Photoinitiator, photosensitive resin composition and application thereof

Abstract

The invention provides a photoinitiator, a photosensitive resin composition and application thereof, the photoinitiator is a 2, 2 '-bis (2-alkoxy phenyl)-4, 4', 5, 5 '-tetraphenyl diimidazole photoinitiator and has a structure as shown in formula (I), and the photosensitive resin composition comprises (A) a 2, 2'-bis (2-alkoxy phenyl)-4, 4 ', 5, 5'-tetraphenyl diimidazole photoinitiator and (B) an alkali soluble polymer; and (C) a compound having an ethylenically unsaturated double bond. According to the photoinitiator disclosed by the invention, the photosensitive resin composition is complete in anti-corrosion pattern and good in linearity of pattern outline, and the photosensitive resin composition is good in dispersion stability, relatively high in resolution ratio and relatively good in sensitivity, and can meet the requirements of European Union halogen instructions.

Description

Technical Field

[0001] This invention belongs to the field of photocuring technology, and more specifically, relates to a photoinitiator, a photosensitive resin composition, and their applications. 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, high resolution, and high image quality have become a research hotspot. As an essential component of photosensitive resin compositions, hexaarylbisimidazole (HABI) compounds possess 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] Among HABI-type photoinitiators, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (commonly known as "BCIM") and 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyldiimidazole (commonly known as "TCDM-HABI") are the most widely used.

[0004] However, with the increasingly stringent requirements of the EU Halogen Directive 2002 / 95 / EC (the regulation for printed circuit board materials), the regulations have become more and more restrictive on the use of halogens (requiring restrictions on chlorine, bromine and total halogens, with bromine and chlorine contents of less than 900 ppm and bromine plus chlorine content of less than 1500 ppm respectively), which has limited the use of BCIM and TCDM-HABI.

[0005] On the other hand, existing technologies suffer from incomplete resist patterns. Furthermore, the HABI-type initiators used in large quantities have poor dispersibility in photosensitive compositions and are easily precipitated in the photosensitive compositions, resulting in insufficient yield.

[0006] Therefore, in order to overcome the shortcomings of existing technologies and meet the production needs of downstream clients for efficient production and reduced maintenance costs, it is very important to develop a type of dry film resist that meets regulatory requirements and has good anti-corrosion patterns and dispersion stability. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the purpose of this invention is to provide a photoinitiator, a photosensitive resin composition and its application, so as to solve the problem of incomplete resist pattern during the development process of the photosensitive resin composition in the prior art, and at the same time meet the requirements of the EU Halogen Directive.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] On one hand, the present invention provides a 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator, characterized in that the photoinitiator has the structure shown in formula (I).

[0010]

[0011] Wherein, R represents a straight-chain or branched alkyl group of C3 to C8.

[0012] In this invention, the C3 to C8 straight-chain or branched alkyl groups can be C3, C4, C5, C6, C7 or C8 straight-chain or branched alkyl groups.

[0013] Preferably, R is selected from n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl.

[0014] In this invention, by way of example, the 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator of this invention may be selected from or include (but is not limited to):

[0015]

[0016]

[0017] The 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator of the present invention mainly comprises two types of linkages, 1-2' and 2'-3, and the content is greater than 98%. In this paper, the component content in the 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator was detected by high performance liquid chromatography.

[0018] In addition to the 1-2' and 2'-3 linkages mentioned above, optionally, the 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator of the present invention may also contain small amounts of isomers at the 1-4', 1-5', 3-4', and 3-5' linkage sites. From the perspective of formulation stability, the content of isomers at other linkage sites is less than 2%.

[0019] The 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator of the present invention, where R represents a C3-C8 straight-chain or branched alkyl group. When the number of carbon atoms is less than or equal to 2, the photoinitiator has poor dispersibility and is prone to precipitation in the dry film; when the number of carbon atoms is greater than or equal to 9, the initiator will migrate to the surface of the film, resulting in poor resolution of the dry film and failure to obtain a good resist pattern.

[0020] In this invention, the preparation method of the 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator shown in formula (Ⅰ) includes the following steps:

[0021] (1) Raw material a and raw material b react in a solvent containing a catalyst to obtain intermediate A;

[0022] (2) Intermediate A and raw material c react in glacial acetic acid to obtain intermediate B;

[0023] (3) Intermediate B reacts in a solvent containing an oxidant to give product C.

[0024] The reaction equation is shown below:

[0025]

[0026] HABI-type initiators are a well-known class of photoinitiators in the photoresist field. They can be prepared by oxidative coupling of triphenylimidazolium 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 existing technologies such as US3784557, US4622286, and US4311783 (the full text of which is incorporated herein by reference).

