CN115128899A

CN115128899A - Photosensitive resin composition with improved system hue stability

Info

Publication number: CN115128899A
Application number: CN202110354531.0A
Authority: CN
Inventors: 严春霞
Original assignee: Changzhou Zhengjie Intelligent Manufacturing Technology Co ltd
Current assignee: Changzhou Zhengjie Intelligent Manufacturing Technology Co ltd
Priority date: 2021-03-26
Filing date: 2021-03-26
Publication date: 2022-09-30
Also published as: TW202237670A; WO2022199625A1

Abstract

The invention discloses a photosensitive resin composition with improved system hue stability, which comprises the following components: (A) the structure of the 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole mixed photoinitiator is shown as a formula (I), wherein the sum of the contents of a compound with a 1-4 ' connecting position shown as a formula (II) and a compound with a 1-5 ' connecting position shown as a formula (III) accounts for less than 3 percent of the mixed photoinitiator; (B) an alkali soluble polymer; (C) a compound having an ethylenically unsaturated double bond; (D) a hydrogen donor; (E) optionally other auxiliaries. The photosensitive resin composition and the dry film thereof have excellent resolution and hue stability, do not have the tendency of resolution reduction after being stored for a long time at the temperature of between 20 ℃ below zero and 40 ℃, and have wide application in the aspects of manufacturing printed circuit boards, protective patterns, conductor patterns, lead frame wires, semiconductor packages and the like.

Description

Photosensitive resin composition with improved system hue stability

Technical Field

The invention belongs to the technical field of photocuring, and particularly relates to a photosensitive resin composition with improved system hue stability and application thereof.

Background

In recent years, with the miniaturization of printed wiring boards used in precision electronic devices such as personal computers, photosensitive resin compositions having high sensitivity, high resolution and high resolution have been the focus of research. The photoinitiator is one of the essential components in the photosensitive resin composition, and is required to have excellent properties such as high initiation efficiency, good compatibility with a system, excellent solubility and the like. The Hexaarylbisimidazole (HABI) compound has a special chemical structure, can be photolyzed under the action of ultraviolet light to generate macromolecular free radicals, and is a very important photoinitiator in the field of photocuring, particularly in the field of free radical polymerization.

Among the HABI-based photoinitiators, 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole (BCIM) is most widely used. BCIM has a plurality of isomers of connection positions, and the BCIM in the prior market is basically formed by mixing a plurality of isomers of connection positions. The application of BCIM in photosensitive resin compositions reported at present does not make further requirements on the internal isomer composition and content, but only directly applies the BCIM mixture in the compositions. On one hand, BCIM (binary coded modulation instant messaging) applications produced by different manufacturers on the market have larger difference, and bring great confusion to downstream manufacturers; on the other hand, the photosensitive resin composition containing the conventional BCIM product and the dry film thereof have low color stability, and have the problem of abnormal color development during long-term storage, which easily causes product defects, so that the problem needs to be solved.

In the process of researching 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole, the research and development team of the applicant finds that BCIM isomers and contents of different connecting positions have obvious influence on the performances of the photosensitive resin composition and a dry film thereof. Therefore, the research on the influence of the structure and the content of the isomer on the performance of the BCIM mixed photoinitiator is an effective means for further improving the practical application performance of the BCIM.

Disclosure of Invention

In view of the development needs of the prior art, the present invention is directed to a photosensitive resin composition with improved system hue stability, wherein the composition and a dry film thereof have excellent resolution and hue stability, and do not have a tendency of resolution reduction after being stored at-20 to 40 ℃ for a long time.

In order to achieve the purpose, the following specific technical scheme is adopted.

A photosensitive resin composition with improved system hue stability comprises the following components:

(A)2,2 ' -di (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 'linking site and the compound of formula (III) having a 1-5' linking site accounts for less than 3% of the mixed photoinitiator,

(B) an alkali soluble polymer;

(C) a compound having an ethylenically unsaturated double bond;

(D) a hydrogen donor;

(E) optionally (optinally), further auxiliaries.

The invention also provides the application of the photosensitive resin composition and the dry film thereof in the aspects of manufacturing printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages and the like.

Detailed Description

In view of the object of the present invention, the photosensitive resin composition of the present invention and various aspects of its application will be described in more detail below.

< photosensitive resin composition >

2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole mixed photoinitiator (A)

The 2,2 ' -di (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole mixed photoinitiator has a structure shown in a formula (I),

unless otherwise stated, percentages referred to herein are percentages by mass.

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

In the 2,2 ' -di (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole mixed photoinitiator of the invention, a compound of formula (IV) with a 1-2 ' connection site and a compound of formula (V) with a2 ' -3 connection site account for the main body, the sum of the contents of the two compounds accounts for more than 96 percent of the mixed photoinitiator,

in addition to the four compounds of the formulae (II), (III), (IV) and (V) described above, the 2,2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyldiimidazole mixed photoinitiator (BCIM) of the present invention may optionally contain minor amounts of isomers at the linking sites, e.g., 3-4', 3-5 ', 1-1', 1-3 ', 3-3'.

The 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole mixed photoinitiator according to the present invention is not particularly limited in the ratio between the compound of formula (II) and the compound of formula (III) and also in the ratio between the compound of formula (IV) and the compound of formula (V), and the object of the present invention can be achieved as long as the sum of the contents of the two satisfies the aforementioned requirements. Herein, the content of the components in the 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole mixed photoinitiator was measured by high performance liquid chromatography.

BCIM is a kind of photoinitiator well known in the field of photoresist, and can be prepared by oxidative coupling of substituted triphenyl imidazoles, the oxidant used in the preparation can be sodium hypochlorite, potassium ferricyanide and the like, the phase transfer catalyst used can be tetrabutyl ammonium bromide, benzyltriethyl ammonium chloride, crown ether (15-crown-5, 18-crown-6), polyethylene glycol and the like, and the specific preparation process can be referred to the description in the prior art such as US3784557, US4622286, US4311783 and the like (the whole content of which is incorporated herein by reference). In BCIM obtained by the existing preparation process, the sum of the contents of the two compounds shown as the formulas (II) and (III) accounts for a higher content of the BCIM mixed photoinitiator.

