TWI838715B - Photosensitive resin composition with improved system color stability, photosensitive resin laminate containing the same and use thereof - Google Patents

Abstract

The present invention discloses a photosensitive resin composition with improved system hue stability, comprising the following components: (A) a 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator, the structure of which is shown in formula (I), wherein the sum of the contents of the compound of formula (II) having a 1-4' connecting position and the compound of formula (III) having a 1-5' connecting position accounts for less than 3% of the mixed photoinitiator; (B) an alkali-soluble polymer; (C) a compound having an olefinic unsaturated double bond; (D) a hydrogen donor; and (E) other optional additives. The photosensitive resin composition and its dry film of the present invention have excellent resolution and color stability, and there is no tendency of resolution reduction after long-term storage at -20-40°C. It has a wide range of applications in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc.

Description

Photosensitive resin composition with improved system color stability, photosensitive resin layer stack containing the same and its use

The present invention belongs to the field of photocuring technology, and specifically relates to a photosensitive resin composition with improved system hue stability and its application.

In recent years, with the miniaturization of printed circuit boards used in precision electronic devices such as personal computers, photosensitive resin compositions with high sensitivity, high resolution and resolution have become a hot topic of research. As one of the essential components in photosensitive resin compositions, photoinitiators are required to have excellent properties such as high initiation efficiency, good compatibility with the system and excellent solubility. Hexaarylbiimidazole (HABI) compounds have a special chemical structure and can photolyze to produce macromolecular free radicals under the action of ultraviolet light. They are a very important type of photoinitiator in the field of photocuring, especially in the field of free radical polymerization.

Among HABI photoinitiators, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (BCIM) is the most widely used. BCIM has multiple isomers at the connecting position, and the BCIM currently available on the market is basically a mixture of multiple isomers at the connecting position. The applications of BCIM in photosensitive resin compositions reported so far have not made further requirements on the composition and content of internal isomers, but simply directly applied the BCIM mixture to the composition. However, on the one hand, the application performance of BCIM produced by different manufacturers in the market varies greatly, which brings great confusion to downstream manufacturers; on the other hand, the photosensitive resin composition containing existing BCIM products and its dry film have low color stability and abnormal color development when stored for a long time, which can easily lead to defective products. This is a difficult problem that needs to be solved urgently.

The applicant's R&D team found in the process of studying 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole that the BCIM isomers and contents at different connection positions have a significant effect on the performance of the photosensitive resin composition and its dry film. Therefore, exploring the effect of the structure and content of the isomers on the performance of the BCIM mixed photoinitiator is an effective means to further improve the practical application performance of BCIM.

In response to the needs of existing technology development, the main purpose of the present invention is to provide a photosensitive resin composition with improved system hue stability. The composition and its dry film have excellent resolution and hue stability, and there is no tendency of resolution reduction after long-term storage at -20-40°C.

In order to achieve the above purpose, the specific technical solutions adopted are as follows.

A photosensitive resin composition with improved system color stability comprises the following components: (A) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator, the structure of which is shown in formula (I),

Wherein, the sum of the contents of the compound of formula (II) having a 1-4' linking position and the compound of formula (III) having a 1-5' linking position accounts for less than 3% of the mixed photoinitiator,

(B) Alkali soluble polymers;

(C) Compounds having olefinic unsaturated double bonds;

(D) Hydrogen donor;

(E) Optionally, other additives.

Another object of the present invention is to provide the application of the above-mentioned photosensitive resin composition and its dry film in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc.

Based on the purpose of the present invention, the photosensitive resin composition of the present invention and various aspects of its application are described in more detail below.

<Photosensitive resin composition>

2,2’-Bis(o-chlorophenyl)-4,4’,5,5’-tetraphenylbiimidazole mixed photoinitiator (A)

The 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator of the present invention has a structure as shown in formula (I),

Wherein, the sum of the contents of the compound of formula (II) having a 1-4' linking position and the compound of formula (III) having a 1-5' linking position accounts for less than 3% of the mixed photoinitiator,

Unless otherwise stated, the percentages mentioned here refer to mass percentages.

Furthermore, the sum of the contents of the two compounds of formula (II) and (III) accounts for less than 1% of the mixed photoinitiator.

In the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention, the compound of formula (IV) having a 1-2' connection position and the compound of formula (V) having a 2'-3 connection position are the main components, and the sum of the contents of the two compounds accounts for more than 96% of the mixed photoinitiator.

In addition to the above-mentioned four compounds of formula (II), (III), (IV), and (V), optionally, the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator (BCIM) of the present invention may also contain a small amount of isomers of the connection positions such as 3-4', 3-5', 1-1', 1-3', and 3-3'.

The 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention has no special restrictions on the ratio between the compound of formula (II) and the compound of formula (III), and there is no special restrictions on the ratio between the compound of formula (IV) and the compound of formula (V). As long as the sum of the contents of the two meets the above requirements, the purpose of the present invention can be achieved. In this article, the component content in the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator is detected by high performance liquid chromatography.

BCIM is a type of photoinitiator known in the field of photoresist, which can be prepared by oxidative coupling of substituted triphenylimidazole compounds. The oxidants used in the preparation can be, for example, sodium hypochlorite, potassium ferric cyanide, etc. The phase transfer catalysts used can be, for example, tetrabutylammonium bromide, benzyltriethylammonium chloride, crown ethers (15-crown-5, 18-crown-6), polyethylene glycol, etc. The specific preparation process can refer to the records in the prior art such as US3784557, US4622286 and US4311783 (the full text of which is hereby introduced as a reference). In the BCIM obtained by the existing preparation process, the sum of the contents of the above-mentioned two compounds of formula (II) and (III) accounts for a relatively high content of the BCIM mixed photoinitiator.

Based on the existing process, the present invention conducts solvent slurrying and recrystallization process on the product to conveniently obtain the BCIM mixed photoinitiator that meets the composition requirements of the present invention. The solvent can be one or a combination of two or more of toluene, benzene, methanol, ethanol, ethyl acetate, dichloromethane, and water.

In 100 parts by weight of the photosensitive resin composition, the content of the BCIM mixed photoinitiator is preferably 1-10 parts by weight. Within this content range, the BCIM mixed photoinitiator can bring better hue stability while showing excellent photosensitivity and resolution.

Alkaline soluble polymer (B)

Alkali-soluble polymers can impart film-forming properties to photosensitive resin compositions. As alkali-soluble polymers, any polymer having such properties can be used without particular limitation.

