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

Abstract

Provided are an anti-plating composition having excellent anti-plating performance and film removal performance, a dry film thereof, a cured product thereof, and an electrode of a solar cell. The electroplating-resistant composition includes (A) a carboxyl-group-containing resin including an acid-modified cresol novolac-type epoxy acrylate resin, (B) a photosensitive monomer, and (C) a photopolymerization initiator including 4, 4 '-difluoro-1, 3, 4-trimethyl-1, 3-pentanediol monoisobutyrate. The preparation method comprises the following steps: adding 2, 4, 4 '-bis (diethylamino) benzophenone, 2-isopropyl thioxanthone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl propane-1-one and 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide into a reaction kettle according to a mass ratio of 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide to obtain a mixture; the invention relates to a preparation method of 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, which comprises the following steps of: mixing 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide and 2-methyl-1-(4-methylthio phenyl)-2-morpholino propane-1-ketone according to a ratio of (1.3-5.0): 1, namely the ratio of the 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide to the 2-methyl-1-(4-methylthio phenyl)-2-morpholino propane-1-ketone is (1.3-5.0): 1.

Description

Technical Field

[0001] This invention relates to an anti-plating composition, specifically to an anti-plating composition for edge-sealing ink used in the manufacture of electrodes for solar cells, as well as 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] Globally, energy and environmental issues are receiving increasing attention, and the utilization of new energy sources such as solar energy is being actively promoted. Solar cells are devices that directly convert light energy into electrical energy through the photoelectric effect or photochemical effect. Currently, crystalline silicon solar cells that operate based on the photovoltaic effect are the mainstream and have been applied in many fields such as transportation, communication, meteorology, satellites, lighting, and power plants.

[0003] Various research and development efforts have been actively undertaken regarding solar cell electrodes, a core component of solar cells, and their manufacturing methods. To further reduce costs and increase efficiency in solar cell production processes, the electroplating method for fabricating metal electrodes has attracted significant attention. This method primarily involves partially or completely replacing expensive silver with lower-cost metals such as copper and nickel. When fabricating electrodes using electroplating, the position and size of the metal electrodes are defined on the surface of the solar cell using a patterned mask, and an anti-plating ink is used to create the mask opening process. Then, an edge-sealing ink is used to seal the ends of the cell, followed by baking to dry the ink, exposure, and development to form the pattern corresponding to the grid line electrodes. After the grid line electrodes are formed by electroplating, an alkaline solution is used to remove the cured anti-plating ink (mask) and the cured edge-sealing ink (end-face cover film). Existing edge-sealing inks used in solar cell manufacturing are prone to plating penetration (electroplating solution seeping in through cracks), indicating that their coating performance and anti-plating properties still need improvement.

[0004] Patent document 1 discloses a method for preparing UV-curable ink based on cycloalkanes. It uses acrylate monomers containing cycloalkanes, other UV-curable monomers, and a photocrosslinking initiator. The resulting ink exhibits rapid UV curing and high transparency. However, it focuses on the ink's curing rate and light transmittance, without addressing the performance requirements of anti-electroplating edge-sealing inks for manufacturing solar cells.

[0005] Patent document 2 discloses a method for manufacturing UV-curable encapsulating ink based on a two-dimensional acrylate monomer containing siloxane side chains. It introduces siloxane chains as side chains into an epoxy monomer, utilizing the epoxy system to improve the adhesion, mechanical properties, and bending resistance of the encapsulating film. It can be used for encapsulation and protection of electronic devices such as solar cells, but the primary focus remains on the ink's curing rate and light transmittance.

[0006] Patent document 3 discloses an ink manufacturing method for patterned photovoltaic backsheets. It uses fluororesin as the main resin and isocyanate end-capping curing agent as raw materials, resulting in ink with stable performance. This ink is primarily used as an encapsulation material layer between the solar backsheet and the solar cell; however, it does not address the performance requirements of anti-electroplation edge-sealing inks used in the manufacture of solar cells.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: CN112457714A

[0010] Patent Document 2: CN113773699A

[0011] Patent Document 3: CN109796806A Summary of the Invention

[0012] The problem the invention aims to solve

[0013] Previously used anti-plating edge-sealing inks for manufacturing solar cell electrodes suffered from insufficient photocurability and thermocurability, as well as low photocuring efficiency, leading to plating seepage during electrode fabrication and resulting in unsatisfactory anti-plating properties. Furthermore, when using alkaline solutions for stripping, if the cured film (covering film) formed by the edge-sealing ink has poor removal properties, prolonged stripping may cause the alkaline solution to corrode the electrode layer. Therefore, there is an urgent need to develop an anti-plating edge-sealing ink that satisfies both anti-plating performance and excellent film removal properties.