On the basis of the prior art, the BCIM mixed photoinitiator which meets the composition requirements of the invention can be conveniently obtained by carrying out solvent pulping and recrystallization processes on the product. The solvent may be one or more of toluene, benzene, methanol, ethanol, ethyl acetate, dichloromethane, and water.

The content of the BCIM mixed photoinitiator in 100 parts by mass of the photosensitive resin composition is preferably 1 to 10 parts by mass. Within the content range, the BCIM mixed photoinitiator can bring better hue stability while showing excellent photosensitive activity and resolution.

Alkali soluble Polymer (B)

The alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition. The alkali-soluble polymer is not particularly limited as long as it has such characteristics.

For example, suitable alkali-soluble polymers may be (meth) acrylic polymers, styrene polymers, epoxy polymers, aliphatic urethane (meth) acrylate polymers, aromatic urethane (meth) acrylate polymers, amide resins, amide epoxy resins, alkyd resins, phenolic resins, and the like.

Further, the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include: polymerizable styrene derivatives substituted at the α -position or at the aromatic ring, such as styrene, vinyltoluene, α -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 -furyl (meth) acrylic acid, and β -styryl (meth) acrylic acid; (meth) acrylate compounds such as alkyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 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, and glycidyl (meth) acrylate; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, propanoic acid, N-vinylcaprolactam; n-vinylpyrrolidone and the like. These polymerizable monomers may be used alone or in combination of two or more.

Further, from the viewpoint of alkali developability 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, which introduces a carboxyl group by using (meth) acrylic acid as a monomer unit; may be a copolymer further comprising, as a monomer unit, an alkyl (meth) acrylate in addition to (meth) acrylic acid; the copolymer may contain, as a monomer component, a polymerizable monomer other than (meth) acrylic acid and alkyl (meth) acrylate (for example, a monomer having an ethylenically unsaturated group) in addition to (meth) acrylic acid.

Further, the carboxyl group-containing alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer, and particularly is a (meth) acrylate polymer obtained by copolymerization of a (meth) acrylate, an ethylenically unsaturated carboxylic acid, and another copolymerizable monomer.

The (meth) acrylic acid ester may 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, and the like. These (meth) acrylates may be used alone or in combination of two or more.

The ethylenically unsaturated carboxylic acid may 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 may be used alone or in combination of two or more.

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

The alkali-soluble polymer may be used alone or in combination of two or more. Examples of the alkali-soluble polymer used in combination of two or more kinds include two or more kinds of alkali-soluble polymers composed of different copolymerization components, two or more kinds of alkali-soluble polymers having different weight average molecular weights, two or more kinds of alkali-soluble polymers having different degrees of dispersion, and the like.

In the photosensitive resin composition of the present invention, the weight average molecular weight of the alkali-soluble polymer is not particularly limited, and it should be adapted to a specific application environment. From the viewpoint of both mechanical strength and alkali developability, the weight average molecular weight is preferably 15000-200000, more preferably 30000-150000, and particularly preferably 30000-120000. When the weight average molecular weight is more than 15000, the developing resistance after exposure tends to be further improved, and when the weight average molecular weight is less than 200000, the developing time tends to be shorter and the compatibility with other components such as a photoinitiator can be maintained. The weight average molecular weight of the alkali-soluble polymer was measured by Gel Permeation Chromatography (GPC) and obtained by conversion using a standard curve of standard polystyrene.

Further, the acid value of the alkali-soluble polymer is preferably from 50 to 300mgKOH/g, more preferably from 50 to 250mgKOH/g, still more preferably from 70 to 250mgKOH/g, and particularly preferably from 100 to 250mgKOH/g, from the viewpoint of satisfactory alkali developability. When the acid value of the alkali-soluble resin is less than 50mgKOH/g, it is difficult to secure a sufficient developing speed, and when it exceeds 300mgKOH/g, the adhesiveness is decreased, a pattern short-circuit is likely to occur, and the problem of decrease in storage stability and increase in viscosity of the composition is likely to occur.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the alkali-soluble resin is preferably 1.5 to 6.0, particularly preferably 1.8 to 3.7. When the molecular weight distribution is in the range, developability is excellent.

The content of the alkali-soluble polymer in 100 parts by mass of the photosensitive resin composition is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass. When the content of the alkali-soluble polymer is 20 parts by mass or more, the durability of the photosensitive resin composition against plating treatment, etching treatment and the like can be ensured to be improved, and when the content is 70 parts by mass or less, the sensitivity of the photosensitive resin composition is favorably improved.

With olefinic unsaturationAnd a double bond compound (C)

The compound having an ethylenically unsaturated double bond can promote film formation of the photosensitive resin composition.

The compound having an ethylenically unsaturated double bond is not particularly limited, and a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule may be used. By way of example, mention may be made of: examples of the urethane acrylate include a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyol, a bisphenol a (meth) acrylate compound, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer such as a (meth) acrylate compound having an urethane bond in the molecule, nonylphenoxy polyethyleneoxy acrylate, γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, phthalic compounds, and alkyl (meth) acrylates. These compounds may 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 polyhydric alcohol include: polyethylene glycol di (meth) acrylate having an ethylene group of 2 to 14, polypropylene glycol di (meth) acrylate having a propylene group of 2 to 14, polyethylene-polypropylene glycol di (meth) acrylate having an ethylene group of 2 to 14 and a propylene group of 2 to 14, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, polypropylene glycol tri (meth) acrylate, polypropylene (meth) acrylate, and the like, Polyethylene glycol mono (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more. Here, "EO" represents ethylene oxide, and the EO-modified compound means a compound having a block structure of an oxyethylene group. "PO" represents propylene oxide, and a PO-modified compound means a compound having a block structure of an oxypropylene group.

Examples of the bisphenol a (meth) acrylate compound include: 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolypropoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolybutoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane and the like. Examples of the 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane include: 2, 2-bis {4- [ (meth) acryloyloxydiethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytriethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyethtetraethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypentaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyhexaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyheptaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyoctaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxynonaethoxy ] phenyl } propane, 2, 2-bis {4- [ (meth) acryloyloxydodecoxyethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytridecyloxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytetradecyloxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydentadecaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydetaxethoxy ] phenyl } propane and the like. The number of ethylene oxide groups in 1 molecule of the 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane is preferably 4 to 20, more preferably 8 to 15. These compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylate compound having a urethane bond in the molecule include: an addition reaction product 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) acryloxytetraethylene glycol isocyanate ] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.

