Photosensitive resin composition, and preparation method therefor and use thereof

Abstract

The present application provides a photosensitive resin composition, and a preparation method therefor and a use thereof. The photosensitive resin composition comprises the following components: (A) a hexaarylbiimidazole mixed photoinitiator; (B) an alkali-soluble polymer; (C) a compound having an ethylenically unsaturated double bond; and (D) a hydrogen donor. The photosensitive resin composition of the present application has excellent compatibility, high photosensitivity, good resolution and developability, and excellent hydrophilicity, so that developing solutions can be reused, no filter screen clogging by development residues will be caused, and significant overall application performance advantages are provided.

Description

A photosensitive resin composition, its preparation method and application Technical Field

[0001] This application relates to the field of photocuring technology, such as a highly photosensitive photosensitive resin composition and its application. Background Technology

[0002] In recent years, with the miniaturization of printed circuit boards used in precision electronic devices such as mobile phones and wearable devices, photosensitive resin compositions with high photosensitivity and high resolution have become a research hotspot. As an essential component of photosensitive resin compositions, hexaarylbisimidazole (HABI) compounds have a unique chemical structure and can photolyze to generate large molecular free radicals under ultraviolet light. They are a very important class of photoinitiators in the field of photocuring, especially in the field of free radical polymerization.

[0003] Currently, exposure equipment containing i-rays (365nm) or h-rays (405nm) light sources is widely used in the manufacture of printed circuit boards (PCBs). In photosensitive resin compositions used for dry film resists, 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyldiimidazole is widely used as a photopolymerization initiator, exhibiting high photosensitivity. However, 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyldiimidazole is generally not used alone, as its resolution is poor when used alone and it produces an inverted trapezoidal shape during development. It is now often used in combination with 2,2'-di(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, which places demands on the photosensitivity of 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyldiimidazole. Its photosensitivity must be high, otherwise it cannot meet the needs of rapid production. At the same time, diimidazole photoinitiators face the problem of poor hue stability during use.

[0004] On the other hand, photosensitivity is crucial in PCB manufacturing. High photosensitivity and excellent color stability not only mean high efficiency and high quality, but also lower exposure energy, lower initiator dosage, and lower cost. Therefore, in the exposure process, to improve production efficiency, shorten exposure time, enhance stability, and reduce costs, it is also necessary to improve the photosensitivity and color stability of the photoresist. Summary of the Invention

[0005] The following is an overview of the subject matter described in detail herein. This overview is not intended to limit the scope of the claims.

[0006] This application provides a photosensitive resin composition, its preparation method, and its application.

[0007] On one hand, this application provides a photosensitive resin composition comprising the following components:

[0008] (A) A mixed photoinitiator of hexaaryl diimidazoles, which is a mixture obtained by oxidative coupling reaction of 2-(2-chlorophenyl)-4,5-diphenyl-imidazole (Formula I), 2',5'-di(2-chlorophenyl)-4'-(3,4-dimethoxyphenyl)-imidazole (Formula II) and 2'',4''-di(2-chlorophenyl)-5''-(3,4-dimethoxyphenyl)-imidazole (Formula III);

[0009]

[0010] It includes the diimidazole compounds and their isomers with the structure shown in P1 and the diimidazole compounds and their isomers with the structure shown in P2, and the sum of the contents of the diimidazole compounds with the structures shown in P1 and P2 constitutes 60% to 90% of the total mass percentage of the diimidazole compounds with the structures shown in P1 and P2 and their isomers.

[0011]

[0012] (B) Alkali-soluble polymers;

[0013] (C) Compounds containing alkene-unsaturated double bonds;

[0014] (D) Hydrogen donor.

[0015] In this application, the photosensitive resin composition and its dry film have excellent photosensitivity properties, while also shortening exposure time and improving production efficiency.

[0016] In this application, the hexaaryl diimidazole mixed photoinitiator is a mixture obtained by reacting raw material INC (Formula I) with raw material TAI. TAI has two isomers: 2',5'-bis(2-chlorophenyl)-4'-(3,4-dimethoxyphenyl)-imidazole (Formula II) and 2'',4''-bis(2-chlorophenyl)-5''-(3,4-dimethoxyphenyl)-imidazole (Formula III). Therefore, through pairwise and mutual reactions between the three monoimidazoles, nine diimidazole compounds with different structures and their isomers can be obtained, namely:

[0017]

[0018]

[0019]

[0020]

[0021] .

[0022] When the applicant was studying the products obtained by the oxidative coupling reaction of INC (Formula I) and TAI (which includes two structures, Formula II and Formula III), he found that the photosensitivity of the mixed initiator varied greatly when the molar ratio of INC to TAI changed, and the content of each component also varied greatly. If only INC is used for the reaction itself, the resulting product 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole has the lowest photosensitivity. If only TAI is used for the reaction itself, the resulting product 2,2',5,5'-tetra(2-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)diimidazole has about 25% higher photosensitivity than 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole. When INC and TAI are used in combination, the resulting product 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyldiimidazole mixed photoinitiator has the highest photosensitivity.

[0023] In one embodiment, the reaction molar ratio of INC (Formula I) to TAI (which includes both Formula II and Formula III) is 97:3 to 20:80, for example, 97:3, 95:5, 92:8, 90:10, 88:12, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70 or 20:80.

[0024] In this application, the preparation method of the hexaaryl diimidazole mixed photoinitiator is as follows: INC (formula I) and TAI (containing two structures, formula II and formula III) are reacted in an organic solvent in the presence of liquid alkali and tetrabutylammonium bromide, and then sodium hypobromide is added to react and obtain the hexaaryl diimidazole mixed photoinitiator.

[0025] Furthermore, to investigate the effects of each component on the photosensitivity of the mixed photoinitiator in greater depth, the applicant first used HPLC analysis, which revealed seven peaks with relatively high content. Then, using a preparative chromatography column, all seven components were separated. Subsequent characterization using 1H NMR, LCMS, and single-crystal diffraction revealed that the two most abundant components were two diimidazole compounds with structures shown in P1 and P2.

[0026]

[0027] In studying the photosensitivity of the seven components, it was found that the bisimidazole compound with structure P2 and its isomers exhibited the highest photosensitivity, followed by the bisimidazole compound with structure P1 and its isomers. The product 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, obtained from the INC reaction itself, showed the lowest photosensitivity. Only when the sum of the contents of the bisimidazole compounds with structures P1 and P2 constituted 60%–90% of the total mass percentage of the bisimidazole compounds with structures P1 and P2 and their isomers (e.g., 60%, 65%, 70%, 75%, 78%, 80%, 85%, 88%, or 90%), could superior photosensitivity and other comprehensive properties be obtained. If the proportion was less than 60%, the system compatibility tended to decrease significantly; if the proportion was greater than 90%, the system photosensitivity and other comprehensive properties tended to decrease significantly.