For example, the applicable alkali-soluble polymer may be (meth) acrylic polymer, styrene polymer, epoxy polymer, aliphatic polyurethane (meth) acrylate polymer, aromatic polyurethane (meth) acrylate polymer, amide resin, amide epoxy resin, alkyd resin, phenolic resin, etc.

Furthermore, the alkali-soluble polymer can be obtained by free radical polymerization of polymerizable monomers. Examples of polymerizable monomers include: polymerizable styrene derivatives substituted at the α-position or on the aromatic ring, such as styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; alkyl(meth)acrylates, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, and (meth)acrylic acid. (Meth)acrylate compounds such as dimethylaminoethyl ester, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propionic acid, N-vinylcaprolactam; N-vinylpyrrolidone, etc. These polymerizable monomers can be used alone or in combination of two or more.

Furthermore, from the perspective of alkali developing property and adhesion, it is preferable to use an alkali-soluble polymer containing a carboxyl group. The alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth)acrylic acid as a monomer unit, wherein the carboxyl group is introduced by using (meth)acrylic acid as a monomer unit; it may be a copolymer containing (meth)acrylic acid alkyl ester as a monomer unit in addition to (meth)acrylic acid; it may also be a copolymer containing a polymerizable monomer other than (meth)acrylic acid and (meth)acrylic acid alkyl ester (such as a monomer having an ethylenic unsaturated group) as a monomer component in addition to (meth)acrylic acid.

Furthermore, the carboxyl-containing alkali-soluble polymer can be obtained by free radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers, in particular, a (meth)acrylate polymer obtained by copolymerization of (meth)acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers.

The (meth)acrylate can be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)acrylate, glycidyl (meth)acrylate, etc. These (meth)acrylates can be used alone or in combination of two or more.

The ethylenically unsaturated carboxylic acid can be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and acrylic acid and methacrylic acid are particularly preferred. These ethylenically unsaturated carboxylic acids can be used alone or in combination of two or more.

The other copolymerizable monomers mentioned above may be (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinylnaphthalene, (meth)acrylonitrile, vinyl acetate, vinylcyclohexane, etc. These other copolymerizable monomers may be used alone or in combination of two or more.

Alkali-soluble polymers can be used alone or in combination of two or more. Examples of alkali-soluble polymers used in combination of two or more include two or more alkali-soluble polymers composed of different copolymer components, two or more alkali-soluble polymers with different weight average molecular weights, and two or more alkali-soluble polymers with different dispersities.

In the photosensitive resin composition of the present invention, there is no particular restriction on the weight average molecular weight of the alkali-soluble polymer, which should be adapted to the specific application environment. Considering the mechanical strength and alkali developability, the weight average molecular weight is preferably 15,000-200,000, more preferably 30,000-150,000, and particularly preferably 30,000-120,000. When the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved. When the weight average molecular weight is less than 200,000, the developing time tends to be shorter, and the compatibility with other components such as the photoinitiator can be maintained. The weight average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC) and converted using a standard curve of standard polystyrene.

Furthermore, from the perspective of good alkali development, the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, further preferably 70-250 mgKOH/g, and particularly preferably 100-250 mgKOH/g. When the acid value of the alkali-soluble resin is lower than 50 mgKOH/g, it is difficult to ensure a sufficient development speed. When it exceeds 300 mgKOH/g, the adhesion is reduced, the pattern is prone to short circuit, and the storage stability of the composition is reduced and the viscosity is increased.

The molecular weight distribution of the alkali-soluble resin [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.5-6.0, and particularly preferably 1.8-3.7. When the molecular weight distribution is within the above range, the developing property is excellent.

In 100 parts by mass of the photosensitive resin composition, the content of the alkali-soluble polymer in the composition is preferably 20-70 parts by mass, and more preferably 30-60 parts by mass. When the content of the alkali-soluble polymer is above 20 parts by mass, it can ensure that the durability of the photosensitive resin composition for plating treatment, etching treatment, etc. is improved. When the content is below 70 parts by mass, it is beneficial to improve the sensitivity of the photosensitive resin composition.

Compounds with olefinic unsaturated double bonds (C)

Compounds with olefinic unsaturated double bonds can promote the film formation of photosensitive resin compositions.

The compound having an ethylenically unsaturated double bond is not particularly limited, and any photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule may be used. For example, the following can be cited: compounds obtained by reacting α,β-unsaturated carboxylic acid with polyols, bisphenol A (meth)acrylate compounds, compounds obtained by reacting α,β-unsaturated carboxylic acid with glycidyl-containing compounds, carbamate monomers such as (meth)acrylate compounds having carbamate bonds in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, (meth)acrylate alkyl esters, etc. These compounds can be used alone or in combination of two or more.

Examples of the compound obtained by reacting the α,β-unsaturated carboxylic acid with a polyol include polyethylene glycol di(meth)acrylate having 2-14 ethylene groups, polypropylene glycol di(meth)acrylate having 2-14 propylene groups, and polyethylene having 2-14 ethylene groups and 2-14 propylene groups. Polypropylene glycol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, EO-modified trihydroxymethylpropane tri(meth)acrylate, PO-modified trihydroxymethylpropane tri(meth)acrylate, EO,PO-modified trihydroxymethylpropane tri(meth)acrylate, tetrahydroxymethylmethane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. These compounds may be used alone or in combination of two or more. Here, "EO" means ethylene oxide, and the EO-modified compound refers to a compound having a block structure of ethylene oxide groups. "PO" stands for propylene oxide, and a PO-modified compound refers to a compound having a block structure of propylene oxide groups.

Examples of the bisphenol A-based (meth)acrylate compound include 2,2-bis{4-[(meth)acryloxypolyethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxypolypropoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxypolybutoxy]phenyl}propane, and 2,2-bis{4-[(meth)acryloxypolyethoxypolypropoxy]phenyl}propane. Examples of the 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane include 2,2-bis{4-[(meth)acryloyloxydiethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytriethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetraethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypentaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyheptaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyoctaethoxy]phenyl}propane, alkane, 2,2-bis{4-[(meth)acryloyloxynonaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyundecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydodecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytridecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetradecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypentadecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexadecethoxy]phenyl}propane and the like. The number of oxyethylene groups in one molecule of the above-mentioned 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane is preferably 4-20, more preferably 8-15. These compounds can be used alone or in combination of two or more.