Examples of the nonylphenoxy polyethyleneoxy acrylate include: nonylphenoxy tetraethenoxy acrylate, nonylphenoxy pentaethyleneoxy acrylate, nonylphenoxy hexaethyleneoxy acrylate, nonylphenoxy heptaethyleneoxy acrylate, nonylphenoxy octaethyleneoxy acrylate, nonylphenoxy nonaethyleneoxy acrylate, nonylphenoxy decaethyleneoxy acrylate, nonylphenoxy undecenyloxy acrylate, and the like. These compounds may be used alone or in combination of two or more.

Examples of the phthalic acid-based compound include: gamma-chloro-beta-hydroxypropyl-beta '- (meth) acryloyloxyethylphthalate, beta-hydroxyalkyl-beta' - (meth) acryloyloxyalkylphthalate, and the like. These compounds may 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, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, n-butyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, hydroxy-2-acrylate, hydroxy-2-acrylate, hydroxy-acrylate, or (meth) acrylate, hydroxy-2-acrylate, hydroxy-acrylate, or (meth) acrylate, hydroxy-acrylate, or (meth), 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofuranediol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexaacrylate are preferable. These compounds may be used alone or in combination of two or more.

The compound having an ethylenically unsaturated double bond is preferably a bisphenol a (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule, from the viewpoint of improving resolution, plating resistance, and adhesion. From the viewpoint that sensitivity and resolution can be improved, bisphenol a (meth) acrylate compounds are preferable. As commercially available products of bisphenol a-based (meth) acrylate compounds, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane (manufactured by shinkamura chemical industries, ltd., BPE-200), 2-bis {4- [ (meth) acryloyloxypolypropoxy ] phenyl) propane (manufactured by shinkamura chemical industries, ltd., BPE-5000; FA-321M manufactured by Hitachi chemical Co., Ltd.), 2-bis {4- [ (meth) acryloyloxypolybutoxy ] phenyl } propane (New Zhongmura chemical Co., Ltd., BPE-1300), and the like.

The content of the compound (C) having an ethylenically unsaturated double bond is preferably 20 to 50 parts by mass, more preferably 25 to 45 parts by mass, in 100 parts by mass of the photosensitive resin composition. When the content of the compound having an ethylenically unsaturated double bond is 20 parts by mass or more, the sensitivity and resolution of the photosensitive resin composition are further improved; when the content is 50 parts by mass or less, the photosensitive resin composition can be more easily made into a thin film, and the durability against etching treatment can be further improved.

Hydrogen donor (D)

The photosensitive resin composition of the present invention further includes a hydrogen donor in order to improve sensitivity. The double imidazole compounds are cracked after illumination, the generated single imidazole free radicals have larger volume, the steric hindrance effect causes the activity to be smaller, and the monomer polymerization is difficult to be initiated independently, and if the double imidazole compounds are used together with a hydrogen donor, the single imidazole free radicals are easy to capture active hydrogen on the hydrogen donor to generate new active free radicals, so as to initiate the monomer polymerization.

As long as the hydrogen donor has the above characteristics, there is no particular limitation in specific kinds, and may include (but is not limited to): amine compounds, carboxylic acid compounds, mercapto group-containing organic sulfur compounds, alcohol compounds, and the like. These compounds may be used alone, or in combination of two or more thereof.

The amine compound is not particularly limited, and may include (but is not limited to): aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone and the like.

The carboxylic acid-based compound is not particularly limited, and may include (but is 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, naphthyloxyacetic acid, etc.

The mercapto group-containing organosulfur compound is not particularly limited and may include (but is not limited to): 2-Mercaptobenzothiazole (MBO), 2-Mercaptobenzimidazole (MBI), dodecylmercaptan, ethylene glycol bis (3-mercaptobutyrate), 1, 2-propanediol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), Trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), 1, 2-propanediol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexa (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1, 2-propanediol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), Butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1, 2-propanediol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), 1, 2-propanediol bis (3-mercaptovalerate), Aliphatic secondary polyfunctional thiol compounds such as diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), and the like; aromatic secondary polyfunctional thiol compounds such as bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, bis (3-mercaptoisobutyl) phthalate and the like.

The alcohol compound is not particularly limited, and may include (but is not limited to): methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, 1, 2-propanediol, 1,2, 3-propanetriol, benzyl alcohol, phenethyl alcohol, etc.

The content of the hydrogen donor (D) may be 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight, in 100 parts by weight of the photosensitive resin composition. When the content of the hydrogen donor is within the above range, it is advantageous to control the sensitivity of the photosensitive resin composition.

Other optional auxiliary agents (E)

In addition to the above components, the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other auxiliary agents as needed. Illustratively, the auxiliary may include at least one of other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photo-colorants, fillers, plasticizers, stabilizers, coating aids, release promoters, and the like.

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, thioxanthones, acridines and other photoinitiators known to those skilled in the art.

Exemplary bisimidazoles include: 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-1, 1 ' -diimidazole, 2 ', 5-tris (2-fluorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-diimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-fluorophenyl) -4- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-diimidazole, 2 ' -bis (2-fluorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-methoxyphenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-chloro-5-nitrophenyl) -4,4 ' -bis (3, 4-dimethoxyphenyl) -5,5 ' -bis (o-chlorophenyl) -diimidazole, 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' -bis (2, 4-dichlorophenyl) -4,4 ', 5, 5' -tetraphenyl-diimidazole and the like. These bisimidazoles may be used alone or in combination of two or more.

Exemplary aromatic ketones include: acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4 '-methylbenzophenone sulfide, 4-benzoyl-4' -ethyldiphenyl sulfide, 4-benzoyl-4 '-propyldiphenyl sulfide, 4' -bis (diethylamino) benzophenone, 4-p-tolylmercapto benzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone, 4 '-bis (dimethylamino) benzophenone, 4' -bis (methyl, ethylamino) benzophenone, acetophenone dimethyl ketal, benzophenone derivatives, and mixtures thereof, Benzil dimethyl ketal,. alpha. '-dimethylbenzyl ketal,. alpha.' -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl etherylphenylacetone, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-butanone, phenylbis (2,4, 6-trimethylbenzoyl) oxyphosphine, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2-hydroxy-1- {3- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,1, 3-trimethyl-inden-5-yl } -2-methyl acetone, 2-hydroxy-1- {1- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,3, 3-trimethyl-inden-5-yl } -2-methyl acetone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) one, and the like. These aromatic ketone compounds may be used alone or in combination of two or more.