[0014] Solution for solving the problem

[0015] The inventors conducted in-depth research and discovered that by using a specific main resin, a specific photopolymerization initiator, and maintaining a specific ratio of photopolymerization initiators, the curing efficiency of the edge-sealing ink can be improved. Even with a short photocuring time, it can be fully cured, resulting in an end-face cover film that is not prone to cracking and exhibits excellent coating and anti-electroplating properties. Furthermore, this end-face cover film is easily removed by washing, demonstrating excellent film removal performance. This led to the completion of this invention.

[0016] That is, the present invention is as follows.

[0017] [1]. 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, wherein the (A) carboxyl-containing resin comprises an acid-modified cresol phenolic varnish-type epoxy acrylate resin, and the (C) photopolymerization initiator comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0018] The mass ratio of 2,4,6-trimethylbenzoyldiphenylphosphine oxide to 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one is 1.3 to 5.0:1.

[0019] [2]. The anti-electroplating composition according to [1] is characterized in that, by mass ratio, the proportions of 4,4'-bis(diethylamino)benzophenone: 2-isopropylthioxanthone: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one: 2,4,6-trimethylbenzoyldiphenylphosphine oxide in the photopolymerization initiator of (C) are 0.25-1:1-4:2-6:7.8-10.

[0020] [3]. The anti-electroplating composition according to [1] or [2] is characterized in that, by mass ratio, the proportions of 4,4'-bis(diethylamino)benzophenone: 2-isopropylthioxanthone: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one: 2,4,6-trimethylbenzoyldiphenylphosphine oxide in the (C) photopolymerization initiator are 0.25-1:1-4:2-6:9.

[0021] [4]. The anti-plating composition according to [1] or [2] is characterized in that the amount of the photopolymerization initiator (C) is 10 to 25 parts by weight relative to 100 parts by weight of the carboxyl-containing resin (A) based on solid content.

[0022] [5]. The anti-plating composition according to any one of [1] to [4] is used as an anti-plating edge-sealing ink in the manufacture of electrodes for solar cells.

[0023] [6]. The present invention also provides a dry film, characterized in that it is obtained by coating an anti-electroplating composition as described in any one of [1] to [4] onto a carrier film and drying it.

[0024] [7]. Furthermore, the present invention also provides a cured product, characterized in that it is obtained by curing the anti-electroplating composition described in any one of [1] to [4].

[0025] [8]. Furthermore, the present invention also provides a cured material, characterized in that it is obtained by curing the resin layer of the dry film described in [6].

[0026] [9]. Furthermore, the present invention also provides an electrode for a solar cell, characterized in that it has the cured material described in [7] or [8].

[0027] The effects of the invention

[0028] According to the present invention, an anti-plating composition possessing both excellent anti-plating properties and film removal properties, as well as its dry film, cured product, and electrodes for solar cells using the same, can be provided. This anti-plating composition is particularly suitable for use as an anti-plating edge-binding ink in the manufacture of electrode sheets for solar cells. Detailed Implementation

[0029] 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.

[0030] 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.

[0031] 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.

[0032] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] This invention relates to an anti-electroplating composition, characterized in that it comprises (A) a carboxyl-containing resin, (B) a photosensitive monomer, and (C) a photopolymerization initiator, wherein the (A) carboxyl-containing resin comprises an acid-modified cresol phenolic varnish-type epoxy acrylate resin, and the (C) photopolymerization initiator comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0037] The mass ratio of 2,4,6-trimethylbenzoyldiphenylphosphine oxide to 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one is 1.3 to 5.0:1.

[0038] The components of the anti-electroplation composition of the present invention will be described in detail below.

[0039] (A) Carboxyl-containing resin

[0040] The anti-electroplating composition of the present invention contains (A) a carboxyl-containing resin having multiple carboxyl groups within its molecule. From the viewpoint of alkaline development and film removal performance, the acid value of (A) a carboxyl-containing resin is preferably 5 to 100 mg KOH / g, more preferably 10 to 95 mg KOH / g, and even more preferably 20 to 90 mg KOH / g.