[0027] In a second aspect, the present invention provides a photosensitive resin composition comprising the following components:

[0028] (A) The 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator as described above;

[0029] (B) Alkali-soluble polymers;

[0030] (C) Compounds containing olefinic unsaturated double bonds.

[0031] In 100 parts by weight of the photosensitive resin composition, the content of 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator is preferably 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 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator exhibits excellent photosensitivity and resolution, and ensures a good resist pattern.

[0032] Alkali-soluble polymer (B)

[0033] Alkali-soluble polymers can impart film-forming properties to photosensitive resin compositions. As alkali-soluble polymers, any polymer possessing this property can be used without particular limitations.

[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, and phenolic resins, etc.

[0035] Furthermore, alkali-soluble polymers can be obtained by 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)acrylates, tetrahydrofurfuryl (meth)acrylates, and di(meth)acrylates. Methamidoethyl acrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2-ethylhexyl methacrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, and other methacrylate 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 are preferred. The alkali-soluble polymer containing carboxyl groups can be an acrylic resin containing (meth)acrylic acid as a monomer unit, wherein the carboxyl group is introduced by using (meth)acrylic acid as a monomer unit; it can be a copolymer that further contains alkyl (meth)acrylate as a monomer unit in addition to (meth)acrylic acid; or it can be a copolymer that further contains polymerizable monomers other than (meth)acrylic acid and alkyl (meth)acrylate (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 and methacrylic acid being particularly preferred. 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 the present invention, 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 is preferably 15,000-200,000 (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), more preferably 30,000-150,000, and particularly preferably 30,000-120,000. When the weight-average molecular weight is greater than 15,000, the 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 alkali developability, the acid value of the alkali-soluble polymer is preferably 50-300 mg KOH / g, such as 50 mg KOH / g, 80 mg KOH / g, 100 mg KOH / g, 130 mg KOH / g, 150 mg KOH / g, 180 mg KOH / g, 200 mg KOH / g, 250 mg KOH / g, 280 mg KOH / g, or 300 mg KOH / g, more preferably 50-250 mg KOH / g, further preferably 70-250 mg KOH / g, and particularly preferably 100-250 mg KOH / g. When the acid value of the alkali-soluble resin is below 50 mg KOH / g, it is difficult to ensure a sufficient development speed. When it exceeds 300 mg KOH / 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 is preferably 1.5-6.0, particularly preferably 1.8-3.7. When the molecular weight distribution is within the range described above, the developability is excellent.

[0045] In 100 parts by weight of the photosensitive resin composition, the content of the alkali-soluble polymer is preferably 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, more preferably 45-65 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 olefinic 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. Propane tri(meth)acrylate, 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, and 2,2-bis{4-[(meth)acryloyloxyoctaethoxy]phenyl}propane. Examples of 2,2-bis{4-[(meth)acryloyloxynonethoxy]phenyl}propane include 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)acryloyloxydecaethoxy]phenyl}propane, and 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane. The number of vinyl oxides per molecule of the above-mentioned 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane is preferably 4-20, more preferably 8-15. These compounds can be used alone or in combination of two or more.

[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, and methyl methacrylate- 2-Hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, benzyl methacrylate, pentyl methacrylate, tetrahydrofurfuryl methacrylate, isooctyl methacrylate, ethoxylated nonylphenol methacrylate, propylene glycol polypropylene ether dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, ethoxylated polytetrahydrofurandiol dimethacrylate, ethoxylated polypropylene glycol dimethacrylate, etc. Preferably, methyl methacrylate, ethyl methacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethoxylated pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexaacrylate are used. 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 compounds having olefinic unsaturated double bonds are preferably bisphenol A-type (meth)acrylate compounds and (meth)acrylate compounds having intramolecular urethane bonds. From the perspective of improving sensitivity and resolution, bisphenol A-type (meth)acrylate compounds are preferred. Examples of commercially available bisphenol A-type (meth)acrylate compounds 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), and 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., BPE-1300), etc.

[0056] In 100 parts by weight of the photosensitive resin composition, the content of the compound (C) having olefinic unsaturated double bonds is preferably 20-60 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, or 50 parts by weight, more preferably 30-50 parts by weight. When the content of the compound having olefinic unsaturated double bonds is 20 parts by weight or more, the sensitivity and resolution of the photosensitive resin composition are further improved; when its content is 60 parts by weight or less, the photosensitive resin composition is easier to form into a thin film, and its durability for etching treatment is further improved.