Exemplary anthraquinones include: 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone-9, 10-diethyl ester, 1,2, 3-trimethylanthracene-9, 10-dioctyl ester, 2-ethylanthrane-9, 10-bis (methyl chlorobutyrate), 2- {3- [ (3-ethyloxetan-3-yl) methoxy ] -3-oxopropyl } anthracene-9, 10-diethyl ester, 9, 10-dibutoxyanthracene, 9, 10-diethoxy-2-ethylanthrane, 9, 10-bis (3-chloropropoxy) anthracene, 9, 10-bis (2-hydroxyethylmercapto) anthracene, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone, 10-bis (3-chloropropoxy) anthracene, 2, 3-diphenylanthraquinone, 1-trimethylanthracene, 10-dibutoxyanthraquinone, 9, 10-diethoxyanthraquinone, 2-dibutoxyanthraquinone, and mixtures thereof, 9, 10-bis (3-hydroxy-1-propylmercapto) anthracene and the like. These anthraquinone compounds may be used alone or in combination of two or more.

Exemplary 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 may be used alone or in combination of two or more.

Exemplary oxime ester compounds may include: 1- (4-phenylthiophenyl) -n-octane-1, 2-dione-2-benzoxy-ate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -ethane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -butane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -propane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -1-cyclohexyl-methane- 1-keto-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentyl) -propane-1-one-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime benzoate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime benzoate, 1- (4-benzoyldiphenyl sulfide) - (3-cyclopentylacetone) -1-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) - (3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (4-benzoyldiphenyl sulfide) -3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) -one-oxime (3-cyclopentyl) -propane-1, 2-dione-2-o-methylbenzoic acid oxime ester, 1- (4-thiophenylphenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- (4-thenoyl-diphenylsulfide-4' -yl) -3-cyclopentyl-propane-1-one-acetic acid oxime ester, 1- (4-benzoyldiphenylsulfide) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-nitro-9-ethylcarbazol-3-yl) -3-cyclohexyl-propane-1-one-acetic acid oxime ester, and salts thereof, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime acetate, 1, 4-diphenylpropane-1, 3-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-3-oxime benzoate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 2-dione, oxime acetate, 2-dione, 2-oxime acetate, 2-dione, oxime acetate, 2-dione, oxime acetate, 2-oxime acetate, and 2-dione, 2-oxime acetate, 2-dione, and 2-dione, wherein, 2- [ (benzoyloxy) imino ] -1-phenylpropan-1-one, 1-phenyl-1, 2-propanedione-2- (oxoacetyl) oxime, 1- (4-thiophenylphenyl) -2- (2-methylphenyl) -ethane-1, 2-dione-2-oxime acetate, 1- (9, 9-dibutyl-7-nitrofluoren-2-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- {4- [4- (thiophene-2-formyl) thiophenyl ] phenyl } -3-cyclopentylpropan-1, 2-dione-oxime acetate, oxime ester of salicylic acid, and process for their preparation, 1- [9, 9-dibutyl-2-yl ] -3-cyclohexylpropylpropane-1, 2-dione-2-oxime acetate, 1- [6- (2-benzoyloxyimino) -3-cyclohexylpropyl-9-ethylcarbazol-3-yl ] octane-1, 2-dione-2-oxime benzoate, 1- (7-nitro-9, 9-diallylfluoren-2-yl) -1- (2-methylphenyl) methanone-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -3-cyclopentyl-propane-1-one-oxime benzoate, methyl acetate, ethyl acetate, or mixtures thereof, 1- [7- (2-methylbenzoyl) -9, 9-dibutylfluoren-2-yl ] -3-cyclohexylpropane-1, 2-dione-2-oxime acetate, 1- [6- (furan-2-formyl) -9-ethylcarbazol-3-yl ] -3-cyclohexylpropane-1, 2-dione-2-ethoxycarbonyloxime ester and the like. These oxime ester compounds may be used alone or in combination of two or more.

Exemplary triazines 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-triazin-6-yl ] phenylthio } propanoic acid, 1,1,1,3,3, 3-hexafluoroisopropyl-3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate, ethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, methyl-ethyl-2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate, methyl-, ethyl-4-yl-, ethyl-4-methyl-s-triazin-6-yl ] phenylthio } propanoate, and their derivatives, 2-ethoxyethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, cyclohexyl-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 } propanoic acid, 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanamide, benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, and the like, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2, 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1, 3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like. These triazine compounds may be used alone or in combination of two or more.

Exemplary coumarins include: 3,3 '-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 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 coumarins may be used alone or in combination of two or more.

Exemplary thioxanthone compounds include: thioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone, and the like. These thioxanthone compounds may be used alone or in combination of two or more.

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

The organic solvent may be any solvent capable of dissolving the above components, and may be, for example, a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, a chlorine-containing solvent, and the like, and is preferably selected in consideration of the solubility, coatability, safety, and the like of the colorant and the alkali-soluble polymer. Preferably, the organic solvent may be ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-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, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, n-butyl acetate, n-butyl, 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-cyclohexen-1-one), diisobutyl ketone (2, 6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol, ethanol, isopropanol, N-propanol, isobutanol, N-butanol, and the like. These solvents may be used alone, or two or more thereof may be used in combination.

Illustratively, dyes, pigments, and photo developers include: tris (4-dimethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, fluoran dye, toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine-green and phthalocyanine-blue and other phthalocyanine systems, auramine base, parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, chrysin green, basic blue 20, brilliant green, eosin, ethyl violet, dittanium sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinadine red, rhodol sodium agar, mirderlein, thymolsulfonphthalein, xylenol blue, methyl orange, tangerine IV, diphenylene flow carbazone, 2, 7-dichlorofluorescein, carmellose red, congo red, wool violet 4B, alpha-naphthylred, phenacetin, methyl violet, victoria pure blue, rhodamine 6G, BOH, Organic pigments such as diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-phenylenediamine, p-toluidine, benzotriazole, tolyltriazole, 4' -diaminobenzidine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl violet, azo-based pigments, and inorganic pigments such as titanium dioxide. In view of good contrast, tris (4-dimethylaminophenyl) methane (i.e. leuco crystal violet, LCV) is preferably used. These dyes, pigments and optical developers may be used singly or in combination of two or more.