[0041] From the perspective of improving photocuring efficiency, (A) the carboxyl-containing resin is preferably a resin having multiple (meth)acryloyl groups in the molecule, which is polymerized and / or cross-linked by means of the olefinic unsaturated double bond of the (meth)acryloyl group and cured when exposed to light.

[0042] Therefore, in order to achieve the objective of this invention, namely, to improve the efficiency of photocuring while making film removal easier, (A) a carboxyl-containing resin contains an acid-modified cresol phenolic varnish-type epoxy acrylate resin (sometimes simply referred to as "acid-modified cresol phenolic resin" in this invention) as an essential component. Alternatively, without affecting the objective of this invention, (A) a carboxyl-containing resin other than the acid-modified cresol phenolic varnish-type epoxy acrylate resin may be optionally included.

[0043] Through in-depth research, the inventors of this invention discovered that when other carboxyl-containing resins (A), including, for example, acid-modified phenolic varnish-type epoxy acrylate resins with similar structures and good chemical resistance, corrosion resistance, and heat resistance, are used instead of acid-modified cresolic varnish-type epoxy acrylate resins, the electroplating resistance and film removal performance of the formed cured film are reduced. Although the detailed mechanism is not yet clear, it is speculated that this may be due to the more tightly crosslinked structure of the acid-modified cresolic varnish-type epoxy acrylate resin.

[0044] Acid-modified cresol phenolic varnish-type epoxy acrylate resins are typically 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.

[0045] As a multifunctional epoxy resin used to synthesize acid-modified cresol varnish-type epoxy acrylate resin, from the viewpoint of maximizing the effects of the present invention, it must correspondingly contain at least a cresol varnish-type epoxy resin. Based on this, without affecting the effects of the present invention, other multifunctional epoxy resins besides the cresol varnish-type epoxy resin may be optionally included. Other multifunctional epoxy resins may include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenolic varnish type epoxy resin, bisphenolic varnish type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic varnish type epoxy resin, triphenylmethane type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phosphorus-containing epoxy resin, anthracene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, aminophenol type epoxy resin, carbamophenol type epoxy resin, alkylphenol type epoxy resin, etc. Without affecting the purpose of this invention, other multifunctional epoxy resins besides these cresol varnish-type epoxy resins may be optionally omitted, used alone, or used in appropriate combinations of two or more.

[0046] Examples of dicarboxylic anhydrides used in the synthesis of acid-modified cresol phenolic varnish-type epoxy acrylate resins include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. These dicarboxylic 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.

[0047] That is, from the viewpoint of further enhancing the effects of the present invention, it is further preferred to react a cresol phenolic varnish-type epoxy resin with (meth)acrylic acid to add tetrahydrophthalic anhydride to the hydroxyl groups present in the side chain to form an epoxy-modified acrylic resin; especially from the viewpoint of film removal performance, it is particularly preferred to react a cresol phenolic varnish-type epoxy resin with acrylic acid to add tetrahydrophthalic anhydride to the hydroxyl groups present in the side chain to form an epoxy-modified acrylic resin.

[0048] As for (A) carboxyl-containing resins other than acid-modified cresol phenolic varnish-type epoxy acrylate resins, both commercially available and synthetic products can be used. Specific examples of synthetic products include the following compounds:

[0049] (1) A carboxyl-containing resin is formed by reacting a multifunctional epoxy resin other than cresol phenolic varnish epoxy resin with an unsaturated monocarboxylic acid such as (meth)acrylic acid to add saturated or unsaturated polycarboxylic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the hydroxyl groups present on the side chain.

[0050] (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.

[0051] (3) A carboxyl-containing resin formed by further adding (meth)acrylate, α-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexyl methyl methacrylate, etc., to the carboxyl-containing resin described in (1) or (2) above.

[0052] The weight-average molecular weight of the acid-modified cresol phenolic varnish-type epoxy acrylate resin, which is an essential component of (A) carboxyl-containing resin, is generally preferably 2,000 to 150,000, more preferably 3,000 to 30,000, further preferably 4,000 to 15,000, and most preferably 6,000 to 10,000. When the weight-average molecular weight is 2,000 or higher, the resolution is good. On the other hand, when the weight-average molecular weight is 150,000 or lower, the developability is good.