[0057] Other optional adjuvants (D)

[0058] In addition to the components described above, the photosensitive resin composition of the present invention may optionally contain appropriate amounts of other additives as needed. Exemplarily, the additives may include at least one of other photoinitiators and / or sensitizers, hydrogen donors, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating aids, release accelerators, etc.

[0059] The other photoinitiators and / or sensitizers may include (but are not limited to): imidazoles, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, triazines, coumarins, thioxanones, acridines and other photoinitiators known to those skilled in the art.

[0060] For example, diimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tris(o-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 ... 2,2'-Di(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-di(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-di(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-di(2-methoxyphenyl)-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(o-chlorophenyl)-diimidazole, 2,2'-di(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5-(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-di(2,4-dichlorophenyl)-4,4'-di(3,4-dimethoxyphenyl)-5,5' 2-(2,4-dichlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-di(2,4-dichlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-di(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.

[0061] 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)diphenyl Benzene, 4-p-Toluene-2-mercaptobenzophenone, 2,4,6-Trimethylbenzophenone, 4-Methylbenzophenone, 4,4'-Bis(dimethylamino)benzophenone, 4,4'-Bis(methyl, ethylamino)benzophenone, Acetophenone dimethyl ketal, Benzoyl dimethyl ketal, α,α'-Dimethylbenzoyl ketal, α,α'-Diethoxyacetophenone, 2-Hydroxy-2-methyl-1-phenylpropanone, 1-Hydroxycyclohexylbenzophenone Ketones, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-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) [4-(2-hydroxy-2-methylpropanoyl)-1,3,3-trimethyl-indene-5-yl}-2-methylpropanone, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methylpropanoyl)-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.

[0062] 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.

[0063] 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.

[0064] 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-one-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-cyclopentane ... 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3- ...-one-acetate oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-[6-(2-methylbenzoyl 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate ester, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate ester, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-propane-1,2-dione-2-benzoic Carbazole-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(4-benzoyldiphenyl 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-phenylthio) 1-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylate oxime ester, 1-(4-thienylcarboxyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-acetate oxime ester, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate ester, 1-(6-nitro-9- Ethylcarbazole-3-yl)-3-cyclohexyl-propane-1-one-acetate oxime ester, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-3-cyclohexyl-propane-1-one-acetate oxime ester, 1-(6-thienylcarbamoyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime acetate ester, 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-dione-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-dione-3-benzoic acid oxime ester, 1-(6-thienyl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetate oxime ester, 2-[(benzoyloxy)imino] 1-Phenylacetane-1-one, 1-Phenylacetane-1,2-propanedione-2-(oxoacetyl)oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane-1,2-dione-2-acetate oxime ester, 1-(9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane-1-one-acetate oxime ester, 1-{4-[4-(thiophene-2-formyl)phenylthio]phenyl}-3-cyclopentylpropane-1-one-acetate oxime ester 2-Diketone-2-acetate oxime ester, 1-[9,9-dibutyl-2-yl]-3-cyclohexylpropylpropane-1,2-diketone-2-acetate oxime ester, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazole-3-yl]octane-1,2-diketone-2-benzoate oxime ester, 1-(7-nitro-9,9-diallylfluoren-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-acetic acid 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.

[0065] 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, cyclo[ ... Hexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-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.

[0066] Exemplary examples 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.

[0067] 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.

[0068] 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.

[0069] The photosensitive resin composition of the present invention also includes a hydrogen donor to improve photosensitivity. When diimidazole compounds are cleaved by light, the resulting monoimidazole radicals are relatively large, and their steric hindrance makes them less reactive, 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 abstract active hydrogen from the hydrogen donor, generating new active radicals that then initiate monomer polymerization.

[0070] There are no particular restrictions on the specific type of hydrogen donor, as long as it possesses the above-mentioned properties. It can include (but is not limited to): amine compounds, carboxylic acid compounds, organosulfur compounds containing thiol groups, or alcohol compounds, etc. These compounds can be used alone or in combination of two or more of them.

[0071] 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.

[0072] 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.

[0073] 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-propanediol 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), etc. esters), 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), Aliphatic secondary polyfunctional thiols such as tetraol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), 1,2-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); and aromatic secondary polyfunctional thiols such as di(1-mercaptoethyl phthalate), di(2-mercaptopropyl phthalate), di(3-mercaptobutyl phthalate), and di(3-mercaptoisobutyl phthalate).

[0074] 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.