Exemplary fillers include: fillers (not including the inorganic pigments) such as silica, alumina, talc, calcium carbonate, and barium sulfate. The filler may be used alone or in combination of two or more.

Exemplary plasticizers include: phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate, ethylene 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, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, trixylyl phosphate, 2-naphthyl diphenyl phosphate, cresyl di-2, 6-xylyl phosphate, aromatic condensed phosphate, tris (chloropropyl) phosphate, tris (tribromoneopentyl) phosphate, halogen-containing condensed phosphate, triethylene glycol dioctoate, triethylene glycol di (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, diethylene glycol monobutyl phthalate, neopentyl glycol monobutyl ether, neopentyl glycol ether, diphenyl ether, and the like, Dibutyl suberate, tris (2-ethyl) phosphate, Brij30[ C ] ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₄ OH]And Brij35[ C ] ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₂₀ OH]And the like. The plasticizer may be used alone or in combination of two or more.

Illustratively, the stabilizers include: 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 hydroquinones and quinones, tert-butyl catechol, 1,2, 3-benzenetrisol, copper resinate, naphthylamine, beta-naphthol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone and chloranil and the like. The stabilizer may be used alone or in combination of two or more.

Exemplary coating aids include: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methylene chloride, and the like. The coating aids may be used singly or in combination.

Exemplary release promoters include: benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, alkyl benzene sulfonic acid such as methyl, propyl, heptyl, octyl, decyl, dodecyl and the like. The peeling accelerator may be used alone or in combination of two or more.

The content of the other auxiliary is 0 to 10 parts by mass, preferably 0.5 to 5 parts by mass, in 100 parts by mass of the photosensitive resin composition.

< Dry film and Wet film applications >

The storage temperature of the photosensitive resin composition of the present invention is preferably from-20 ℃ to 40 ℃ from the viewpoint of ensuring excellent resolution and color stability of the photosensitive resin composition and its dry film.

The photosensitive resin composition can be prepared into a dry film, namely a photosensitive resin laminated body, and is applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires and semiconductor packages, and required patterns are formed on different substrates through different procedures.

The photosensitive resin composition of the present invention can be applied to a substrate corresponding to each of the respective manufacturing steps by a wet film coater, that is, applied as a wet film to manufacture of a printed circuit board, a protective pattern, a conductor pattern, a lead wire, and a semiconductor package, and a desired pattern is formed on a different substrate through different processes.

Dry film applications

The dry film, namely, the photosensitive resin laminate of the present invention comprises: a photosensitive resin layer formed by the photosensitive resin composition and a support for supporting the photosensitive resin layer.

Generally, the fabrication of dry films includes: coating the photosensitive resin composition on a support, and drying to form a photosensitive resin layer; optionally, a cover film (protective layer) is attached as necessary. Preferably, the drying condition is 60-100 deg.C for 0.5-15 min. The thickness of the photosensitive resin layer is preferably 5 to 95 μm, more preferably 10 to 50 μm, and still more preferably 15 to 30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation property is not good, and if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be poor.

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

The photosensitive resin composition is not particularly limited, and can be applied by a conventional method such as spray coating, roll coating, spin coating, slit coating, compression coating, curtain coating, dye coating, line coating, blade coating, roll coating, blade coating, spray coating, or dip coating.

Further, the present invention provides an application of the above dry film in manufacturing a printed circuit board, comprising:

(1) a laminating step: laminating the photosensitive resin laminate on a copper-clad laminate or a flexible substrate;

(2) an exposure step: exposing the photosensitive resin layer in the photosensitive resin laminate to light and irradiating the exposed portion with active light in an image-like manner to perform photocuring;

(3) a developing process: removing the unexposed portion of the photosensitive resin layer with a developing solution to form a protective pattern;

(4) a conductor pattern forming step: etching or plating the part of the surface of the copper-clad laminated plate or the flexible substrate, which is not covered by the protection pattern;

(5) a stripping procedure: and peeling the protective pattern from the copper-clad laminate or the flexible substrate.

Further, the present invention provides the use of the above dry film in the manufacture of a protective pattern, comprising the laminating process, the exposing process and the developing process as described above, except that: the photosensitive resin laminate in the laminating step may be laminated on various substrates made of different materials.

Further, the present invention provides an application of the dry film in the production of a conductor pattern, comprising the above-mentioned laminating process, exposing process, developing process and conductor pattern forming process, except that: the photosensitive resin laminate is laminated on a metal plate or a metal-coated insulating plate in the laminating step.

Further, the present invention provides an application of the above dry film in manufacturing a lead frame wire, comprising the above-mentioned laminating process, exposing process, developing process, and conductor pattern forming process, except that: in the lamination step, the photosensitive resin laminate is laminated on the metal plate, and in the conductor pattern formation step, the portion not covered with the protective pattern is etched.

Further, the present invention provides an application of the above dry film in manufacturing a semiconductor package, comprising the above-mentioned laminating process, exposing process, developing process, and conductor pattern forming process, except that: in the laminating step, the photosensitive resin laminate is laminated on a wafer having a large-scale integrated circuit, and in the conductor pattern forming step, a portion not covered with the protective pattern is plated.

Wet film applications

The photosensitive resin composition of the present invention can be used by directly coating on a substrate in a wet film manner, and is used for the production of printed wiring boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.

Without limitation, the photosensitive resin composition may be coated on the substrate by a conventional method such as roll coating, knife coating, spray coating, dip coating, etc., and dried to form the photosensitive resin layer.

After the photosensitive resin layer is formed on the substrate, subsequent processes such as an exposure process, a development process, a conductor pattern formation process, and a peeling process can be performed in a manner referred to dry film application.