[0028] Optionally, when the sum of the contents of the diimidazole compounds with structures P1 and P2 is 65% to 85% of the total mass percentage of the diimidazole compounds with structures P1 and P2 and their isomers, better photosensitivity, lower development residue, and overall performance can be obtained.

[0029] The content of each component in the hexaaryl diimidazole mixed photoinitiator of this application was detected by high performance liquid chromatography.

[0030] Hexaaryl diimidazole photoinitiators are a well-known class of photoinitiators in the photoresist field. They can be prepared by oxidative coupling of triphenylimidazole compounds. Examples of oxidants used in the preparation process include sodium hypochlorite and potassium ferricyanide, while examples of phase transfer catalysts include tetrabutylammonium bromide, benzyltriethylammonium chloride, crown ethers (15-crown ether-5, 18-crown ether-6), and polyethylene glycol. Specific preparation processes can be found in relevant technologies such as US3784557, US4622286, and US4311783 (the full text of which is incorporated herein by reference).

[0031] In one embodiment, based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of component (A) is 1-10 parts by weight, for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight. Within this content range, the hexaaryl diimidazole mixed photoinitiator of this application exhibits excellent photosensitivity and resolution.

[0032] Alkali-soluble polymer (B)

[0033] Alkali-soluble polymers can impart film-forming properties to photosensitive resin compositions. As alkali-soluble polymers, any polymer with such properties can be used without particular restrictions.

[0034] For example, suitable alkali-soluble polymers may be (meth)acrylate polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethane (meth)acrylate polymers, amide resins, amide epoxy resins, alkyd resins, or phenolic resins, etc.

[0035] Furthermore, alkali-soluble polymers can be obtained via free radical polymerization of polymerizable monomers. Examples of polymerizable monomers include: polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene, which are substituted at the α-position or on an aromatic ring; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohols such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid derivatives; alkyl (meth)acrylates, benzyl (meth)acrylates, phenoxyethyl (meth)acrylate, 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, glycidyl (meth)acrylate, and other (meth)acrylate compounds; maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, and other maleic acid monoesters; fumaric acid, cinnamic acid, α-cyanocinonic 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.

[0036] Furthermore, considering alkali reproducibility and adhesion, alkali-soluble polymers containing carboxyl groups can be selected. Alkali-soluble polymers containing carboxyl groups can be acrylic resins containing (meth)acrylic acid as monomer units, which introduce carboxyl groups by using (meth)acrylic acid as a monomer unit; they can be copolymers that further contain alkyl (meth)acrylates as monomer units in addition to (meth)acrylic acid; or they can be copolymers that further contain polymerizable monomers other than (meth)acrylic acid and alkyl (meth)acrylates (such as monomers with vinyl unsaturated groups) as monomer components.

[0037] Furthermore, carboxyl-containing alkali-soluble polymers can be obtained by free radical polymerization of carboxyl-containing polymerizable monomers with other polymerizable monomers, especially (meth)acrylate polymers copolymerized from (meth)acrylates, vinyl unsaturated carboxylic acids and other copolymerizable monomers.

[0038] The (meth)acrylates mentioned 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.

[0039] The vinyl unsaturated carboxylic acids mentioned can be acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, or itaconic acid, with acrylic acid or methacrylic acid being optional. These vinyl unsaturated carboxylic acids can be used alone or in combination of two or more.

[0040] Other copolymerizable monomers may include (meth)acrylamide, (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.

[0041] 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 those composed of different copolymer components, those with different weight-average molecular weights, and those with different dispersities.

[0042] In the photosensitive resin composition of this application, there is no particular limitation on the weight-average molecular weight of the alkali-soluble polymer, which should be adapted to the specific application environment. Considering both mechanical strength and alkali developability, the weight-average molecular weight can be selected from 15,000 to 200,000 (e.g., 15,000, 18,000, 20,000, 30,000, 50,000, 80,000, 100,000, 130,000, 150,000, 180,000, or 200,000), further selected from 30,000 to 150,000, and particularly preferred from 30,000 to 120,000. When the weight-average molecular weight is greater than 15,000, the resistance to developer after exposure tends to be further improved; when the weight-average molecular weight is less than 200,000, the development time tends to be shorter, and compatibility with other components such as photoinitiators can be maintained. The weight-average molecular weight of the alkali-soluble polymer was determined by gel permeation chromatography (GPC) and converted using a standard curve of standard polystyrene.

[0043] Furthermore, considering good alkaline developability, the acid value of the alkali-soluble polymer can be selected from 50-300 mgKOH / g, for example, 50 mgKOH / g, 80 mgKOH / g, 100 mgKOH / g, 130 mgKOH / g, 150 mgKOH / g, 180 mgKOH / g, 200 mgKOH / g, 250 mgKOH / g, 280 mgKOH / g, or 300 mgKOH / g. More specifically, it can be selected from 50-250 mgKOH / g, and even more specifically, from 70-250 mgKOH / g, with 100-250 mgKOH / g being particularly preferred. When the acid value of the alkali-soluble resin is below 50 mgKOH / g, it is difficult to ensure sufficient development speed. When it exceeds 300 mgKOH / g, the adhesion decreases, pattern short circuits easily occur, and the storage stability of the composition decreases, while the viscosity increases.

[0044] The molecular weight distribution [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] of the alkali-soluble resin can be selected from 1.5 to 6.0, and more preferably from 1.8 to 3.7. When the molecular weight distribution is within the range described, the developability is excellent.

[0045] In one embodiment, based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of the alkali-soluble polymer is 20-70 parts by weight, for example, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 65 parts by weight, 68 parts by weight, or 70 parts by weight, optionally 30-60 parts by weight. When the content of the alkali-soluble polymer is 20 parts by weight or more, the durability of the photosensitive resin composition for plating, etching, etc., can be improved; when the content is 70 parts by weight or less, it is beneficial to improve the sensitivity of the photosensitive resin composition.

[0046] Compounds containing alkene-unsaturated double bonds (C)

[0047] Compounds with olefinic unsaturated double bonds can promote film formation in photosensitive resin compositions.