Examples of the (meth)acrylate compound having an urethane bond in the above-mentioned molecule include: addition reaction products of a (meth)acrylic monomer having an OH group at the β position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.), tris[(meth)acryloyloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO,PO modified urethane di(meth)acrylate, etc. These compounds may be used alone or in combination of two or more.

Examples of the nonylphenoxy polyvinyloxy acrylate include nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy hexavinyloxy acrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxy decavinyloxy acrylate, and nonylphenoxy undecvinyloxy acrylate. These compounds may be used alone or in combination of two or more.

Examples of the above-mentioned phthalic acid compounds include: γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl phthalate, etc. These compounds can be used alone or in combination of two or more.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and tert-butyl (meth)acrylate. 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, amyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, propylene glycol polypropylene ether di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethoxylated polytetrahydrofurandiol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, etc. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethoxylated trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexaacrylate are preferred. These compounds can be used alone or in combination of two or more.

From the perspective of improving resolution, coating resistance, and adhesion, the compound having an ethylenically unsaturated double bond is preferably a bisphenol A (meth)acrylate compound and a (meth)acrylate compound having an urethane bond in the molecule. From the perspective of improving sensitivity and resolution, a bisphenol A (meth)acrylate compound is preferred. As commercially available products of bisphenol A-based (meth)acrylate compounds, there are, for example, 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-200), 2,2-bis{4-[(meth)acryloyloxypolypropoxy]phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-5000; manufactured by Hitachi Chemical Co., Ltd., FA-321M), 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-1300), etc.

In 100 parts by mass of the photosensitive resin composition, the content of the compound (C) having an olefinic unsaturated double bond is preferably 20-50 parts by mass, more preferably 25-45 parts by mass. When the content of the compound having an olefinic unsaturated double bond is above 20 parts by mass, the sensitivity and resolution of the photosensitive resin composition will be further improved; when its content is below 50 parts by mass, the photosensitive resin composition is easier to form into a thin film, and the durability to etching treatment is further improved.

Hydrogen donor (D)

The photosensitive resin composition of the present invention also includes a hydrogen donor to improve the photosensitivity. After being irradiated with light, the biimidazole compound is cleaved to produce a monoimidazole free radical with a large volume. The steric hindrance effect makes the activity small, and it is difficult to initiate monomer polymerization alone. However, if used in combination with a hydrogen donor, the monoimidazole free radical can easily take the active hydrogen on the hydrogen donor to generate new active free radicals, thereby initiating monomer polymerization.

As long as the hydrogen donor has the above characteristics, there is no special restriction on the specific type, which may include (but not limited to): amine compounds, carboxylic acid compounds, organic sulfur compounds containing hydroxyl groups or alcohol compounds, etc. These compounds can be used alone or in combination of two or more thereof.

There is no special restriction on amine compounds, and they may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

There is no particular limitation on carboxylic acid compounds, and they may include (but are not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

There is no particular limitation on the organic sulfur compound containing alkyl groups, and the organic sulfur compound may include (but is not limited to): 2-alkylbenzothiazole (MBO), 2-alkylbenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-alkylbutyrate), 1,2-propylene glycol bis(3-alkylbutyrate), diethylene glycol bis(3-alkylbutyrate), butanediol bis(3-alkylbutyrate), octanediol bis(3-alkylbutyrate), trihydroxymethylpropane tris(3-alkylbutyrate), pentaerythritol tetra(3-alkylbutyrate), dipentaerythritol hexa(3-alkylbutyrate), ethylene glycol bis(2-alkylpropionate), propylene glycol bis(2-alkylpropionate), diethylene glycol bis(2-alkylpropionate), Ester), butanediol di(2-butyl propionate), octanediol di(2-butyl propionate), trihydroxymethylpropane tri(2-butyl propionate), pentaerythritol tetra(3-butyl propionate), dipentaerythritol hexa(2-butyl propionate), ethylene glycol di(3-butyl isobutyrate), 1,2-propylene glycol di(3-butyl isobutyrate), Diethylene glycol di(3-butylene isobutyrate), butanediol di(3-butylene isobutyrate), octanediol di(3-butylene isobutyrate), trihydroxymethylpropane tri(3-butylene isobutyrate), pentaerythritol tetra(3-butylene isobutyrate), dipentaerythritol hexa(3-butylene isobutyrate), ethylene glycol di(2-butylene isobutyrate), 1, 2-Propanediol di(2-butyl isobutyrate), diethylene glycol di(2-butyl isobutyrate), butanediol di(2-butyl isobutyrate), octanediol di(2-butyl isobutyrate), trihydroxymethylpropane tri(2-butyl isobutyrate), pentaerythritol tetra(2-butyl isobutyrate), dipentaerythritol hexa(2-butyl isobutyrate) , ethylene glycol di(4-benzene valerate), 1,2-propylene glycol di(4-benzene isovalerate), diethylene glycol di(4-benzene valerate), butanediol di(4-benzene valerate), octanediol di(4-benzene valerate), trihydroxymethylpropane tri(4-benzene valerate), pentaerythritol tetra(4-benzene valerate), dipentaerythritol tetra(4-benzene valerate) Aliphatic secondary multifunctional thiol compounds such as ethylene glycol hexa(4-butyl valerate), ethylene glycol di(3-butyl valerate), 1,2-propylene glycol di(3-butyl valerate), diethylene glycol di(3-butyl valerate), butanediol di(3-butyl valerate), octanediol di(3-butyl valerate), trihydroxymethylpropane tri(3-butyl valerate), pentaerythritol tetra(3-butyl valerate), dipentaerythritol hexa(3-butyl valerate); aromatic secondary multifunctional thiol compounds such as di(1-butyl ethyl ester), di(2-butyl propyl ester), di(3-butyl butyl ester), di(3-butyl isobutyl ester), etc.

There is no special restriction on alcohol compounds, and they may include (but are not limited to): methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, 1,2-propylene glycol, 1,2,3-propylene triol, benzyl alcohol, phenylethyl alcohol, etc.

In 100 parts by weight of the photosensitive resin composition, the content of the hydrogen donor (D) can be 0.01-20 parts by weight, preferably 0.01-10 parts by weight. When the content of the hydrogen donor is within the above range, it is beneficial to adjust the sensitivity of the photosensitive resin composition.

Other optional additives (E)

In addition to the above components, the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other additives as needed. For example, the additives may include at least one of other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating aids, and stripping accelerators.

The other photoinitiators and/or sensitizers may include (but are not limited to): bisimidazoles, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, triazines, coumarins, thioxanthines, acridines and other photoinitiators known to those skilled in the art.