[0053] Relative to the total mass of the anti-plating composition based on solid components, the amount of carboxyl resin in (A) is preferably 50 to 90% by mass, more preferably 60 to 80% by mass. When the amount of carboxyl resin in (A) is within the above range, the anti-plating composition has moderate viscosity, can improve coatability, and has good anti-plating performance.

[0054] (B) Photosensitive monomers

[0055] The (B) photosensitive monomer contained in the anti-plating composition of the present invention refers to a compound having multiple vinyl unsaturated groups in its molecule. This (B) photosensitive monomer undergoes photocuring upon 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 anti-plating composition of the present invention in alkaline aqueous solutions. Preferably, the (B) photosensitive monomer is a compound having multiple (meth)acryloyl groups in its molecule.

[0056] 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, tripentaerythritol, and trihydroxyethyl isocyanurate, or their ethylene oxide adducts or propylene oxide adducts; polyacrylates of phenoxy acrylates, 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.

[0057] 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 carboxyl-containing resins mentioned in (A) above); 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).

[0058] These (B) photosensitive monomers can be used alone or in mixtures of two or more.

[0059] From the viewpoint of maximizing the effects of the present invention, (B) the photosensitive monomer is preferably a monomer with two or more functional groups. That is, from the viewpoint of improving anti-plating properties and film removal properties, (B) the photosensitive monomer is preferably a compound having two or more (meth)acryloyl groups in its molecule. More preferably, it is a compound having 3 to 8 (meth)acryloyl groups in its molecule, and even more preferably, it is a compound having 5 to 6 (meth)acryloyl groups in its molecule. For example, (meth)acrylates having multiple (meth)acryloyl groups in their molecules can be listed as obtained by reacting pentaerythritol, dipentaerythritol, and / or tripentaerythritol with (meth)acrylic acid.

[0060] The amount of photosensitive monomer (B) is preferably 12 to 35 parts by mass, more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total mass of carboxyl-containing resin (A) based on solid components. By including photosensitive monomer (B) in this amount, the anti-plating composition can possess superior anti-plating properties and film removal properties.

[0061] If the amount of photosensitive monomer (B) exceeds 35 parts by mass, the content of carboxyl-containing resin (A) will be relatively low, resulting in reduced photocurability and developability during exposure, making it difficult to obtain satisfactory electroplating resistance. If the aforementioned amount is less than 12 parts by mass, it will be difficult to improve photocurability, difficult to form patterns through alkaline development after irradiation with active energy rays, and poor resistance to copper plating. From the viewpoint of further enhancing the effects of the present invention, 15 to 30 parts by mass is more preferable.

[0062] (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 weight-average molecular weight is 200 or higher, the resolution is good. On the other hand, when the weight-average molecular weight is 3000 or lower, the developability is good.

[0063] Commercially available (B) photosensitive monomers include, for example, MT3501A and MT3501G (manufactured by Zhangjiagang Dongya Di'ai Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate).

[0064] (C) Photopolymerization initiator

[0065] The (C) photopolymerization initiator in the anti-electroplating composition of the present invention comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide as essential components. Through in-depth research, the inventors of the present invention have discovered that by simultaneously using the above-mentioned specific (C) photopolymerization initiator, and ensuring that the ratio of 2,4,6-trimethylbenzoyldiphenylphosphine oxide to 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one is within a specific range, the cured film obtained by the anti-electroplating composition of the present invention exhibits excellent copper plating resistance and film removal properties at various exposure intensities; that is, it possesses excellent coating properties and is more easily removed by alkaline washing.

[0066] By using the four specific photopolymerization initiators described above 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, thereby preventing plating seepage during electroplating and exhibiting excellent anti-plating performance, while also possessing excellent film removal performance. Surprisingly, as shown in the embodiments and comparative examples of the present invention, if one or more of the photopolymerization initiators are replaced with other photopolymerization initiators of the same type, both the anti-plating performance and the film removal performance will be affected.

[0067] From the viewpoint of maximizing the effects of the present invention, the mixing ratio of 2,4,6-trimethylbenzoyldiphenylphosphine oxide to 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, i.e., 2,4,6-trimethylbenzoyldiphenylphosphine oxide : 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, should be in the range of 1.3 to 5.0:1 by mass. Furthermore, the ratio of 4,4'-bis(diethylamino)benzophenone : 2-isopropylthioxanthone : 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one : 2,4,6-trimethylbenzoyldiphenylphosphine oxide, should be in the range of 0.25 to 1:1 to 4:2 to 6:7.8 to 10 by mass, more preferably in the range of 0.25 to 1:1 to 4:2 to 6:9. When these specific photopolymerization initiators are combined in the above proportions, it can be ensured that the anti-electroplating composition of the present invention still forms a cured film that meets the requirements of the present invention even under shorter exposure times or lower exposure intensities.