[0048] There are no particular limitations on compounds containing olefinic unsaturated double bonds; any photopolymerizable compound having at least one ethylene unsaturated bond within its molecule can be used. Examples include: compounds obtained from the reaction of α,β-unsaturated carboxylic acids with polyols; bisphenol A-type (meth)acrylate compounds; compounds obtained from the reaction of α,β-unsaturated carboxylic acids with compounds containing glycidyl groups; carbamate monomers such as (meth)acrylate compounds with intramolecular urethane bonds; nonylphenoxypolyethyleneoxyacrylates; γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate; β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate; β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate; phthalic acid compounds; and alkyl (meth)acrylates. These compounds can be used alone or in combination of two or more.

[0049] Examples of compounds obtained from the reaction of the aforementioned α,β-unsaturated carboxylic acids with polyols include: polyethylene glycol di(meth)acrylate with 2-14 ethylenes, polypropylene glycol di(meth)acrylate with 2-14 propylene groups, polyethylene-polypropylene glycol di(meth)acrylate with 2-14 ethylenes and 2-14 propylene groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and EO-modified trimethylolpropane tri(meth)acrylate. These compounds include (meth)acrylates, PO-modified trimethylolpropane tri(meth)acrylate, EO and PO-modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane 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 can be used alone or in combination of two or more. Here, "EO" represents ethylene oxide, and compounds modified with "EO" refer to compounds with a vinyl oxide block structure. "PO" represents propylene oxide, and compounds modified with "PO" refer to compounds with a propylene oxide block structure.

[0050] Examples of the aforementioned bisphenol A class (meth)acrylate compounds include: 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypolypropoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane, and 2,2-bis{4-[(meth)acryloyloxypolyethoxypolypropoxy]phenyl}propane, etc. Examples of the aforementioned 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)acryloyloxypentethoxy]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, 2,2-bis{4-[(meth)acryloyloxynonethoxy]phenyl}propane, 2, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyundecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydodecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetradecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecapentadecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, etc. The number of vinyl oxides per molecule of the above-mentioned 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane may be selected from 4 to 20, and more preferably from 8 to 15. These compounds can be used alone or in combination of two or more.

[0051] Examples of (meth)acrylate compounds containing an intramolecular urethane bond include: addition reaction products of (meth)acrylate monomers with an OH group at the β-position and diisocyanate compounds (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.); tris[(meth)acryloyloxytetraethylenediol isocyanate]hexamethylene isocyanurate; EO-modified urethane di(meth)acrylate; PO-modified urethane di(meth)acrylate; and EO, PO-modified urethane di(meth)acrylate. These compounds can be used alone or in combination of two or more.

[0052] Examples of the aforementioned nonylphenoxy polyethylene acrylates include: nonylphenoxy tetraethylene acrylate, nonylphenoxy pentaethylene acrylate, nonylphenoxy hexaethylene acrylate, nonylphenoxy heptaethylene acrylate, nonylphenoxy octaethylene acrylate, nonylphenoxy nonaethylene acrylate, nonylphenoxy decaethylene acrylate, and nonylphenoxy undecaethylene acrylate. These compounds can be used alone or in combination of two or more.

[0053] Examples of the aforementioned phthalic acid compounds include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate and β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl phthalate. These compounds can be used alone or in combination of two or more.

[0054] Examples of the aforementioned alkyl methacrylates include: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, isobornyl methacrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, benzyl methacrylate, pentyl methacrylate, tetrahydrofurfuryl methacrylate, isooctyl methacrylate, 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 these, options include methyl methacrylate, ethyl methacrylate, 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. These compounds can be used alone or in combination of two or more.

[0055] From the perspective of improving resolution, plating resistance, and adhesion, the compound having olefinic unsaturated double bonds can be selected from bisphenol A-type (meth)acrylate compounds and (meth)acrylate compounds with intramolecular urethane bonds. From the perspective of improving sensitivity and resolution, bisphenol A-type (meth)acrylate compounds can be selected. As commercially available bisphenol A-type (meth)acrylate compounds, examples include 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., BPE-200), 2,2-bis{4-[(meth)acryloyloxypolypropoxy]phenyl)propane (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., BPE-5000; manufactured by Hitachi Chemical Co., Ltd., FA-321M), 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane (Shin-Nakamura Chemical Industry Co., Ltd., BPE-1300), etc.

[0056] In one embodiment, based on 100 parts by mass of the total amount of the photosensitive resin composition, the content of the compound (C) having olefinic unsaturated double bonds is 20-50 parts by mass, for example, 20 parts by mass, 25 parts by mass, 30 parts by mass, 35 parts by mass, 40 parts by mass, 45 parts by mass, or 50 parts by mass, optionally 25-45 parts by mass. When the content of the compound having olefinic unsaturated double bonds is 20 parts by mass or more, the sensitivity and resolution of the photosensitive resin composition are further improved; when its content is 50 parts by mass or less, the photosensitive resin composition is easier to form into thin films, and its durability for etching treatment is further improved.

[0057] Hydrogen donor (D)

[0058] The photosensitive resin composition of this application also includes a hydrogen donor to improve photosensitivity. When diimidazole compounds are exposed to light, they cleave, producing large-volume monoimidazole radicals. Steric hindrance results in low reactivity, making it difficult for them to initiate monomer polymerization on their own. However, when used in conjunction with a hydrogen donor, the monoimidazole radicals readily capture active hydrogen from the donor, generating new active radicals that then initiate monomer polymerization.

[0059] There are no particular restrictions on the specific type of hydrogen donor that possesses the above-mentioned properties, and it may include (but is not limited to): amine compounds, carboxylic acid compounds, organosulfur compounds containing thiol groups, or alcohol compounds, etc. These compounds may be used alone or in combination of two or more of them.

[0060] There are no particular limitations on amine compounds, which may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyl diethanolamine, 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.

[0061] Carboxylic acid compounds are not particularly limited and 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, naphthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

[0062] There are no particular limitations on organosulfur compounds containing thiol groups, which may include (but are not limited to): 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-mercaptobutyrate), 1, 2-Propanedylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(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 tri(2-mercaptopropionate), pentaerythritol tetra(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 tri(3-mercaptoisobutyrate), pentaerythritol tetra(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 tri(2-mercaptoisobutyrate), pentaerythritol tetra(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 tri(4-mercaptovalerate), pentaerythritol tetra(4-mercaptovalerate), dipentaerythritol hexa(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), 1, Aliphatic secondary polyfunctional thiols such as 2-propanediol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane tri(3-mercaptovalerate), pentaerythritol tetra(3-mercaptovalerate), and dipentaerythritol hexa(3-mercaptovalerate); aromatic secondary polyfunctional thiols such as 1-mercaptoethyl phthalate, 2-mercaptopropyl phthalate, 3-mercaptobutyl phthalate, and 3-mercaptoisobutyl phthalate.