Exemplarily, the biimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2',5-tri(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, 2,2',5-tri(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-biimidazole, 2,2'-bis(2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-diimidazole, -bis(2-chloro-5-nitrophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5-(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5' -bis(o-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-bis(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole and their analogs. These bisimidazole compounds can be used alone or in combination of two or more.

Exemplarily, the aromatic ketone compounds include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyl diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino) diphenyl Benzophenone, 4-p-tolylbenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethylamino)benzophenone, acetophenone dimethyl ketal, benzoyl dimethyl ketal, α,α'-dimethylbenzoyl ketal, α,α'-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylbenzophenone , 2-Hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, 2-methyl 1-(4-methylphenyl)-2-pyroline 1-acetone, 2-benzyl-2-dimethylamino-1-(4-pyrolinephenyl) 1-butanone, phenylbis(2,4,6-trimethylbenzyl)phosphine oxide, 2,4,6(trimethylbenzyl)diphenylphosphine oxide, 2-Hydroxy-1-{3-[4-(2-hydroxy-2-methyl-propionyl )-phenyl]-1,1,3-trimethyl-inden-5-yl}-2-methylpropanone, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-inden-5-yl}-2-methylpropanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone and the like. These aromatic ketone compounds can be used alone or in combination of two or more.

Illustratively, anthraquinone compounds include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-di(4-chlorobutyric acid methyl ester), 2-{3-[(3-ethyloxycyclobutane-3-yl)methoxy]-3-oxopropyl}anthracene-9,10-diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-di(3-chloropropoxy)anthracene, 9,10-di(2-hydroxyethinyl)anthracene, 9,10-di(3-hydroxy-1-propinyl)anthracene, and the like. These anthraquinone compounds can be used alone or in combination of two or more.

Exemplarily, benzoin and benzoin alkyl ether compounds include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like. These benzoin and benzoin alkyl ether compounds can be used alone or in combination of two or more.

Exemplarily, the oxime ester compound may include: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-ethane-1-one-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-butane-1-one-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-propane-1-one-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-1-cyclohexane 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3-cyclopentyl)-propane-1-one-acetic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3-cyclopentyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(6- 1-(4-Benzyldiphenylsulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-(2-methylbenzyl)-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(4-Benzyldiphenylsulfide)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-(2-methylbenzyl)-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 2-o-Methylbenzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-(4-thienyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-acetic acid oxime ester, 1-(4-benzoyl diphenyl sulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazole-3-yl)-3-cyclohexyl-propane-1-one-acetic acid oxime ester, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-3-cyclohexyl- Propane-1-one-acetic acid oxime ester, 1-(6-thienyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanofuryl-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-acetic acid oxime ester, 1-(6-furfuryl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester 、1-(6-furanofurylcarbonyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime acetate、1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-3-benzoic acid oxime ester、1-(6-thienylcarbonyl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester、2-[(benzoyloxy)imino]-1-phenylpropane-1-one、1-phenyl-1,2-propanedione-2-(oxoacetyl)oxime、1-(4-phenylthiophenyl)-2-(2-methylphenyl) -ethane-1,2-dione-2-acetic acid oxime, 1-(9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane-1-one-acetic acid oxime, 1-{4-[4-(thiophene-2-carbonyl)phenylthio]phenyl}-3-cyclopentylpropane-1,2-dione-2-acetic acid oxime, 1-[9,9-dibutyl-2-yl]-3-cyclohexylpropylpropane-1,2-dione-2-acetic acid oxime, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl]octane-1,2-dione-2-benzoic acid oxime Ester, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-3-cyclopentyl-propane-1-one-benzoic acid oxime ester, 1-[7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-acetic acid oxime ester, 1-[6-(furan-2-carbonyl)-9-ethylcarbazole-3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxycarbonyl oxime ester and the like. These oxime ester compounds can be used alone or in combination of two or more.

Exemplarily, the triazine compounds include: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methyleneoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propanoate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 2-ethoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, Hexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxyphenylvinyl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxyphenylvinyl-s-triazine and the like. These triazine compounds can be used alone or in combination of two or more.

Exemplarily, coumarin compounds include: 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3-benzoyl-7-methoxycoumarin and the like. These coumarin compounds can be used alone or in combination of two or more.

Exemplarily, the thiothione compounds include: thiothione, 2,4-dimethylthiothione, 2,4-diethylthiothione, 2,4-diisopropylthiothione, 2-chlorothiothione, 1-chloro-4-propoxythiothione, isopropylthiothione, diisopropylthiothione and the like. These thiothione compounds can be used alone or in combination of two or more.

Exemplarily, acridine compounds include: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluorophenylacridine, 1,7-di(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane and the like. These acridine compounds can be used alone or in combination of two or more.

The organic solvent can be any solvent as long as it can dissolve the aforementioned components. For example, it can be a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, a chlorine-containing solvent, etc. It is preferably selected by taking into account the solubility, coating properties, safety, etc. of the colorant and alkali-soluble polymer. Preferably, the organic solvent can be ethyl solvent (ethylene glycol monoethyl ether), methyl solvent (ethylene glycol monomethyl ether), butyl solvent (ethylene glycol monobutyl ether), methyl methoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid solvent (ethylene glycol monomethyl ether acetate), acetic acid Methoxybutyl ester (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5,5-trimethyl-2-cyclohexene-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactamide or NMP), methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, etc. These solvents can be used alone or in combination of two or more thereof.

For example, dyes, pigments and photochromic agents include: tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, alkane dyes, toluenesulfonic acid monohydrate, alkali fuchsin, phthalocyanine green and phthalocyanine blue and other phthalocyanine series, auramine, para-fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, adamantium green, alkali blue 20, brilliant green, eosin, ethyl violet, erythromycin sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinadin red, rose red sodium agar, Mittanil yellow, thyme ... Phenolsulfonphthalein, xylenol blue, methyl orange, orange IV, diphenylcarbazone, 2,7-dichlorofluorescein, panmethyl red, Congo red, Benzyl red 4B, α-naphthyl red, phenacetin, methyl violet, Victoria blue BOH, rhodamine 6G, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-aminodiamine, p-toluidine, benzotriazole, methyl benzotriazole, 4,4'-diamine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl violet, azo series and other organic pigments, and titanium dioxide and other inorganic pigments. In consideration of good contrast, tris (4-dimethylaminophenyl) methane (i.e., hidden crystal violet, LCV) is preferably used. These dyes, pigments and photochromic agents can be used alone or in combination of two or more.