[0068] Furthermore, without affecting the purpose of this invention, the anti-electroplating composition of this invention may further contain other photopolymerization initiators besides the specific photopolymerization initiator described above. Examples of other photopolymerization initiators include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc., which are diacyl groups. Phosphine oxides; monoacyl phosphine oxides such as 2,6-dimethoxybenzoyl diphenylphosphine oxide, 2,6-dichlorobenzoyl diphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphine phosphate, 2-methylbenzoyl diphenylphosphine oxide, and isopropyl neopentanoylphenylphosphine phosphate; hydroxyl-containing phosphine oxides such as 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1-one. Acetophenones; benzoin, benzoyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michlechne, methylbenzophenone, 4,4'-dichlorobenzophenone, etc.; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1 -[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and other acetophenone derivatives; thioxanone, 2-ethylthioxanone, 2,4-dimethylthioxanone, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-diisopropylthioxanone and other thioxanone derivatives; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone and other anthraquinone derivatives; acetophenone dimethyl ketal, benzoyl dimethyl ketal and other ketals; ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, p-dimethylbenzoate and other benzoate esters;Oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-acetone 1-(O-acetyl oxime); titanium compounds such as bis(n5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrolo-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butylin, anisolein ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. Without affecting the effectiveness of the present invention, these other photopolymerization initiators may be optionally omitted, used alone, or in combination of two or more. ;

[0069] The total amount of photopolymerization initiator (C) is preferably 5 to 30 parts by weight relative to 100 parts by weight of carboxyl-containing resin (A) based on solids, more preferably 8 to 25 parts by weight, and even more preferably 10 to 25 parts by weight. If the amount of photopolymerization initiator used is less than the range described above, the photocurability of the composition tends to deteriorate; on the other hand, if the amount is excessive, the properties as an anti-electroplating composition may be reduced, and therefore this is not preferred.

[0070] Other ingredients

[0071] 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.

[0072] The anti-plating composition of the present invention may contain a (D) colorant, and commonly used organic colorants may be used. It should be noted that the (D) colorant contained in the anti-plating composition of the present invention preferably does not include substances that are inorganic fillers.

[0073] As coloring agents for (D), examples 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.

[0074] This type of (D) colorant can be used alone or in a mixture of two or more. Commercially available (D) colorants include FASTOGEN BLUE FA5380 blue pigment manufactured by DIC Corporation and 7007-UV(YST) (registered trademark) LP-81(HA)-1 green pigment manufactured by Indco Pigment Technology Co., Ltd.

[0075] Furthermore, the anti-electroplation composition of the present invention may also contain (E) an organic solvent, which is used in the preparation of the composition and viscosity adjustment.

[0076] As (E) organic solvents, examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, there are 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.

[0077] This type of (E) organic solvent can be used alone or in mixtures of two or more. Commercially available (E) organic solvents include carbitol acetate (CA), manufactured by Jiangsu Tianyin Chemical Co., Ltd., etc.

[0078] In addition, the anti-electroplation composition of the present invention may also be formulated with, as needed, heat-inhibiting polymerization agents, 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.

[0079] 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.

[0080] Commercially available examples of other components in the anti-electroplating composition of the present invention include, for example, the silicone defoamer KS-66 manufactured by Shin-Etsu Chemical Industry Co., Ltd., the dispersant BYK-145 manufactured by BYK-CHEMIE GmbH, and the fumed silica AEROSIL#974 manufactured by EPOCHCORPORATION as a thickener.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] For example, the anti-plating composition of the present invention can be adjusted to a viscosity suitable for the 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 the carrier film can be peeled off, thereby forming a layer formed by the anti-plating composition on the surface of the solar cell. Then, the surface is selectively exposed to active energy rays through a photomask with a predetermined exposure pattern, and 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. Next, coating is applied to the edge region of the solar cell, i.e., the end face, or it can be wrapped with an edge-sealing adhesive to form an edge-sealing film (or the entire surface and end face of the solar cell can be initially coated, and the coating film is formed after simultaneous heating and drying with the surface). Then, the surface of the solar cell with the anti-plating mask and the edge area of ​​the solar cell with the edge coating are exposed and electroplated to form a metal layer as an electrode on the surface of the solar cell at the pattern notch. Then, the anti-plating mask and the edge coating are removed by washing with NaOH or KOH solution at a temperature of, for example, 40 to 70°C. Then, a solder layer is deposited by PVD, and after sintering, a solar cell module with electrodes is obtained.