[0063] There are no particular restrictions on alcohol compounds, which 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-propanediol, 1,2,3-propanetriol, benzyl alcohol, phenethyl alcohol, etc.

[0064] In one embodiment, based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of the hydrogen donor (D) can be 0.01-20 parts by weight, for example, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight. 0.01-10 parts by weight is optional. When the content of the hydrogen donor is within the above range, it is advantageous for controlling the photosensitivity of the photosensitive resin composition.

[0065] Other optional adjuvants (E)

[0066] In addition to the components described above, the photosensitive resin composition of this application may optionally contain appropriate amounts of other additives as needed. Exemplarily, additives may include at least one of other photoinitiators and / or sensitizers, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating aids, peel accelerators, etc.

[0067] The other photoinitiators and / or sensitizers may include (but are not limited to): imidazolium, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, triazines, coumarins, thioxanones, acridines and other photoinitiators known to those skilled in the art.

[0068] For example, diimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetraphenyl-diimidazole, 2,2', 5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4', 5'-diphenyl-1,1'-diimidazole, 2,2', 5-tris(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4', 5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4', 5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4', 5'-diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4', 5,5'-tetraphenyl-diimidazole, and 2,2'-bis(2-fluorophenyl)-4, 4', 5, 5'-Tetraphenyl-diimidazole, 2, 2'-Di(2-methoxyphenyl)-4, 4', 5, 5'-tetraphenyl-diimidazole, 2, 2'-Di(2-chloro-5-nitrophenyl)-4, 4'-Di(3, 4-dimethoxyphenyl)-5, 5'-Di(2-chlorophenyl)-diimidazole, 2, 2'-Di(2-chloro-5-nitrophenyl)-4-(3, 4-dimethoxyphenyl)-5-(2-chlorophenyl)-4', 5'-diphenyl-diimidazole, 2, 2'-Di(2, 4-dichlorophenyl)-4, 4'-Di(3, 4-dimethoxyphenyl)-5, 5'-Di(2-chlorophenyl)-diimidazole, 2-(2, 4-dichlorophenyl)-4-(3, 4-Dimethoxyphenyl)-2',5-bis(2-chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(2-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole and their analogues. These diimidazole compounds can be used alone or in combination of two or more.

[0069] For example, 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)benzophenone, 4-p-toluenethiobenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethylamino)benzophenone, acetophenone dimethyl ketal, benzoylayl dimethyl ketal, α,α'-dimethylbenzoylayl ketal, α, α'-Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylpropanone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholine-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)-1-butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-1-{3-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,1,3-trimethyl-indene-5-yl}-2-methylpropanone, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3, 3-Trimethyl-indene-5-yl}-2-methylpropanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylprop-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)one and their analogues. These aromatic ketones can be used alone or in combination of two or more.

[0070] Exemplary examples include anthraquinones such as 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone-9,10-diethyl ester, 1,2,3-trimethylanthraquinone-9,10-dioctyl ester, 2-ethylanthraquinone-9,10-di(4-chlorobutyrate methyl ester), 2-{3-[(3-ethyloxetane-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-hydroxyethimercapto)anthracene, 9,10-di(3-hydroxy-1-propimercapto)anthracene, and their analogues. These anthraquinones can be used alone or in combination of two or more.

[0071] For example, benzoin and benzoin alkyl ether compounds include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and similar compounds. These benzoin and benzoin alkyl ether compounds can be used alone or in combination of two or more.

[0072] For example, oxime esters 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-acetate oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-butane-1-one-acetate oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-propane-1- Keto-acetate oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-1-cyclohexyl-methane-1-one-acetate oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3-cyclopentyl)-propane-1-one-acetate oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1, 2-Diketone-2-cyclohexylcarboxylate oxime, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3-cyclopentyl)-propane-1,2-dione-2-acetate oxime, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(4-benzoyl diphenyl sulfide)-3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-o-methylbenzoate oxime, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylate oxime, 1-(4-thienyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-acetate oxime, 1-(4-benzoyl diphenyl sulfide)-(3-cyclopentyl)-propane-1, 2-Diketone-2-oxime acetate, 1-(6-nitro-9-ethylcarbazole-3-yl)-3-cyclohexyl-propane-1-one-acetate oxime, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-3-cyclohexyl-propane-1-one-acetate oxime, 1-(6-thienylcarbamoyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanoyl-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-acetate oxime, 1-(6-furfuryl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1, 2-Diketone-2-acetate oxime, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-Diketone-2-acetate oxime ester, 1-(6-furanoyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-diketone-3-benzoic acid oxime ester, 1-(6-thiophenoyl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1,2-diketone-2-acetate 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-diketone-2-acetate oxime ester, 1-(9, 9-Dibutyl-7-nitrofluorene-2-yl)-3-cyclohexyl-propane-1-one-acetate oxime ester, 1-{4-[4-(thiophene-2-formyl)phenylthio]phenyl}-3-cyclopentylpropane-1,2-dione-2-acetate oxime ester, 1-[9,9-dibutyl-2-yl]-3-cyclohexylpropylpropane-1,2-dione-2-acetate oxime ester, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazole-3-yl]octane-1,2-dione-2-benzoate oxime ester, 1-(7-nitro-9, 9-Diallylfluorene-2-yl)-1-(2-methylphenyl)methyl ketone acetate oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-3-cyclopentylpropane-1-one-benzoate oxime ester, 1-[7-(2-methylbenzoyl)-9,9-dibutylfluorene-2-yl]-3-cyclohexylpropane-1,2-dione-2-acetate oxime ester, 1-[6-(furan-2-formyl)-9-ethylcarbazole-3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxyformyl oxime ester, and their analogues. These oxime esters can be used alone or in combination of two or more.

[0073] For example, 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-triazin-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid ester, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 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}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-S-triazin-6-yl]phenylthio}propionic acid, 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 their analogues. These triazine compounds can be used alone or in combination of two or more.

[0074] For example, 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 their analogues. These coumarin compounds can be used alone or in combination of two or more.

[0075] For example, thioxanthone compounds include: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone, and similar compounds. These thioxanthone compounds can be used alone or in combination of two or more.

[0076] For example, acridine compounds include: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluorophenylacridine, 1,7-di(9-acridyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine, 1,7-bis(9-acridyl)heptane, 1,5-bis(9-acridylpentane), 1,3-bis(9-acridyl)propane, and their analogues. These acridine compounds can be used alone or in combination of two or more.