For example, fillers include: silicon dioxide, aluminum oxide, talc, calcium carbonate, barium sulfate and other fillers (excluding the above-mentioned inorganic pigments). Fillers can be used alone or in combination of two or more.

Exemplarily, the plasticizer includes: phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate, glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, and n-butylbenzenesulfonamide, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tritolyl phosphate, trixyl phosphate, methyl phosphate, trimethylol ... Phenyl diphenyl phosphate, trixyl phosphate, 2-naphthyl diphenyl phosphate, tolyl di-2,6-xyl phosphate, aromatic condensation phosphate, tris(chloropropyl) phosphate, tris(tribromoneopentyl) phosphate, halogen-containing condensation phosphate, triethylene glycol dioctanoate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate _, tris(2-ethylethyl) phosphate, Brij30[ _{C12H25 ( OCH2CH2} ) _4OH ], and Brij35[ _C12H25 ( _OCH2CH2 ) _20OH ] _, etc. The plasticizer may be used alone or in combination _of two or more.

For example, the stabilizer includes: hydroquinone, 1,4,4-trimethyl-diazobicyclo (3.2.2)-non-2-ene-2,3-dioxide, 1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinone and quinone, tert-butyl o-catechol, 1,2,3-pyrogallol, copper resinate, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloranil, etc. The stabilizer can be used alone or in combination of two or more.

Exemplarily, coating aids include: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, γ-butyrolactone, dichloromethane, etc. Coating aids can be used alone or in combination of two or more.

Exemplarily, the stripping accelerator includes: benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl and other alkylbenzenesulfonic acids, etc. The stripping accelerator can be used alone or in combination of two or more.

In 100 parts by mass of the photosensitive resin composition, the content of the other additives is 0-10 parts by mass, preferably 0.5-5 parts by mass.

<Dry film and wet film applications>

From the perspective of ensuring that the photosensitive resin composition and its dry film have excellent resolution and color stability, the storage temperature of the photosensitive resin composition of the present invention is preferably between -20°C and 40°C.

The photosensitive resin composition of the present invention can be prepared into a dry film, i.e. a photosensitive resin layer stack, and applied in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages, and the required patterns are formed on different substrates through different processes.

The photosensitive resin composition of the present invention can also be applied to the corresponding substrate in each corresponding manufacturing step by a wet film coating machine, that is, it can be used as a wet film in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages, and the required patterns can be formed on different substrates through different processes.

Dry film application

The dry film of the present invention is a photosensitive resin layer stack, which includes: a photosensitive resin layer formed by a photosensitive resin composition and a support body supporting the photosensitive resin layer.

Generally, the preparation of dry film includes: applying a photosensitive resin composition on a support, drying to form a photosensitive resin layer; optionally, laminating a cover film (protective layer) as needed. Preferably, the drying condition is 60-100°C for 0.5-15min. The thickness of the photosensitive resin layer is preferably 5-95μm, more preferably 10-50μm, and more preferably 15-30μm. If the thickness of the photosensitive resin layer is less than 5μm, the insulation is poor, and if the thickness of the photosensitive resin layer exceeds 95μm, the resolution may be poor.

As a support, specific examples can be various types of plastic films, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polyalkyl methacrylate, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, ethylene chloride-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene and the like. In addition, a composite material composed of two or more materials can also be used. Preferably, polyethylene terephthalate with excellent light transmittance is used. The thickness of the support is preferably 5-150μm, more preferably 10-50μm.

There is no particular limitation on the coating of the photosensitive resin composition. For example, conventional methods such as spray coating, drum coating, rotary coating, slit coating, compression coating, curtain coating, dye coating, line coating, blade coating, roller coating, scraper coating, spray coating, and dipping coating can be used.

Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:

(1) Lamination process: stacking the photosensitive resin layer on the copper-clad laminate or flexible substrate;

(2) Exposure process: exposing the photosensitive resin layer in the photosensitive resin layer stack, irradiating the active light in an image-like manner to photo-cure the exposed part;

(3) Development process: remove the unexposed part of the photosensitive resin layer with a developer to form a protective pattern;

(4) Conductor pattern forming process: etching or plating the portion of the copper-clad laminate or flexible substrate surface not covered by the protective pattern;

(5) Peeling process: peeling the protective pattern from the copper-clad laminate or flexible substrate.

Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of protective patterns, including the lamination process, exposure process and development process as described above, the difference being that in the lamination process, the photosensitive resin layer stack can be laminated on substrates of various materials.

Furthermore, the present invention provides the application of the above dry film in manufacturing a conductor pattern, including the lamination process, exposure process, development process and conductor pattern forming process as described above, except that: in the lamination process, the photosensitive resin layer is laminated on a metal plate or a metal-coated insulating plate.

Furthermore, the present invention provides the application of the above dry film in manufacturing lead frame wires, including the above-mentioned lamination process, exposure process, development process, and conductor pattern forming process, except that: In the lamination process, the photosensitive resin layer is laminated on the metal plate, and in the conductor pattern forming process, the portion not covered by the protective pattern is etched.

Furthermore, the present invention provides the application of the above dry film in the manufacture of semiconductor packaging, including the above-mentioned lamination process, exposure process, development process, and conductor pattern forming process, the difference being that: in the lamination process, the photosensitive resin layer is laminated on a chip with a large-scale integrated circuit, and in the conductor pattern forming process, the portion not covered by the protective pattern is coated.

Wet film applications

The photosensitive resin composition of the present invention can be directly coated on a substrate in a wet film manner for use in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, etc.

Without limitation, the photosensitive resin composition can be applied to the substrate by conventional methods such as roller coating, scraper coating, spray coating, and dip coating, and a photosensitive resin layer is formed after drying.

After forming a photosensitive resin layer on the substrate, subsequent processes such as exposure process, development process, conductor pattern formation process and stripping process can be carried out in the same way as dry film application.

In the exposure process, the exposure may be performed by a mask exposure method (a method in which a negative or positive mask pattern of a wiring pattern is irradiated with active light in an image-like manner), a projection exposure method, or a method in which active light is irradiated in an image-like manner by a direct drawing exposure method such as a laser direct imaging exposure method or a digital optical processing exposure method. As a light source for active light, a known light source may be used, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure indicator lamp, a high pressure indicator lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser, and a gallium nitride-based blue-violet laser, etc., which effectively radiates ultraviolet light. In addition, a light source that effectively radiates visible light such as a floodlight for photography and a fluorescent lamp may be used. The photosensitive resin composition of the present invention has no particular limitation on the type of active light source, and the exposure amount is preferably 10-1000 mJ/cm ² .