[0087] Example

[0088] 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.

[0089] It should be noted that, unless otherwise specified, "parts" and "%" below refer to quality standards.

[0090] 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 11 were obtained.

[0091] Table 1

[0092]

[0093] Table 2

[0094]

[0095] Note: "-" indicates that TPO / 907 cannot be retrieved because the Omnirad 907 usage is 0.

[0096] *1(A) Acid-modified cresol phenolic resin, prepared as in Synthesis Example 1 below, with a solid content of 64% by mass and an acid value of 84.2 mg KOH / g.

[0097] *2 (Comparative Example) Acid-modified copolymer resin, the acid-modified acrylic copolymer resin prepared in Synthesis Example 2 below, has a solid content of 54% by mass and an acid value of 109 mg KOH / g.

[0098] *3 (Comparative Example) Acid-modified phenolic resin: The acid-modified phenolic resin prepared in Synthesis Example 3 below has a solid content of 64% by mass and an acid value of 58 mg KOH / g.

[0099] *4(B) Photosensitive monomer, MT3501G, manufactured by Zhangjiagang Dongya Di'ai Chemical Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (100% solids).

[0100] *5(D) Blue Pigment, FASTOGEN BLUE FA5380, manufactured by DIC Corporation.

[0101] *6 Silicone-based defoamer, KS-66, manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0102] *7 Dispersant, BYK-145, manufactured by BYK-CHEMIE GmbH

[0103] *8 Thixotropic agent, composed of 50% RHEOBYK-R 606 (thixotropic agent, manufactured by BYK Chemical) and 50% dipropylene glycol methyl ether (DPM).

[0104] *9 Melamine, manufactured by Guangzhou Jiachun Electronics Co., Ltd.

[0105] *10(C) Photopolymerization initiator, EAB, 4,4'-bis(diethylamino)benzophenone, manufactured by BASF, Germany.

[0106]

[0107] *11 (Comparative Example) Photopolymerization initiator, EDB, ethyl 4-dimethylaminobenzoate, manufactured by BASF, Germany

[0108] *12(C) Photopolymerization initiator, ITX, 4-isopropylthioxanthone, manufactured by Hubei Gurun Technology Co., Ltd.

[0109]

[0110] *13(C) Photopolymerization initiator, Omnirad 907, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, manufactured by IGM RESINS BV.

[0111]

[0112] *14 (Comparative Example) Photopolymerization initiator, Omnirad 369, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, manufactured by IGM Resins BV.

[0113] *15(C) Photopolymerization initiator, TPO, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF, Germany.

[0114]

[0115] *16 Thickener, Fumed Silica, AEROSIL #974, manufactured by EPOCH CORPORATION

[0116] *17(E) Solvent, Carbitol Acetate (CA), manufactured by Jiangsu Tianyin Chemical Co., Ltd.

[0117] Synthesis example 1

[0118] 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 acid-modified cresol phenolic varnish-type epoxy acrylate resin with a solid content of 84.2 mg KOH / g and a solid content of 64% by mass.

[0119] Synthesis example 2

[0120] In a 2-liter detachable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet, 900 g of diethylene glycol dimethyl ether as solvent and 21.4 g of tert-butyl peroxide-2-ethylhexanoate (PERBUTYL O, manufactured by Nippon Yushi Co., Ltd.) as polymerization initiator were added, and the mixture was heated to 90°C. After addition, the mixture was allowed to mature for 3 hours. Then, along with 21.4 g of peroxydicarbonate-bis(4-tert-butylcyclohexyl) peroxide (PEROYL TCP, manufactured by Nippon Yushi Co., Ltd.) as polymerization initiator, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (PLACCEL FM1, manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.) were added dropwise, and the mixture was allowed to mature for another 6 hours to obtain a carboxyl-containing copolymer resin. The reaction was carried out under a nitrogen atmosphere.

