An electrode for a solar cell, characterized in that, The cured product having the characteristics of claim 8 or 9.

Images