In the developing process, the unexposed part of the photosensitive resin layer is removed with a developer. If there is a support on the photosensitive resin layer, the support can be removed first by using an automatic stripper, and then an alkaline aqueous solution, an aqueous developer, an organic solvent or other developer can be used to remove the unexposed part. Examples of alkaline aqueous solutions can be 0.1-5 mass% sodium carbonate solution, 0.1-5 mass% potassium carbonate solution, 0.1-5 mass% sodium hydroxide solution, etc., and the pH value is preferably 9-11. Surfactants, defoaming agents, organic solvents, etc. can also be added to the alkaline aqueous solution. The developing method can be conventional methods such as immersion, spraying, and brushing.

In the etching process, the conductive layer of the circuit forming substrate that is not covered is etched away using the anti-etching pattern (i.e., protective pattern) formed on the substrate as a mask, thereby forming a conductive pattern. The etching process method can be selected according to the conductive layer to be removed. For example, as etching solutions, copper oxide solutions, iron oxide solutions, alkaline etching solutions, hydrogen peroxide etching solutions, etc. can be listed.

In the plating process, copper, solder, etc. are plated on the insulating plate of the circuit forming substrate which is not covered, using the anti-etching pattern formed on the substrate as a mask. After the plating process, the anti-etching pattern is removed to form a conductor pattern. The plating process can be either electroplating or electroless plating, and electroless plating is preferred. As electroless plating treatment, there can be listed: copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as Watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, gold plating such as hard gold plating and soft gold plating.

The removal of the anti-corrosion pattern can be performed by using an aqueous solution with a stronger alkalinity than the alkaline aqueous solution used in the development process. As an example of a strongly alkaline aqueous solution, a 1-10 mass% sodium hydroxide aqueous solution can be used.

Figure 1 is a high performance liquid chromatogram of product a1.

Figure 2 is the HPLC chromatogram of product a2.

Figure 3 is the single crystal diffraction pattern of BCIM at the 1-2’ position.

Figure 4 is the single crystal diffraction pattern of 2’-3 BCIM.

Figure 5 is the single crystal diffraction pattern of BCIM at the 1-5’ position.

Figure 6 is the single crystal diffraction pattern of BCIM at the 1-4’ position.

Figure 7 is the XRD analysis spectrum of 1-2’ BCIM.

Figure 8 is the XRD analysis spectrum of 2’-3 BCIM.

Figure 9 is the XRD analysis spectrum of product a2.

The present invention will be further described in detail below in conjunction with specific embodiments, but they should not be construed as limiting the scope of protection of the present invention.

1. Preparation of BCIM Mixed Photoinitiator

1.1 Preparation of BCIM mixed photoinitiators a1 and a2

Under nitrogen protection, 976g of 2-(o-chlorophenyl)-4,5-diphenylimidazole (INC), 20g of 30% liquid alkali, 10g of tetrabutylammonium bromide and 6000g of toluene were added to a 10L reactor, heated and stirred, and 500g of sodium hypochlorite (11% aqueous solution) was added dropwise at an internal temperature of 60°C. After the addition was completed, the reaction was kept warm, and a sample was taken for central control by HPLC until INC was less than 1%, indicating that the reaction was complete, and the insulation was terminated. After the insulation reaction was completed, the mixture was washed four times with 1000g of pure water, and then the aqueous layer was extracted once with 1000g of toluene. The organic layer was distilled under reduced pressure until the solvent was completely evaporated, 1000g of methanol was added, and the mixture was stirred, filtered, rinsed, and dried to obtain 933g of product a1. Product a1 was detected using a high performance liquid chromatograph. Figure 1 is a high performance liquid chromatogram of product a1, showing that BCIM at positions 1-2' and 2'-3 accounted for 95.61% of product a1, BCIM at positions 1-4' and 1-5' accounted for 1.69%, and BCIM at other connecting positions accounted for 0.97%.

Under nitrogen protection, 500g of product a1 and 3000g of toluene were added to a 5000mL four-necked flask, heated and stirred at an internal temperature of 60°C until dissolved, then distilled under reduced pressure until about 800g of toluene remained, cooled to 25°C, filtered, rinsed, and dried to obtain 432g of product a2. Product a2 was detected using a high performance liquid chromatograph. Figure 2 is a high performance liquid chromatogram of product a2, showing that 1-2' BCIM and 2'-3 BCIM accounted for 99.55% of product a2, and 1-4' BCIM and 1-5' BCIM accounted for 0.33%.

1.2 Separation and characterization of components of BCIM mixed photoinitiator

Here, we first explain the mechanism of BCIM reaction generation: the nitrogen atom in the triarylimidazole molecule loses the H atom and becomes negatively charged. The presence of the o-chlorophenyl group makes the 2-position C in the triarylimidazole more active. The charge effect makes the 2-position C atom positively charged, so the negatively charged N atom attacks the positively charged C atom, and finally the electron is transferred to generate BCIM. The specific reaction mechanism process is as follows:

According to the reaction mechanism of BCIM, BCIM should be a biimidazole compound composed of four connecting positions: 1-2', 1'-2, 2-3' and 2'-3. Since INC is a symmetrical structure, 1-2' and 1'-2 are the same structure, and 2-3' and 2'-3 are the same structure. Therefore, BCIM should be a biimidazole compound composed of two connecting positions: 1-2' and 2'-3. Its components are: 1-2' BCIM: 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole; 2'-3 BCIM: 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole. The structures are shown in formulas (Ⅳ) and (Ⅴ).

Although the presence of o-chlorophenyl makes the 2-position C in triarylimidazole more active, similarly, the charge effect can also make the 4-position C and 5-position C atoms positively charged, generating 1-5' BCIM and 1-4' BCIM.

The specific reaction mechanism of 1-5' BCIM is as follows:

The specific reaction mechanism of 1-4' BCIM is as follows:

In order to accurately verify the structural composition of the product, pure 1-2' BCIM, 2'-3 BCIM, 1-4' BCIM, and 1-5' BCIM were obtained by existing known technical means such as column analysis, chromatographic separation, and single crystal separation. Figure 3 is a single crystal diffraction pattern of 1-2' BCIM, Figure 4 is a single crystal diffraction pattern of 2'-3 BCIM, Figure 5 is a single crystal diffraction pattern of 1-5' BCIM, and Figure 6 is a single crystal diffraction pattern of 1-4' BCIM.