[0121] Next, 363.9 g of 3,4-epoxycyclohexyl methacrylate (DAICEL CHEMICAL INDUSTRIES, LTD., producing Cyclomer A200), 3.6 g of dimethyl benzylamine as a ring-opening catalyst, and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were added to the obtained carboxyl-containing copolymer resin. The mixture was heated to 100°C and stirred to carry out the ring-opening addition reaction of the epoxy. After 16 hours, a solution of an acid-modified copolymer resin without aromatic rings was obtained, containing 54% by mass (solids) of the resin. The solids component of this resin had an acid value of 109 mg KOH / g and a weight-average molecular weight of 25,000.

[0122] Synthesis example 3

[0123] To 650 parts of diethylene glycol monoethyl ether acetate, 950 parts of phenolic varnish-type epoxy resin (manufactured by DIC Corporation, EPICLONN-770, softening point 65-75℃, epoxy equivalent 190) (glycidyl base (total aromatic rings): 5.0 mol), 360 parts (5.0 mol) of acrylic acid, and 1.5 parts of hydroquinone were added. The mixture was heated to 100℃ and stirred until uniformly dissolved. 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 (4.0 mol) of tetrahydrophthalic anhydride were added, and the reaction was carried out at 110℃ for 4 hours. Furthermore, 770 parts (5.4 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 acid-modified phenolic varnish-type epoxy acrylate resin with a solid content of 58 mg KOH / g and a solid content of 64% by mass.

[0124] The anti-electroplation compositions obtained in Examples 1-9 and Comparative Examples 1-11 were evaluated for performance as follows.

[0125] Evaluation methods and benchmarks

[0126] (1) Copper plating resistance (coating performance)

[0127] The anti-electroplating compositions of the above examples and comparative examples were coated onto the end face of a solar cell, dried at 80°C for 20 minutes, and then placed at 20°C for 10 minutes 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 optimal exposure was used for pattern exposure, and development was performed for 60 seconds using a 1% (w / w) sodium carbonate aqueous solution at 30°C and a spray pressure of 2 kg to obtain the evaluation substrate. Alternatively, under the same conditions, only the exposure was changed to 200 mJ / cm². 2 A slightly lower exposure than the optimal exposure (hereinafter referred to as "slightly lower exposure"), and simply changing the exposure to 600mJ / cm 2 Pattern exposure was performed at an exposure level slightly higher than the optimal exposure level (hereinafter referred to as "slightly higher exposure level"). After development for 60 seconds using a 1% sodium carbonate aqueous solution at 30°C and a spray pressure of 2kg, evaluation substrates corresponding to slightly lower and slightly higher exposure levels were obtained.

[0128] The evaluation substrate obtained above was used in a copper plating process to evaluate its resistance to copper plating.

[0129] In the copper electroplating process, the electroplating solution is prepared as follows: copper sulfate (CuSO4·5H2O) 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 5-50μm.

[0130] The evaluation criteria are: whether the anti-plating composition peels off from the end face of the battery cell after copper plating, or whether copper is electroplated onto the end face.

[0131] The evaluation criteria are as follows:

[0132] After copper plating, there was no peeling of the anti-plating composition on the surface of the battery cell, and the end faces were not electroplated with copper.

[0133] After copper plating, there are very few areas on the surface of the battery cell where the anti-plating composition peels off, or very few areas on the end face where copper is electroplated.

[0134] After copper plating, the surface of the battery cell exhibits peeling of the anti-plating composition, or there are copper-plated marks on the end faces.

[0135] (2) Coating removal performance (film removal ability)

[0136] The coating removal performance of the evaluation substrates obtained in (1) above is evaluated according to the following conditions.

[0137] A 5% (w / w) sodium hydroxide solution was kept at 60°C for 5 minutes.

[0138] The evaluation criteria are as follows:

[0139] After soaking in the stripping solution, there was no residue left on the substrate surface.

[0140] After soaking in the wash solution, there was slight residue, but no residue remained after rinsing with water. △

[0141] After soaking in the wash remover, residue remains, and residue is still present after rinsing with water. ×

[0142] The results of the aforementioned evaluation tests are shown in Tables 1 and 2 above.

[0143] As can be seen from Tables 1 and 2, under the same conditions, the only difference between Example 1 and Comparative Examples 1 and 2 is that the acid-modified copolymer resin and acid-modified phenolic resin were replaced with acid-modified cresolic resin. Example 1 showed excellent film removal ability and copper plating resistance at all exposure levels. In contrast, Comparative Examples 1 and 2 showed poorer film removal ability at the optimal exposure level and at slightly higher exposure levels, as well as poorer copper plating resistance at slightly lower exposure levels.