[0077] The organic solvent can be any solvent capable of dissolving the aforementioned components. Exemplarily, it can be a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, or a chlorine-containing solvent. Preferably, the selection is made considering factors such as the solubility, coatability, and safety of the colorant and the alkali-soluble polymer. In one embodiment, the organic solvent can be an ethyl cellosolve (ethylene glycol monoethyl ether), a methyl cellosolve (ethylene glycol monomethyl ether), a butyl cellosolve (ethylene glycol monobutyl ether), or a methyl methoxybutanol (3... 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, ethylene glycol monomethyl ether acetate, methoxybutyl acetate (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-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, etc. These solvents can be used alone or in combination of two or more.

[0078] For example, dyes, pigments, and photochromic agents include: tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, fluorane dyes, toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine green and phthalocyanine blue and other phthalocyanine series, auramine base, parafuchsin, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green, adamantine green, basic blue 20, brilliant green, eosin, ethyl violet, erythrosine sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinadin red, rose red sodium agar, mitanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, orange IV, diphenyllucarbazone, 2, Organic pigments such as 7-dichlorofluorescein, panmethyl red, Congo red, Benzopurpureus 4B, α-naphthyl red, phenacetin, methyl violet, Victoria Blue BOH, rhodamine 6G, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-ethylenediamine, p-toluidine, benzotriazole, methylphentriazole, 4,4'-didiamine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl violet, and azo dyes, as well as inorganic pigments such as titanium dioxide, are used. Tris(4-dimethylaminophenyl)methane (i.e., leuco crystal violet, LCV) can be used if good contrast is desired. These dyes, pigments, and photodevelopers can be used individually or in mixtures of two or more.

[0079] For example, the filler includes: silica, alumina, talc, calcium carbonate, barium sulfate, etc. (excluding the aforementioned inorganic pigments). The filler can be used alone or in combination with two or more.

[0080] For example, plasticizers include: phthalates 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; and phenyl phosphates such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trimethylbenzene phosphate, trimethylbenzene phosphate, tolyl diphenyl phosphate, trimethylbenzene phosphate, 2-naphthyl diphenyl phosphate, and tolyl di-2-phenyl phosphate. 6-Dimethyl phosphate, aromatic condensed phosphate, tri(chloropropyl) phosphate, tri(tribromoneopentyl) phosphate, halogenated condensed phosphate, triethylene glycol dioctanoate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl octanoate, tri(2-ethylethyl) phosphate, Brij30 [C 12 H 25 [(OCH2CH2)4OH], and Brij35 [C 12 H 25 (OCH2CH2) 20 Plasticizers such as [OH] can be used alone or in combination with two or more.

[0081] For example, stabilizers include: hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide, 1-phenyl-3-pyrazolidineone, p-methoxyphenol, alkyl and aryl-substituted hydroquinones and quinones, tert-butylcatechol, 1,2,3-pyrogallol, copper resin, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluenequinone, and chloroquinone, etc. Stabilizers can be used alone or in combination of two or more.

[0082] For example, 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.

[0083] For example, 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 with two or more.

[0084] In one embodiment, based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of the other additives is 0-10 parts by weight, for example 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, optionally 0.5-5 parts by weight.

[0085] <Dry Film and Wet Film Applications>

[0086] The photosensitive resin composition of this application can be prepared into a dry film, i.e. a photosensitive resin laminate, and applied in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packages, forming the desired patterns on different substrates through different processes.

[0087] The photosensitive resin composition of this application can also be coated onto the corresponding substrates in each corresponding manufacturing step by a wet film coating machine, that is, it is used as a wet film in the manufacturing of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packages, and the desired patterns are formed on different substrates through different processes.

[0088] Dry film applications

[0089] The dry film of this application, namely a photosensitive resin laminate, comprises: a photosensitive resin layer formed by a photosensitive resin composition and a support supporting the photosensitive resin layer.

[0090] Typically, the preparation of a dry film involves: coating a photosensitive resin composition onto a support and drying it to form a photosensitive resin layer; optionally, applying a cover film (protective layer) as needed. Preferably, the drying conditions are drying at 60-100°C for 0.5-15 min. The thickness of the photosensitive resin layer can be selected from 5-95 μm, more preferably 10-50 μm, and even more preferably 15-30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation performance is poor, while if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be poor.

[0091] Specific examples of the support can be various types of plastic films, such as polyethylene terephthalate, polyvinyl naphthalate, polypropylene, polyethylene, cellulose acetate, polymethyl methacrylate, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, ethylene-vinyl chloride copolymer, polytetrafluoroethylene, polytrifluoroethylene, and similar materials. Furthermore, composite materials composed of two or more materials can also be used. In one embodiment, polyethylene terephthalate, which has excellent light transmittance, is used. The thickness of the support can be selected from 5-150 μm, and more preferably from 10-50 μm.

[0092] There are no special restrictions on the coating of photosensitive resin compositions. Conventional methods such as spraying, roller coating, rotary coating, slot coating, compression coating, curtain coating, dye coating, line coating, doctor blade coating, roller coating, squeegee coating, spraying, and dip coating can be used.

[0093] Furthermore, this application provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:

[0094] (1) Lamination process: The photosensitive resin laminate is laminated onto a copper-clad laminate or a flexible substrate;

[0095] (2) Exposure process: Expose the photosensitive resin layer in the photosensitive resin laminate to the active light in an image-like manner to cure the exposed part.

[0096] (3) Development process: The unexposed parts of the photosensitive resin layer are removed with a developing solution to form a protective pattern;

[0097] (4) Conductor pattern formation process: Etching or plating the parts of the copper-clad laminate or flexible substrate surface that are not covered by the protective pattern;

[0098] (5) Peeling process: Peel the protective pattern from the copper-clad laminate or flexible substrate.

[0099] Furthermore, this application 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 laminate can be laminated on substrates of various materials.

[0100] Furthermore, this application provides the application of the above-mentioned dry film in the manufacture of conductor patterns, including the lamination process, exposure process, development process and conductor pattern formation process as described above, the difference being that: in the lamination process, the photosensitive resin laminate is laminated on a metal plate or a metal-coated insulating plate.

[0101] Furthermore, this application provides the application of the above-mentioned dry film in the manufacture of lead frame lines, including the lamination process, exposure process, development process and conductor pattern formation process as described above, the difference being that: in the lamination process, the photosensitive resin laminate is laminated on the metal plate, and in the conductor pattern formation process, the part not covered by the protected pattern is etched.

[0102] Furthermore, this application provides the application of the above-mentioned dry film in the manufacture of semiconductor packaging, including the lamination process, exposure process, development process and conductor pattern formation process as described above, the difference being that: in the lamination process, the photosensitive resin laminate is laminated on the wafer having a large-scale integrated circuit, and in the conductor pattern formation process, the part not covered by the protected pattern is plated.