In the exposure step, exposure may be performed by a mask exposure method (a method of irradiating actinic rays in an image form through a negative or positive mask pattern of a wiring pattern) or a projection exposure method, or may be performed by a method of irradiating actinic rays in an image form through a direct writing exposure method such as a laser direct imaging exposure method or a digital optical processing exposure method. As the light source of the active light, known light sources, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure lamp, a high pressure lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser, a gallium nitride-based blue-violet laser, and the like, which efficiently emit ultraviolet rays, can be used. Further, a light source that efficiently emits visible light, such as a floodlight for photography or a fluorescent lamp, may be used. The photosensitive resin composition of the present invention is not particularly limited with respect to the type of light source of the active light, and the exposure dose is preferably 10 to 1000mJ/cm ² 。

In the developing step, the unexposed portion of the photosensitive resin layer is removed with a developing solution. When the support is present on the photosensitive resin layer, the support may be removed by an automatic stripper or the like, and then the unexposed portion may be removed by using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Examples of the alkaline aqueous solution may be a 0.1 to 5 mass% sodium carbonate solution, a 0.1 to 5 mass% potassium carbonate solution, a 0.1 to 5 mass% sodium hydroxide solution, etc., and the pH is preferably 9 to 11. The alkaline aqueous solution may further contain a surfactant, a defoaming agent, an organic solvent, and the like. The developing method may be a conventional method such as dipping, spraying, brushing, etc.

In the etching treatment, the conductor layer of the circuit-forming substrate which is not covered is etched and removed using the resist pattern (i.e., the resist pattern) formed on the substrate as a mask, thereby forming a conductor pattern. The method of the etching process may be selected according to the conductor layer to be removed. Examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkaline etching solution, and a hydrogen peroxide etching solution.

In the plating treatment, copper, solder, or the like is plated on the insulating plate of the circuit-forming substrate that is not covered, using the resist pattern formed on the substrate as a mask. After the plating treatment, the resist pattern is removed to form a conductor pattern. The plating treatment may be electroplating or electroless plating, and is preferably electroless plating. Examples of the electroless plating treatment include: copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-uniform solder (high-high solder) plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating.

The resist pattern can be removed by an aqueous solution having a stronger basicity than the basic aqueous solution used in the developing step. As an example of the strongly alkaline aqueous solution, for example, a1 to 10 mass% aqueous solution of sodium hydroxide can be used.

Drawings

FIG. 1 is a high performance liquid chromatogram of product a 1.

FIG. 2 is a high performance liquid chromatogram of product a 2.

FIG. 3 is a single crystal diffraction pattern of BCIM at the 1-2' position.

FIG. 4 is a single crystal diffractogram of BCIM at the 2' -3 position.

FIG. 5 is a single crystal diffraction pattern of BCIM at the 1-5' position.

FIG. 6 is a single crystal diffraction pattern of BCIM at the 1-4' position.

FIG. 7 is an XRD analysis spectrum of BCIM at position 1-2'.

FIG. 8 is an XRD analysis spectrum of BCIM at 2' -3 position.

Fig. 9 is an XRD analysis pattern of product a 2.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.

Preparation of BCIM Mixed photoinitiators

1.1 preparation of BCIM Mixed photoinitiators a1, a2

Under the protection of nitrogen, 976g of 2- (o-chlorophenyl) -4, 5-diphenylimidazole (INC), 20g of 30% caustic soda liquid, 10g of tetrabutylammonium bromide and 6000g of toluene are put into a 10L reaction kettle, heated and stirred, 500g of sodium hypochlorite (11% aqueous solution) is dropwise added at the internal temperature of 60 ℃, the reaction is kept at a constant temperature after the dropwise addition is finished, and a sample is taken and is subjected to central control by HPLC until INC is less than 1%, the reaction is completed, and the heat preservation is finished. After the reaction is finished, washing the reaction product with 1000g of pure water for four times, then extracting the aqueous layer once with 1000g of toluene, distilling the organic layer under reduced pressure until the solvent is completely evaporated, adding 1000g of methanol, stirring, filtering, leaching and drying to obtain 933g of a1 product. The product a1 was detected using high performance liquid chromatography. FIG. 1 is a high performance liquid chromatogram of the product a1, which shows that the ratio of BCIM at 1-2 'position to BCIM at 2' -3 position in the product a1 is 95.61%, the ratio of BCIM at 1-4 'position to BCIM at 1-5' position is 1.69%, and the ratio of BCIM at other connecting positions is 0.97%.

Under the protection of nitrogen, 500g of product a1 and 3000g of toluene are put into a 5000mL four-neck flask, the internal temperature is 60 ℃, the mixture is heated and stirred until the mixture is clear, then the mixture is distilled under reduced pressure until about 800g of toluene is remained, the temperature is reduced to 25 ℃, and the mixture is filtered, leached and dried to obtain 432g of product a 2. The product a2 was detected using high performance liquid chromatography. FIG. 2 is a high performance liquid chromatogram of the product a2, showing that BCIM at positions 1-2 'and 2' -3 accounts for 99.55%, and BCIM at positions 1-4 'and 1-5' accounts for 0.33% of the product a 2.

1.2 separation and characterization of the Components of the BCIM Mixed photoinitiator

Here, the mechanism of BCIM reaction generation is first explained: the nitrogen atom in the triarylimidazole molecule loses H atom and has negative charge, the 2-position C in the triarylimidazole is more active due to the existence of the o-chlorophenyl group, and the C atom at the 2-position has positive charge due to the charge effect, so the N atom with the negative charge attacks the C atom with the positive charge, and finally, electrons are transferred to generate BCIM. The specific reaction mechanism is shown as follows:

according to the reaction mechanism of BCIM, BCIM should be a bisimidazole compound composed of four connection sites of 1-2 ', 1' -2, 2-3 'and 2' -3, because 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 bisimidazole compound consisting of two linking sites, 1-2 'and 2' -3, which respectively have the following compositions: 1-2' position BCIM: 2,2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -diimidazole; 2' -3-position BCIM: 2,2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-2', 3-diimidazole. The structure is shown in formulas (IV) and (V).

Although the presence of the ortho-chlorophenyl group makes the C at the 2-position of triarylimidazole more reactive, the same charge effects can also make the C at the 4-position and the C at the 5-position positively charged, resulting in a BCIM at the 1-5 'position and a BCIM at the 1-4' position.