In order to more vividly characterize 1-2' BCIM and 2'-3 BCIM, powder XRD analysis was performed on 1-2' BCIM, 2'-3 BCIM and product a2. Figure 7 is the XRD analysis spectrum of 1-2' BCIM, Figure 8 is the XRD analysis spectrum of 2'-3 BCIM, and Figure 9 is the XRD analysis spectrum of product a2. It can be seen from Figures 7-9 that product a2 is mainly composed of a mixture of 1-2' BCIM and 2'-3 BCIM, and the content of 1-2' BCIM is higher than that of 2'-3 BCIM. The content of BCIM at other connection positions is very small, so there is no obvious diffraction peak in the XRD spectrum.

1.3 Sensitivity test

Referring to the formula shown in Table 1, a photosensitive resin composition was prepared for sensitivity testing. The unit of dosage of each substance in the table is g.

Table 1

In Table 1 above, dipentaerythritol hexaacrylate (DPHA) was purchased from Tianjin Beilian Fine Chemicals Development Co., Ltd., hidden crystal violet (LCV) was purchased from Changzhou Qiangli Electronic New Materials Co., Ltd., N-phenylglycine (NPG) was purchased from Shenzhen Pengshunxing Technology Co., Ltd., and propylene glycol methyl ether acetate (PGMEA) was purchased from Jinan Huifengda Chemical Co., Ltd.

一

社制，商品名EXM-1201)，以60mJ/cm²的照射能量曝光感光層。曝光後，以30℃的1質量%碳酸鈉水溶液用最少顯影時間的2倍的時間噴射顯影，除去未曝光部分，進行顯影。然後，通過測定形成的光固化膜的階段曝光尺的格數，來評價感光性樹脂組合物的光敏度。光敏度用階段曝光尺的格數表示，該階段曝光尺的格數越高，表示光敏度高，結果如表2所示。 The photosensitive resin composition was stirred thoroughly and evenly applied on the surface of a 25 μm thick polyethylene terephthalate film as a support using a rod coater. The film was dried in an oven at 95°C for 5 minutes to form a photosensitive resin layer. The film was exposed using a Stouffer 21-step exposure ruler and an exposure machine with a high-pressure mercury lamp (

one

The photosensitive layer was exposed to 60 mJ/ ^cm2 of irradiation energy using a 1 mass% sodium carbonate aqueous solution at 30°C for twice the minimum development time. The unexposed portion was removed and developed. Then, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of grids of the stage exposure scale of the photocured film formed. The photosensitivity is expressed by the number of grids of the stage exposure scale. The higher the number of grids of the stage exposure scale, the higher the photosensitivity. The results are shown in Table 2.

Table 2

The sensitivity of product a2 is consistent with that of 1-2' BCIM and 2'-3 BCIM, and that of 1-4' BCIM and 1-5' BCIM. However, 1-4' BCIM and 1-5' BCIM have higher steric hindrance than 1-2' BCIM and 2'-3 BCIM, and the energy required for cleavage is lower than that of 1-2' BCIM and 2'-3 BCIM, so they show higher sensitivity. However, since the energy required for cleavage is lower, they show poor stability.

1.4 Preparation of BCIM mixed photoinitiators a3-a11

a3: The separated 1-2' BCIM single crystal;

a4: The separated 2’-3 BCIM single crystal;

a5: Through compounding, a mixture of 50% 1-2' BCIM and 50% 2'-3 BCIM is obtained;

a6: Through compounding, a mixture of 49% 1-2' BCIM, 50% 2'-3' BCIM, 0.5% 1-4' BCIM, and 0.5% 1-5' BCIM is obtained;

a7: Through compounding, a mixture of 47% 1-2' BCIM, 50% 2'-3' BCIM, and 3% 1-4' BCIM is obtained;

a8: Through compounding, a mixture of 47% 1-2' BCIM, 50% 2'-3' BCIM, and 3% 1-5' BCIM is obtained;

a9: Through compounding, a mixture of 48% 1-2' BCIM, 47% 2'-3 BCIM, 2.5% 1-4' BCIM, and 2.5% 1-5' BCIM was obtained;

a10: Through compounding, the components obtained are 48% 1-2' BCIM, 47% 2'-3' BCIM, and 5% 1-4' BCIM;

a11: Through compounding, the components obtained are 48% 1-2' BCIM, 47% 2'-3' BCIM, and 5% 1-5' BCIM.

2. Preparation of photosensitive resin composition

Referring to the formula shown in Table 3, the components are mixed evenly to prepare a photosensitive resin composition. Unless otherwise specified, the parts shown in Table 3 are parts by mass.

table 3

The meaning of each component code in Table 3 is shown in Table 4.

Table 4

Preparation of alkali-soluble polymer B: Under a nitrogen atmosphere, 500 g of a mixed solvent of methylcellulose and toluene (mass ratio 3:2) was added to a flask equipped with a stirrer, a reflux cooler, a thermometer and a dropping funnel. After stirring and heating to 80°C, a solution prepared by mixing 100 g of methacrylic acid, 200 g of ethyl methacrylate, 100 g of ethyl acrylate, 100 g of styrene and 0.8 g of azobisisobutyronitrile was slowly dripped into the flask for 4 hours. After the dripping was completed, the reaction was continued for 2 hours. Then, 100g of a mixed solvent (same composition as above) containing 1.2g of azobisisobutyronitrile was added dropwise into the flask for 10 minutes. After the addition, the mixture was further reacted at 80°C for 3 hours, and then the temperature was raised to 90°C for another 2 hours. After the reaction, alkali-soluble polymer B was obtained by filtration, with an acid value of 196mgKOH/g and a weight-average molecular weight of about 80,000.

3. Performance evaluation

3.1 Evaluation method

<Dry film production>

The photosensitive resin composition was fully stirred and evenly applied on the surface of a 25μm thick polyethylene terephthalate film as a support using a rod coater. It was dried in a dryer at 95°C for 5 minutes to form a 40μm thick photosensitive resin layer. A 15μm thick polyethylene film as a protective layer was then laminated on the surface of the photosensitive resin layer without the polyethylene terephthalate film laminated thereon to obtain a dry film.

<Substrate surface leveling>

As a substrate, a 1.2 mm thick copper-clad laminated with a 35 μm thick rolled copper foil was used, and the surface was wet-polished with a polishing roll [Scotch-Brite (registered trademark) HD#600 manufactured by 3M, passed twice].