[0103] wet film application

[0104] The photosensitive resin composition of this application can be directly coated onto a substrate by wet film application for use in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, semiconductor packages, etc.

[0105] Non-limitingly, the photosensitive resin composition can be coated onto the substrate using conventional methods such as roller coating, blade coating, spray coating, and dip coating, and then dried to form a photosensitive resin layer.

[0106] After the photosensitive resin layer is formed on the substrate, subsequent processes such as exposure, development, conductor pattern formation, and stripping can be performed in the same manner as dry film applications.

[0107] In the exposure process, exposure can be achieved through methods such as mask exposure (where a negative or positive mask pattern of a wiring diagram illuminates the active light in an image-like manner), projection exposure, or direct drawing exposure methods such as laser direct imaging exposure or digital optical processing exposure to illuminate the active light in an image-like manner. As the light source for the active light, known light sources can be used, such as gas lasers like carbon arc lamps, mercury vapor arc lamps, ultra-high pressure lamps, high pressure lamps, xenon lamps, argon lasers, solid-state lasers like YAG lasers, semiconductor lasers, and gallium nitride-based blue-violet lasers, which effectively emit ultraviolet light. In addition, light sources that effectively emit visible light, such as photographic floodlights and fluorescent lamps, can also be used. The photosensitive resin composition of this application does not have particular limitations on the type of light source for the active light, and the exposure amount can be selected from 10-1000 mJ / cm². 2 .

[0108] In the developing process, the unexposed portions of the photosensitive resin layer are removed using a developing solution. If a support is present on the photosensitive resin layer, the support can be removed first using an automatic stripper, and then the unexposed portions can be removed using a developing solution such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent. Examples of alkaline aqueous solutions include 0.1-5% by mass sodium carbonate solution, 0.1-5% by mass potassium carbonate solution, and 0.1-5% by mass sodium hydroxide solution, with a pH value of 9-11. Surfactants, defoamers, and organic solvents can also be added to the alkaline aqueous solution. Developing methods can include conventional methods such as immersion, spraying, and brushing.

[0109] In the etching process, a resist pattern (i.e., a protective pattern) formed on a substrate is used as a mask to etch away the uncovered conductive layer of the substrate used for circuit formation, thereby forming a conductive pattern. The etching method can be selected depending on the conductive layer to be removed. Examples of etching solutions include copper oxide solutions, iron oxide solutions, alkaline etching solutions, and hydrogen peroxide-based etching solutions.

[0110] In the plating process, using a resist pattern formed on a substrate as a mask, copper and solder are plated onto the insulating plate of the circuit forming substrate that is not covered. After the plating process, the resist pattern is removed to form a conductor pattern. The plating process can be either electroplating or electroless plating, with electroless plating being the preferred option. Examples of electroless plating include: 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; and gold plating such as hard gold plating and soft gold plating.

[0111] The resist pattern can be removed by using an aqueous solution that is more alkaline than the alkaline aqueous solution used in the developing process. An example of a strongly alkaline aqueous solution is a 1-10% by mass sodium hydroxide aqueous solution.

[0112] Compared with related technologies, this application has the following advantages:

[0113] The photosensitive resin composition of this application has excellent compatibility, high photosensitivity, good resolution and developability, and excellent hydrophilicity, which allows the developer to be reused and prevents the development debris from clogging the filter. The overall application performance is significantly superior.

[0114] After reading and understanding the accompanying diagrams and detailed descriptions, the other aspects can be understood. Attached Figure Description

[0115] The accompanying drawings are used to provide a further understanding of the technical solutions in this paper and form part of the specification. They are used together with the embodiments of this application to explain the technical solutions in this paper and do not constitute a limitation on the technical solutions in this paper.

[0116] Figure 1 is a high-performance liquid chromatogram of product A1.

[0117] Figure 2 shows the structural spectrum of P6 obtained by single-crystal diffraction.

[0118] Figure 3 shows the structural spectrum of P2 obtained by single-crystal diffraction.

[0119] Figure 4 shows the structural spectrum of P1 obtained by single-crystal diffraction. Detailed Implementation

[0120] The technical solution of this application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely to help understand this application and should not be regarded as specific limitations on this application.

[0121] 1. Preparation of hexaaryl-diimidazole mixed photoinitiators

[0122] 1.1 Preparation of A1

[0123] Under nitrogen protection, 41.2 g of INC [2-(2-chlorophenyl)-4,5-diphenyl-imidazolium], 70.2 g of TAI [containing 2,5-di(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazolium and 2,4-di(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-imidazolium], 6.1 g of 30% caustic soda solution, 4.6 g of tetrabutylammonium bromide, and 500 g of chlorobenzene were added to a 1 L four-necked flask. The mixture was heated and stirred, and 97.2 g of sodium hypobromite was added dropwise at 60-65 °C. After the addition was complete, the reaction was maintained at this temperature. Samples were taken and controlled by HPLC. The reaction was considered complete when both TAI and INC were less than 1%. After the reaction was completed, the mixture was washed four times with 160 g of pure water, and then the aqueous layer was extracted once with 50 g of chlorobenzene. The organic layer was then distilled under reduced pressure. 100g of methanol was added to the material obtained by distillation, and the mixture was heated and stirred until it was clear. The clear solution was then added dropwise to a solution prepared by 30g of methanol and 50g of pure water. After the addition was completed, the solution was filtered, washed, and dried to obtain 103.1g of product A1.

[0124] Product A1 was analyzed using high performance liquid chromatography (Shimadzu, LC-20AT type), and the results are shown in Figure 1. It contained 7 peaks, with a total content of 96.02%. Product A1 was a mixture obtained by pairwise self-coupling and mutual coupling of three different monoimidazoles.

[0125] To accurately verify the structural composition of the product, a preparative chromatography column (model: Elite, SinoChrom C8) was used to separate all seven components, obtaining pure P1, P2, P3, P4, P5, P6 and P7, which were then subjected to structural confirmation.

[0126] P6 exhibits only one peak in the liquid phase, but single-crystal diffraction reveals two peak shapes (see Figure 2). Based on the structural characteristics, it can be determined that the main product of the coupling of two imidazoles is a mixture formed by the hydrogen-containing N atom on one imidazole and the C atom at the 2-position on the other imidazole. Therefore, the main structure of P6 consists of products with both 2'-1 and 2'-3 connection sites, as shown in the following structural formula:

[0127] .

[0128] The structure of P2 was confirmed by single-crystal diffraction, as shown in Figure 3.

[0129] The structure of P1 was confirmed by single-crystal diffraction, as shown in Figure 4.