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

the specific reaction mechanism course of the 1-4' BCIM is shown as follows:

in order to accurately verify the structure composition of the product, pure 1-2 ' BCIM, 2 ' -3 ' BCIM, 1-4 ' BCIM and 1-5 ' BCIM are respectively obtained by the prior known technical means such as column chromatography, chromatographic separation, single crystal separation and the like. FIG. 3 is a single crystal diffraction pattern of BCIM at the 1-2 'position, FIG. 4 is a single crystal diffraction pattern of BCIM at the 2' -3 position, FIG. 5 is a single crystal diffraction pattern of BCIM at the 1-5 'position, and FIG. 6 is a single crystal diffraction pattern of BCIM at the 1-4' position.

In order to more visually characterize BCIM at positions 1-2 'and BCIM at positions 2' -3, the BCIM at positions 1-2 ', the BCIM at positions 2' -3 and the product a2 were respectively subjected to powder XRD analysis. FIG. 7 is an XRD analysis spectrum of BCIM at position 1-2 ', FIG. 8 is an XRD analysis spectrum of BCIM at position 2' -3, and FIG. 9 is an XRD analysis spectrum of product a 2. As can be seen from FIGS. 7 to 9, the 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 BCIM content of other connecting positions is very little, so no obvious diffraction peak appears in an XRD spectrum.

1.3 light sensitivity test

Photosensitive resin compositions were prepared for sensitivity test with reference to the formulations shown in Table 1, in which the amount of each material was in g.

TABLE 1

In table 1, dipentaerythritol hexaacrylate (DPHA) was purchased from north linkage fine chemicals development ltd, tianjin, Leucocrystane (LCV) was purchased from chengzhou strong electronic new materials ltd, N-phenylglycine (NPG) was purchased from penzhen peng shunxing science and technology ltd, and Propylene Glycol Methyl Ether Acetate (PGMEA) was purchased from dennan junfeng chemical ltd.

The photosensitive resin composition was sufficiently stirred, and the composition was uniformly applied to the surface of a 25 μm-thick polyethylene terephthalate film as a support by using a bar coater. Drying in an oven at 95 deg.C for 5min to form a photosensitive resin layer. Exposure was carried out with a Stouffer 21-stage exposure scale, and an exposure machine (オ - ク, trade name EXM-1201) equipped with a high-pressure mercury lamp was set at 60mJ/cm ² Is irradiated withThe energy exposes the photosensitive layer. After exposure, the substrate was subjected to spray development with a1 mass% aqueous solution of sodium carbonate at 30 ℃ for a time 2 times as long as the minimum development time to remove the unexposed portion, and development was performed. Then, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of scales of the stage exposure scale of the formed photocurable film. The photosensitivity was represented by the number of grids of the exposure scale in the stage, and the higher the number of grids of the exposure scale in the stage, the higher the photosensitivity, and the results are shown in table 2.

TABLE 2

The product a2 has the same sensitivity as that of 1-2 ' BCIM and 2 ' -3 ' BCIM, and the sensitivity of 1-4 ' BCIM and 1-5 ' BCIM. However, the BCIM at the 1-4 'position and the BCIM at the 1-5' position show higher sensitivity because the steric hindrance of the structures is larger than that of the BCIM at the 1-2 'position and the BCIM at the 2' -3 position, and the energy required for the cleavage is lower than that of the BCIM at the 1-2 'position and the BCIM at the 2' -3 position. But exhibits poor stability due to the low energy required for its cleavage.

1.4 preparation of BCIM Mixed photoinitiator a3-a11

a 3: separating the obtained 1-2' BCIM single crystal;

a 4: separating the obtained 2' -3-bit BCIM single crystal;

a 5: through compounding, a mixture with 50 percent of 1-2 'BCIM and 50 percent of 2' -3 BCIM is obtained;

a 6: through compounding, a mixture with 49 percent of 1-2 ' BCIM, 50 percent of 2 ' -3 ' BCIM, 0.5 percent of 1-4 ' BCIM and 0.5 percent of 1-5 ' BCIM is obtained;

a 7: obtaining a mixture with 47 percent of 1-2 ' BCIM, 50 percent of 2 ' -3 BCIM and 3 percent of 1-4 ' BCIM through compounding;

a 8: obtaining a mixture with 47 percent of 1-2 ' BCIM, 50 percent of 2 ' -3 BCIM and 3 percent of 1-5 ' BCIM through compounding;

a 9: through compounding, a mixture with 48 percent of 1-2 ' BCIM, 47 percent of 2 ' -3 ' BCIM, 2.5 percent of 1-4 ' BCIM and 2.5 percent of 1-5 ' BCIM is obtained;

a 10: obtaining 1-2 ' BCIM, 47% 2 ' -3 BCIM and 5% 1-4 ' BCIM by compounding;

a 11: through compounding, the components of 48 percent of 1-2 'BCIM, 47 percent of 2' -3 'BCIM and 5 percent of 1-5' BCIM are obtained.

2. Preparation of photosensitive resin composition

The components were uniformly mixed to obtain a photosensitive resin composition according to the formulation shown in Table 3. Unless otherwise specified, the parts shown in table 3 are parts by mass.

TABLE 3

The designations of the components in Table 3 have the meanings indicated in Table 4.

TABLE 4

Preparation of alkali-soluble Polymer B: 500g of a mixed solvent of methyl cellosolve and toluene (mass ratio: 3:2) was added to a flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere, and after stirring and heating to 80 ℃, a solution prepared by mixing 100g of methacrylic acid, 200g of ethyl methacrylate, 100g of ethyl acrylate, 100g of styrene and 0.8g of azobisisobutyronitrile was slowly dropped into the flask for 4 hours, and the reaction was continued for 2 hours after the completion of the dropping. Then, 100g of a mixed solvent (composition as above) in which 1.2g of azobisisobutyronitrile was dissolved was dropped into the flask for 10 minutes, and after completion of the dropping, the reaction was further carried out at 80 ℃ for 3 hours, and the temperature was raised to 90 ℃ to continue the reaction for 2 hours. After completion of the reaction, the reaction mixture was filtered to obtain an alkali-soluble polymer B having an acid value of 196mgKOH/g and a weight-average molecular weight of about 80000.

3. Evaluation of Performance

3.1 evaluation mode

< preparation of Dry film >

The photosensitive resin composition was sufficiently stirred, uniformly applied on the surface of a 25 μm-thick polyethylene terephthalate film as a support by using a bar coater, dried at 95 ℃ for 5 minutes in a dryer to form a photosensitive resin layer having a thickness of 40 μm, and then a 15 μm-thick polyethylene film as a protective layer was laminated on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a dry film.