[0075] The organic solvent can be any solvent capable of dissolving the aforementioned components. Exemplary examples include glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, and chlorine-containing solvents. Preferably, the selection is based on factors such as the solubility, coatability, and safety of the colorant and the alkali-soluble polymer. Preferably, the organic solvent can 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 monotert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid cellosolve (ethylene glycol monomethyl ether acetate), acetic acid... Methoxybutyl ester (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5,5-trimethyl-2-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.

[0076] 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-based dyes, 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, thymolphthalein... Organic pigments such as phenol sulfonphthalein, xylenol blue, methyl orange, orange IV, diphenyllucarbazone, 2,7-dichlorofluorescein, panmethyl red, Congo red, Benzopurpureus 4B, α-naphthyl red, phenacetin, methyl violet, Victoria Pure Blue BOH, rhodamine 6G, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-ethylenediamine, p-toluidine, benzotriazole, methylphentriazole, 4,4'-diamine, 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. For good contrast, tris(4-dimethylaminophenyl)methane (i.e., leuco crystal violet, LCV) is preferred. These dyes, pigments, and photodevelopers can be used individually or in mixtures of two or more.

[0077] 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.

[0078] 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 methyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trimethylbenzene phosphate, and trimethylbenzene phosphate. Phenylacetic diphenyl phosphate, tris(dimethyl) phosphate, 2-naphthyl diphenyl phosphate, tolyl di-2,6-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.

[0079] For example, stabilizers include: hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide, 1-phenyl-3-pyrazolone, p-methoxyphenol, alkyl and aryl-substituted hydroquinones and quinones, tert-butylcatechol, 1,2,3-phenylpyrogallol, 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.

[0080] 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.

[0081] 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.

[0082] In 100 parts by weight 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, preferably 0.5-5 parts by weight.

[0083] <Application>

[0084] The photosensitive resin composition of the present invention 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.

[0085] The photosensitive resin composition of the present invention 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.

[0086] Dry film applications

[0087] The dry film of the present invention, namely a photosensitive resin laminate, comprises: a photosensitive resin layer formed by a photosensitive resin composition and a support supporting the photosensitive resin layer.

[0088] Typically, the preparation of a dry film includes: 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 is preferably 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.

[0089] 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. Preferably, polyethylene terephthalate, which has excellent light transmittance, is used. The thickness of the support is preferably 5-150 μm, more preferably 10-50 μm.

[0090] 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.

[0091] Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:

[0092] (1) Lamination process: The photosensitive resin laminate is laminated onto a copper-clad laminate or a flexible substrate;

[0093] (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.

[0094] (3) Development process: The unexposed parts of the photosensitive resin layer are removed with a developing solution to form a protective pattern;

[0095] (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;

[0096] (5) Peeling process: Peel the protective pattern from the copper-clad laminate or flexible substrate.

[0097] Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of protective patterns, including the lamination process, exposure process and development process as described above, the difference being that: in the lamination process, the photosensitive resin laminate can be laminated on substrates of various materials.

[0098] Furthermore, the present invention 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.

[0099] Furthermore, the present invention 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 portion not covered by the protected pattern is etched.

[0100] Furthermore, the present invention 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 portion not covered by the protected pattern is plated.

[0101] wet film application

[0102] The photosensitive resin composition of the present invention 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.

[0103] 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.

[0104] 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.

[0105] Process steps

[0106] In the exposure process, exposure can be categorized into mask exposure (a method where a negative or positive mask pattern of the wiring diagram illuminates the active light source in an image-like manner), projection exposure, or direct drawing exposure methods such as laser direct imaging exposure and digital optical processing exposure to illuminate the active light source 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, all of 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.

[0107] The photosensitive resin composition of the present invention does not have particular limitations on the type of light source for the active light, and the exposure amount is preferably 10-1000 mJ / cm. 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 preferred pH 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 preferred. Examples of electroless plating include: copper plating such as copper sulfate plating and copper pyrophosphate plating; soldering 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 the prior art, the present invention has the following beneficial effects:

[0113] The photoinitiator of the present invention enables the photosensitive resin composition to produce a complete resist pattern with good linearity of the pattern outline. At the same time, the photosensitive resin composition has good compatibility, which can solve the problem of easy precipitation during the development process. It also has good developability, good hydrophilicity, high resolution, and good sensitivity, and can meet the requirements of the EU Halogen Directive. Detailed Implementation

[0114] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0115] 1. Preparation of 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator

[0116] 1.1 Preparation of Intermediate A

[0117]

[0118] Under nitrogen protection, 80.0 g of salicylaldehyde (starting material a), 83.9 g of n-propane bromide (starting material b), 135.0 g of potassium carbonate, 1.2 g of potassium iodide, 1.2 g of tetrabutylammonium bromide, and 500.0 g of acetonitrile were added to a 1 L four-necked flask. After the addition was complete, stirring was started, and the mixture was heated to reflux and maintained at this temperature for 6 hours. Samples were taken and controlled by HPLC. The reaction was considered complete when the salicylaldehyde content was less than 0.5%, and the temperature was then maintained at this temperature. After cooling to 25.0 °C, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 101.0 g of intermediate A with a purity of 99.71%.