[0130]

[0131] The structure of P2, P3, P4, P5, P6 and P7 was verified using LCMS (model: Shimadzu, LCMS-2020).

[0132] Mass spectrometry analysis of P2, P3, and P5 yielded a molecular fragment peak at 755 nm using the instrument's accompanying software. The molecular weight of the product was 754, which matched that of T+1, proving that the three products have similar structures, the same molecular weight, and are isomers.

[0133] Mass spectrometry analysis of P1, P4, and P7, using the instrument's accompanying software, yielded a molecular fragment peak at 849. The molecular weight of the product was 848, consistent with T+1, proving that the three products have similar structures, the same molecular weight, and are isomers.

[0134] Based on the above experimental analysis, product A1 is determined to be composed of P1, P2, P3, P4, P5, P6, and P7, with P2, P3, and P5 being isomers, and P1, P4, and P7 being isomers. The sum of the contents of P1 and P2 constitutes 74% of the total mass percentage of P1, P2, P3, P4, P5, and P7.

[0135] 1.2 Preparation of A2-A13

[0136] Products A2-A13 are mixtures obtained by coupling three different monoimidazoles. The difference is that the molar ratio of INC to TAI is different. The details of each product are shown in Table 1 and Table 2 below.

[0137]

[0138]

[0139] 2. Preparation of photosensitive resin composition

[0140] Referring to the formulation shown in Table 3, mix all components thoroughly to obtain the photosensitive resin composition. Unless otherwise specified, all parts shown in Table 3 are parts by weight.

[0141]

[0142] The meanings of the component codes in Table 3 are shown in Table 4.

[0143]

[0144] Preparation of alkali-soluble polymer B: Under a nitrogen atmosphere, 500 g of a mixed solvent of methyl cellosolve and toluene (mass ratio 3:2) was added to a flask equipped with a stirrer, reflux cooler, thermometer, and 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 added dropwise to the flask over 4 hours. After the addition was completed, the reaction continued for 2 hours. Next, 100 g of a mixed solvent (composition as above) containing 1.2 g of azobisisobutyronitrile was added dropwise over 10 minutes. After the addition was completed, the reaction was further carried out at 80°C for 3 hours, and then the temperature was raised to 90°C for another 2 hours. After the reaction was completed, the alkali-soluble polymer B was obtained by filtration, with an acid value of 196 mg KOH / g and a weight-average molecular weight of approximately 80,000.

[0145] 3. Performance Evaluation

[0146] 3.1 Evaluation Method

[0147] <Dry film preparation>

[0148] The photosensitive resin composition was thoroughly stirred and uniformly coated onto the surface of a 25 μm thick polyethylene terephthalate film as a support using a rod coater. The film was then dried at 95°C for 5 minutes in a dryer to form a 40 μm thick photosensitive resin layer. A 15 μm thick polyethylene film was then laminated onto the surface of the unlaminated polyethylene terephthalate film as a protective layer to obtain a dry film.

[0149] <Substrate Surface Leveling>

[0150] As a substrate, a 1.2 mm thick copper-clad laminate with 35 μm thick rolled copper foil was used, and the surface was wet polished with a polishing roller [Scotch-Brite (registered trademark) HD#600 manufactured by 3M, twice].

[0151] Lamination

[0152] The polyethylene film protective layer is peeled off from the dry film and then laminated onto a copper-clad laminate preheated to 60°C using a hot roller laminator (Asahi Kasei AL-70) at a roller temperature of 105°C. The gas pressure is 0.35 MPa and the lamination speed is 1.5 m / min.

[0153] <Exposure>

[0154] The mask was placed on a polyethylene terephthalate film serving as a support, and then subjected to ultra-high pressure mercury lamp (HMW-201KB manufactured by ORCMANU FACTURING CO., LTD.) at a pressure of 60 mJ / cm².2 The irradiation energy exposes the photosensitive layer.

[0155] <Development>

[0156] The polyethylene terephthalate film was peeled off, and a dry film developer (a dry film developer manufactured by Fuji Kiko Co., Ltd.) was used. A 1% by mass Na₂CO₃ aqueous solution at 30°C was sprayed onto the photosensitive resin layer, and the unexposed portions of the photosensitive resin layer were dissolved and removed in a time twice the minimum development time. The minimum development time is defined as the shortest time required for the complete dissolution of the unexposed portions of the photosensitive resin layer.

[0157] 3.2 Evaluation Content

[0158] (1) Compatibility

[0159] The photosensitive resin composition was thoroughly stirred and then uniformly coated onto the surface of a 25 μm thick polyethylene terephthalate film, which served as a support, using a rod coater. The film was dried at 95°C for 5 minutes to form a photosensitive resin layer. The surface of the photosensitive resin layer was then visually inspected and graded as follows:

[0160] ○: Uniform surface;

[0161] ●: Undissolved substances precipitate on the surface.

[0162] (2) Sensitivity

[0163] The photosensitivity of the photosensitive resin layer was evaluated by exposing it for 15 minutes using a 41-level staged exposure meter manufactured by Stouffer, which features 41 levels of brightness variation from transparent to black. After exposure, development was performed for twice the minimum development time, and the layers were graded based on the exposure level of 8 in the staged exposure meter, which resulted in complete residue of the resist film.

[0164] ○: Exposure is 20mJ / cm 2 the following;

[0165] ◎: Exposure is 20mJ / cm 2 -50mJ / cm 2 Excluding end values;

[0166] ●: Exposure intensity is 50mJ / cm 2 above.

[0167] (3) Resolution

[0168] The resolution of the dry film was measured after exposure and development using a photomask with a wiring pattern of Line / Space = 10:10-150:150 (unit: μm). Resolution is the minimum value of the pattern after the unexposed areas are completely removed from the resist pattern formed after exposure and development.

[0169] ○: Resolution value below 30μm;

[0170] ◎: Resolution values ​​are between 30μm and 50μm, excluding end values;

[0171] ●: Resolution value is above 50μm.

[0172] (4) Evaluation of hue stability

[0173] The polyethylene film was peeled off from the photosensitive resin laminate, and the transmittance of light at a wavelength of 600 nm was measured using a UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240). At the same time, a polyethylene terephthalate film, the same type 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 a blank value.

[0174] The transmittance of a photosensitive resin laminate prepared using a photosensitive resin composition solution stored at 23°C for 3 days was compared with that of a photosensitive resin laminate prepared using a photosensitive resin composition solution before storage, and the differences between them were classified as follows.