< leveling of substrate surface >

As the substrate, a copper-clad laminate having a thickness of 1.2mm in which a rolled copper foil having a thickness of 35 μ M was laminated was used, and the surface was subjected to wet polishing roll polishing [ Scotch-Brite (registered trademark) HD #600 manufactured by 3M, twice passage ].

< lamination >

The polyethylene film protective layer was peeled off from the dry film, and then laminated on a copper clad laminate preheated to 60 ℃ at a roll temperature of 105 ℃ using a hot roll laminator (AL-70 manufactured by asahi chemical corporation). The gas pressure was 0.35MPa, and the lamination speed was 1.5 m/min.

< Exposure >

The mask was placed on a polyethylene terephthalate film as a support, and passed through an ultra-high pressure mercury lamp (HMW-201 KB manufactured by ORCMANUFACTURINGCO., LTD.) at 60mJ/cm ² The photosensitive layer is exposed to the irradiation energy of (1).

< development >

The polyethylene terephthalate film was peeled off, and 1 mass% of Na at 30 ℃ was added using an alkali developing machine (developing machine for dry film manufactured by fujikikoco., ltd.) to the film ₂ CO ₃ Spraying the aqueous solution onto the photosensitive resin layerThe unexposed portions of the photosensitive resin layer were dissolved and removed for a time 2 times the minimum development time. The minimum time required for the photosensitive resin layer of the unexposed portion to completely dissolve was set as the minimum developing time.

3.2 content of evaluation

(1) Resolution ratio

After exposure development using a photomask having a wiring pattern of Line/Space of 10:10 to 150:150 (unit: μm), the resolution of the dry film was measured. The resolution is the minimum value of the pattern from which unexposed portions are removed in the resist pattern formed by development after exposure. The evaluation criteria are as follows:

o: the resolution value is below 30 μm;

very good: the resolution value is 30-50 μm, not including the end value;

x: the resolution value is above 50 μm.

(2) Maintaining temporal resolution

The dry film was stored in the dark at 23 ℃ under an atmosphere of 50% humidity for 2 weeks, and then the resolution was evaluated by the same method as the above-mentioned resolution test.

(3) Evaluation of hue stability

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

The light transmittance of the photosensitive resin laminate produced using the photosensitive resin composition solution stored at-20 to 40 ℃ for 3 days was compared with that of the photosensitive resin laminate produced using the photosensitive resin composition solution before storage, and the differences were classified as follows.

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

very good: an absolute value of a difference in transmittance at 600nm is 1% or more and less than 5%;

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

(4) Evaluation of hue stability before and after Exposure

Before exposure, the chromaticity values L, a, and b before exposure of the photosensitive resin laminate prepared from the photosensitive resin composition solution were measured by a transmission method in an alice X-rite (shanghai kaider color management ltd) colorimeter. 60mJ/cm for photosensitive resin laminate prepared from photosensitive resin composition solution ² The irradiation energy of (3) is used for exposure, and after exposure of the photosensitive resin laminate made of the photosensitive resin composition solution, the values of L, a, b and Δ L, Δ a, Δ b, Δ E of the photosensitive resin laminate made of the photosensitive resin composition solution after exposure are compared and tested by the same method of transmission in a color difference meter, with the chromaticity of the photosensitive resin laminate made of the photosensitive resin composition solution before exposure as a measurement standard. The ranking based on their difference is as follows.

O: Δ E is less than 5;

very good: Δ E is 5 or more and less than 10;

x: Δ E is 10 or more.

3.3 evaluation results

The evaluation results are shown in table 5.

TABLE 5

The photosensitive resin composition and the dry film thereof have excellent resolution and hue stability, and the resolution does not tend to be reduced even after long-term storage. The photosensitive resin composition can be widely used in the form of dry film and wet film in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims

1. A photosensitive resin composition with improved system hue stability comprises the following components:

(B) an alkali soluble polymer;

(C) a compound having an ethylenically unsaturated double bond;

(D) a hydrogen donor;

(E) optionally, other adjuvants.

2. The photosensitive resin composition according to claim 1, wherein: in the mixed photoinitiator of the component (A), the sum of the contents of the two compounds of the formulas (II) and (III) accounts for less than 1 percent of the mixed photoinitiator.

3. The photosensitive resin composition according to claim 1, wherein: in the mixed photoinitiator of the component (A), the compound of the formula (IV) with 1-2 'linking position and the compound of the formula (V) with 2' -3 linking position account for the main body, the sum of the contents of the two compounds accounts for more than 96 percent of the mixed photoinitiator,

4. the photosensitive resin composition according to claim 1, wherein: the alkali-soluble polymer is selected from one or a combination of more than two of (methyl) acrylic polymer, styrene polymer, epoxy polymer, aliphatic polyurethane (methyl) acrylate polymer, aromatic polyurethane (methyl) acrylate polymer, amide resin, amide epoxy resin, alkyd resin and phenolic resin.

5. The photosensitive resin composition according to claim 4, wherein: the alkali-soluble polymer is selected from alkali-soluble polymers containing carboxyl groups, preferably (meth) acrylate polymers obtained by copolymerizing (meth) acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers.

6. The photosensitive resin composition according to claim 1, wherein: the compound having an ethylenically unsaturated double bond is selected from one or a combination of two or more of a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A-based (meth) acrylate compound, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a (meth) acrylate compound having an amino ester bond in the molecule, nonylphenoxy polyethyleneoxy acrylate, γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, phthalic compounds, and alkyl (meth) acrylates, one or a combination of two or more of a bisphenol a-based (meth) acrylate compound and a (meth) acrylate compound having a urethane bond in the molecule is preferable.

7. The photosensitive resin composition according to claim 1, wherein: the hydrogen donor is selected from one or the combination of more than two of amine compounds, carboxylic acid compounds, organic sulfur compounds containing sulfydryl and alcohol compounds.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein: the storage temperature of the photosensitive resin composition is between-20 ℃ and 40 ℃.

9. A photosensitive resin laminate comprising: a photosensitive resin layer formed of the photosensitive resin composition according to any one of claims 1 to 8, and a support for supporting the photosensitive resin layer.

10. Use of the photosensitive resin composition according to any one of claims 1 to 8 and the photosensitive resin laminate according to claim 9 for the production of printed wiring boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.