[0144] Compared with Comparative Examples 3, 4, 5, 9, and 10, Example 1 differs in that Comparative Examples 3, 4, 5, and 10 respectively only omits the use of EAB, ITX, Omnirad 907, or TPO as (C) photopolymerization initiators, while Comparative Example 9 omits Omnirad 907 and reduces the amount of TPO. Example 1 exhibits excellent film removal ability and copper plating resistance at all exposure levels. In contrast, Comparative Examples 3, 4, 5, 9, and 10 show deterioration in copper plating resistance at the optimal exposure level, at slightly lower exposure levels, and in film removal performance at slightly higher exposure levels.

[0145] The only difference between Example 1 and Comparative Examples 6 and 11 is that TPO / 907 in Comparative Examples 6 and 11 is outside the scope of this invention. Example 1 exhibits excellent film removal ability and copper plating resistance at all exposure levels. In contrast, Comparative Examples 6 and 11 show deterioration in copper plating resistance at the optimal exposure level, at slightly lower exposure levels, and in film removal performance at slightly higher exposure levels.

[0146] Compared to Comparative Example 7, Example 1 differs only in that Comparative Example 7 uses Omnirad 369 instead of Omnirad 907. Compared to Comparative Example 8, Example 1 differs only in that EDB is used instead of EAB. Example 1 exhibits excellent film removal ability and copper plating resistance at all exposure levels. In contrast, Comparative Examples 7 and 8 show deterioration in copper plating resistance at the optimal exposure level, at slightly lower exposure levels, and in film removal performance at slightly higher exposure levels.

[0147] As can be seen from Examples 1 to 9, in this invention, by simultaneously using specific photopolymerization initiators such as EAB, ITX, Omnirad 907, and TPO, and keeping the ratio of TPO to Omnirad 907 within a specific range, the cured films obtained under various exposure intensities all exhibit excellent resistance to copper plating and film removal performance, that is, they possess excellent coating performance and are easier to remove by alkaline washing.

[0148] These results demonstrate that the anti-electroplation composition of the present invention exhibits excellent resistance to copper plating and excellent film removal properties, making it particularly suitable for use as an edge-sealing ink for solar cell electroplating.

[0149] 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.

[0150] 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, A plating resist composition comprising (A) a carboxyl group-containing resin, (B) a photosensitive monomer, and (C) a photopolymerization initiator, wherein the (A) carboxyl group-containing resin comprises an acid-modified cresol novolak-type epoxy acrylate resin, the (C) photopolymerization initiator comprises 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, The complex ratio of 2,4,6-trimethylbenzoyldiphenylphosphine oxide to 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, i.e., 2,4,6-trimethylbenzoyldiphenylphosphine oxide:2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, is 1.3 to 5.0:1 in terms of mass ratio.

2. The anti-electroplating composition of claim 1, wherein, The complex ratio of 4,4'-bis(diethylamino)benzophenone:2-isopropylthioxanthone:2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one:2,4,6-trimethylbenzoyldiphenylphosphine oxide in the (C) photopolymerization initiator is 0.25 to 1:1 to 4:2 to 6:7.8 to 10 in terms of mass ratio.

3. The anti-electroplating composition according to claim 1 or 2, characterized in that, The complex ratio of 4,4'-bis(diethylamino)benzophenone:2-isopropylthioxanthone:2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one:2,4,6-trimethylbenzoyldiphenylphosphine oxide in the (C) photopolymerization initiator is 0.25 to 1:1 to 4:2 to 6:9 in terms of mass ratio.

4. The anti-electroplating composition according to claim 1 or 2, characterized in that, The complex amount of the (C) photopolymerization initiator is 10 to 25 parts by weight with respect to 100 parts by weight of the (A) carboxyl group-containing resin in terms of solid content.

5. The plating resist composition according to any one of claims 1 to 4 for use as a plating resist ink in manufacturing an electrode of a solar cell.

6. A dry film characterized by, It is obtained by coating the plating resist composition according to any one of claims 1 to 4 on a support film and drying.

7. A cured product, characterized by, It is obtained by curing the plating resist composition according to any one of claims 1 to 4.

8. A cured product, characterized by, It is obtained by curing the resin layer of the dry film according to claim 6.

9. An electrode for a solar cell, characterized by, It has the cured product according to claim 7 or 8.

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