[0175] ○: The absolute value of the difference in transmittance at 600nm is less than 1%;

[0176] ◎: The absolute value of the difference in transmittance at 600nm is greater than 1% and less than 5%;

[0177] ●: The absolute value of the difference in transmittance at 600nm is greater than 5%.

[0178] The evaluation results are shown in Table 5.

[0179]

[0180] As can be seen, the photosensitive resin composition of this application has good hue stability, excellent compatibility and photosensitivity, and high photosensitivity, which can shorten exposure time and improve production efficiency. This photosensitive resin composition can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, semiconductor packaging, etc., in both dry film and wet film forms. It can also be used in the manufacture of color filters and liquid crystal display components.

[0181] The applicant declares that this application illustrates the photosensitive resin composition, its preparation method, and its application through the above embodiments, but this application is not limited to the above embodiments, that is, it does not mean that this application must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of the raw materials used in this application, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of this application.

Claims

1. A photosensitive resin composition comprising the following components: (A) A mixed photoinitiator of hexaaryl diimidazoles, which is a mixture obtained by oxidative coupling reaction of 2-(2-chlorophenyl)-4,5-diphenyl-imidazole as shown in Formula I, 2',5'-di(2-chlorophenyl)-4'-(3,4-dimethoxyphenyl)-imidazole as shown in Formula II and 2'',4''-di(2-chlorophenyl)-5''-(3,4-dimethoxyphenyl)-imidazole as shown in Formula III; It includes the diimidazole compounds and their isomers with the structure shown in P1 and the diimidazole compounds and their isomers with the structure shown in P2, and the sum of the contents of the diimidazole compounds with the structures shown in P1 and P2 constitutes 60% to 90% of the total mass percentage of the diimidazole compounds with the structures shown in P1 and P2 and their isomers. (B) Alkali-soluble polymers; (C) Compounds containing alkene-unsaturated double bonds; (D) Hydrogen donor.

2. The photosensitive resin composition according to claim 1, wherein, The sum of the contents of the diimidazole compounds with structures P1 and P2 in the total mass percentage of the diimidazole compounds with structures P1 and P2 and their isomers is 65% to 85%.

3. The photosensitive resin composition according to claim 1 or 2, wherein, Based on a total amount of 100 parts by mass of the photosensitive resin composition, the content of component (A) is 1-10 parts by mass.

4. The photosensitive resin composition according to any one of claims 1-3, wherein, The alkali-soluble polymer is selected from one or more of the following: (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. Optionally, the alkali-soluble polymer is selected from alkali-soluble polymers containing carboxyl groups, and may be a (meth)acrylate polymer copolymerized from (meth)acrylate, vinyl unsaturated carboxylic acid and other copolymerizable monomers.

5. The photosensitive resin composition according to any one of claims 1-4, wherein, The weight-average molecular weight of the alkali-soluble polymer is 15,000-200,000. Optionally, the acid value of the alkali-soluble polymer is 50-300 mg KOH / g.

6. The photosensitive resin composition according to any one of claims 1-5, wherein, Based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of the alkali-soluble polymer is 20-70 parts by weight, optionally 30-60 parts by weight.

7. The photosensitive resin composition according to any one of claims 1-6, wherein, The compound having an olefinic unsaturated double bond is selected from compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols, bisphenol A-type (meth)acrylate compounds, compounds obtained by reacting α,β-unsaturated carboxylic acids with compounds containing glycidyl groups, (meth)acrylate compounds with intramolecular urethane bonds, nonylphenoxypolyethyleneoxyacrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, and alkyl (meth)acrylates, or a combination of two or more thereof. Alternatively, it may be selected from bisphenol A-type (meth)acrylate compounds and (meth)acrylate compounds with intramolecular urethane bonds, or a combination of two or more thereof.

8. The photosensitive resin composition according to any one of claims 1-7, wherein, Based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of the compound having olefinic unsaturated double bonds is 20-50 parts by weight, optionally 25-45 parts by weight.

9. The photosensitive resin composition according to any one of claims 1-8, wherein, The hydrogen donor is selected from one or more of amine compounds, carboxylic acid compounds, organosulfur compounds containing thiol groups, and alcohol compounds.

10. The photosensitive resin composition according to claim 9, wherein, The amine compound is selected from one or more of the following: triethanolamine, methyl diethanolamine, triisopropanolamine, 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, or 4,4'-bis(diethylamino)benzophenone. Optionally, the carboxylic acid compound is selected from one or more combinations of 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, naphthioacetic acid, N-naphthylglycine, or naphthoxyacetic acid; Optionally, the thiol-containing organosulfur compound is selected from 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-mercaptobutyrate), 1, 2-Propanedylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(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 tri(2-mercaptopropionate), pentaerythritol tetra(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 tri(3-mercaptoisobutyrate), pentaerythritol tetra(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 tri(2-mercaptoisobutyrate), pentaerythritol tetra(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 tri(4-mercaptovalerate), pentaerythritol tetra(4-mercaptovalerate), dipentaerythritol hexa(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate), 1, Aliphatic secondary polyfunctional thiols such as 2-propanediol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane tri(3-mercaptovalerate), pentaerythritol tetra(3-mercaptovalerate), and dipentaerythritol hexa(3-mercaptovalerate); aromatic secondary polyfunctional thiols such as one or more of phthalic acid di(1-mercaptoethyl ester), phthalic acid di(2-mercaptopropyl ester), phthalic acid di(3-mercaptobutyl ester), or phthalic acid di(3-mercaptoisobutyl ester); Optionally, the alcohol compound is selected from one or more of 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, or phenylethanol.

11. The photosensitive resin composition according to any one of claims 1-10, wherein, Based on 100 parts by weight of the total amount of the photosensitive resin composition, the content of the hydrogen donor is 0.01-20 parts by weight, optionally 0.01-10 parts by weight.

12. The photosensitive resin composition according to any one of claims 1-11, wherein, The photosensitive resin composition further includes (E) other additives; Optionally, the other additives are selected from at least one or a combination of two or more of other photoinitiators and / or sensitizers, dyes, photochromic agents, pigments, fillers, plasticizers, stabilizers, coating aids or release accelerators.

13. The photosensitive resin composition according to any one of claims 12, wherein, Based on a total amount of 100 parts by weight of the photosensitive resin composition, the content of the other additives is 0-10 parts by weight, optionally 0.5-5 parts by weight.

14. A photosensitive resin laminate, wherein, The photosensitive resin laminate comprises a photosensitive resin layer formed from the photosensitive resin composition as described in any one of claims 1-13 and a support supporting the photosensitive resin layer.

15. The use of the photosensitive resin composition according to any one of claims 1-13 or the photosensitive resin laminate according to claim 14 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packages.

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