<Layer pressure>

The polyethylene film protective layer was peeled off from the dry film and then laminated onto the copper-clad press plate preheated to 60°C at a roll temperature of 105°C using a hot roll laminating press (AL-70 manufactured by Asahi Kasei). The gas pressure was 0.35MPa and the laminating speed was 1.5m/min.

<Exposure>

The mask was placed on a polyethylene terephthalate film as a support, and the photosensitive layer was exposed with an ultra-high pressure mercury lamp (HMW-201KB manufactured by ORC MANUFACTURING CO., LTD.) at an irradiation energy of 60 mJ/ ^cm2 .

<Image>

Peel off the polyethylene terephthalate film, use an alkaline developer (developer for dry films manufactured by Fuji Kiko Co., Ltd.), spray a 1 mass % Na ₂ CO ₃ aqueous solution at 30°C on the photosensitive resin layer, and dissolve and remove the unexposed portion of the photosensitive resin layer for twice the minimum developing time. The shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve is the minimum developing time.

3.2 Evaluation Content

(1) Resolution

The resolution of the dry film is measured after exposure and development using a photomask with a wiring pattern of Line/Space=10:10-150:150 (unit: μm). The resolution is the minimum value of the pattern after the unexposed part of the anti-etching pattern formed by development after exposure is cleared. The evaluation criteria are as follows:

○: Resolution value is below 30μm;

◎: Resolution value is 30μm-50μm, excluding end value;

×: The resolution value is above 50μm.

(2) Maintaining time resolution

The dried film was stored in a dark place at 23°C and 50% humidity for 2 weeks, and then the resolution was evaluated by the same method as the above resolution test.

(3) Hue stability evaluation

The polyethylene film was peeled off from the photosensitive resin laminate, and the transmittance of light with a wavelength of 600 nm was measured using a UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240). At this time, a polyethylene terephthalate film identical to that used in the photosensitive resin laminate was placed on the reference side of the spectrometer, and the transmittance derived from the polyethylene terephthalate film was used as the blank value.

The transmittance of the photosensitive resin layer stack made from the photosensitive resin composition solution stored at -20-40°C for 3 days was compared with that of the photosensitive resin layer stack made from the photosensitive resin composition solution before storage, and the transmittance was graded as follows based on the difference.

○: The absolute value of the difference in transmittance at 600nm is less than 1%;

◎: The absolute value of the difference in transmittance at 600nm is greater than 1% and less than 5%;

×: The absolute value of the difference in transmittance at 600nm is 5% or more.

(4) Evaluation of hue stability before and after exposure

Before the photosensitive resin layer stack made of the photosensitive resin composition solution is exposed, the chromaticity, i.e., L, a, and b values of the photosensitive resin layer stack made of the photosensitive resin composition solution before exposure are tested using the transmission method in an X-Rite (Shanghai Kaide Color Management Co., Ltd.) colorimeter. The photosensitive resin layer stack made of the photosensitive resin composition solution was exposed to 60 mJ/ ^cm2 of irradiation energy. After the exposure, the L, a, b and ΔL, Δa, Δb, ΔE values of the photosensitive resin layer stack made of the photosensitive resin composition solution after the exposure were measured by the colorimeter transmission method, with the chromaticity of the photosensitive resin layer stack made of the photosensitive resin composition solution before exposure as the measurement standard. The values were graded as follows based on their differences.

○: ΔE is less than 5;

◎: ΔE is greater than 5 and less than 10;

×: ΔE is 10 or more.

3.3 Evaluation results

The evaluation results are shown in Table 5.

table 5

The photosensitive resin composition and its dry film of the present invention have excellent resolution and color stability, and there is no tendency of resolution reduction even after long-term storage. The photosensitive resin composition can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc. in the form of dry films and wet films.

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principle of the present invention shall be equivalent replacement methods and shall be included in the protection scope of the present invention.

Claims (10)

A photosensitive resin composition with improved system color stability comprises the following components: (A) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator, the structure of which is shown in formula (I),

The total content of the compound of formula (II) having a 1-4' linking position and the compound of formula (III) having a 1-5' linking position accounts for less than 0.33% of the mixed photoinitiator, and the total content of the compound of formula (IV) having a 1-2' linking position and the compound of formula (V) having a 2'-3 linking position accounts for more than 99.55% of the mixed photoinitiator.

Formula (III)

Wherein, when the mixed photoinitiator of component (A) contains two compounds of formula (IV) and formula (V), the content of the compound of formula (IV) is less than or equal to the content of the compound of formula (V); (B) an alkali-soluble polymer; (C) a compound having an olefinic unsaturated double bond; (D) a hydrogen donor; and (E) optionally, other auxiliary agents. The photosensitive resin composition as described in claim 1, wherein the alkali-soluble polymer is selected from one or a combination of two or more of (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethane (meth)acrylate polymers, amide resins, amide epoxy resins, alkyd resins and phenolic resins. The photosensitive resin composition as described in claim 2, wherein the alkali-soluble polymer is selected from carboxyl-containing alkali-soluble polymers. The photosensitive resin composition as described in claim 3, wherein the alkali-soluble polymer is selected from (meth)acrylate polymers obtained by copolymerization of (meth)acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers. The photosensitive resin composition as described in claim 1, wherein the compound having an olefinic unsaturated double bond is selected from a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, a bisphenol A-type (meth)acrylate compound, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a compound containing a glycidyl group, a (meth)acrylate compound having an urethane bond in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, and a combination of one or more of the following: alkyl (meth)acrylates. The photosensitive resin composition as described in claim 5, wherein the compound having an olefinic unsaturated double bond is selected from one or a combination of two or more of bisphenol A type (meth)acrylate compounds and (meth)acrylate compounds having an urethane bond in the molecule. The photosensitive resin composition as described in claim 1, wherein the hydrogen donor is selected from one or a combination of two or more of amine compounds, carboxylic acid compounds, organic sulfur compounds containing alkyl groups and alcohol compounds. A photosensitive resin composition as described in any one of claims 1 to 7, wherein the storage temperature of the photosensitive resin composition is between -20°C and 40°C. A photosensitive resin layer stack, comprising: a photosensitive resin layer formed by the photosensitive resin composition as described in any one of claims 1 to 8 and a support body supporting the photosensitive resin layer. Application of the photosensitive resin composition as described in any one of claims 1 to 8 and the photosensitive resin layer stack as described in claim 9 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.

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