[0119] The structure of intermediate A was confirmed using LCMS. Mass spectrometry analysis, with the aid of the instrument's software, yielded a molecular fragment peak at 165 molecule. The molecular weight of the product was 164, which was consistent with T+1.

[0120] 1.2 Preparation of Intermediate B

[0121]

[0122] Under nitrogen protection, 60.0 g of benzoyl, 51.5 g of intermediate A, 66.1 g of ammonium acetate, and 560.0 g of acetic acid were added to a 1 L four-necked flask. After the addition was complete, stirring was started, the temperature was raised to reflux, and the reaction was maintained at this temperature for 10 h. Samples were taken and controlled by HPLC. The reaction was considered complete when the benzoyl content was less than 1.0%, and the reflux was stopped. After cooling to 30.0 °C, 300.0 g of pure water was added dropwise to the flask. After a large amount of solid precipitated, the mixture was filtered and washed to obtain crude intermediate B with a purity of 96.41%. The crude product was added to a four-necked flask, and three times the amount of methanol (mass ratio) was added. Stirring was started, the temperature was raised to 50.0 °C, and the mixture was stirred and maintained at this temperature for 2 h. After cooling to 25.0 ± 2.0 °C, the mixture was filtered, washed, and dried to obtain 90.1 g of intermediate B with a purity of 99.03%.

[0123] The structure of intermediate A was confirmed using LCMS. Mass spectrometry analysis, with the aid of the instrument's software, yielded a molecular fragment peak at 355 ppm. The molecular weight of the product was 354 ppm, which was consistent with T+1.

[0124] The structure of intermediate B in the product was further confirmed using NMR, and the data are as follows:

[0125] 1 H NMR (400MHz, DMSO-d6)13.60(s,1H),7.80(d,1H),7.53-7.48(m,7H),7.28-7.16(m,6H),4.05(dd,2H),1.83-1.68(m,2H),1.05-1.02(m,3H)ppm.

[0126] 1.3 Preparation of Product A1

[0127]

[0128] Under nitrogen protection, 100.0 g of intermediate B, 4.5 g of tetrabutylammonium bromide, 120.0 g of potassium ferricyanide, and 400.0 g of toluene were added to a 1 L four-necked flask. After the addition was complete, stirring was started, and the temperature was raised to an internal temperature of 60.0 °C. Then, 245.0 g of a 30% NaOH aqueous solution was added dropwise. After the addition was complete, the reaction was maintained at this temperature for 4 hours. Samples were taken and analyzed by HPLC. The reaction was considered complete when the content of intermediate B was less than 1.0%, and the temperature maintenance was then stopped. Wash five times with 200.0g of pure water. Distill the organic layer under reduced pressure. Add 200.0g of methanol to the distillate and concentrate under reduced pressure again until no fraction remains. Add another 200.0g of methanol to the flask, heat to 50℃, stir for 2 hours, then cool to 20.0±2.0℃, filter, rinse, and dry to obtain 89.2g of product A1 with a purity of 99.24%.

[0129] The structure of product A1 was confirmed using LCMS. Mass spectrometry analysis, with the aid of the instrument's software, yielded a molecular fragment peak at 707. The molecular weight of the product was 706, which was consistent with T+1.

[0130] 1.4 Preparation of products A2 to A10

[0131] Following the synthesis method of product A1, raw material b, i.e., n-bromopropane, was replaced with different haloalkanes to prepare products A2 to A10. The analysis of each product is shown in Table 1 below.

[0132] Table 1

[0133]

[0134]

[0135] 1.5 Preparation of comparative products A11-A14

[0136]

[0137] Following the synthesis method of product A1, raw material b, i.e., n-bromopropane, was replaced with different haloalkanes to prepare comparative products A11 to A14. The analysis of each product is shown in Table 2 below.

[0138] Table 2

[0139]

[0140] 2. Preparation of photosensitive resin composition

[0141] 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.

[0142] Table 3

[0143]

[0144]

[0145] The meanings of the component codes in Table 3 are shown in Table 4.

[0146] Table 4

[0147]

[0148]

[0149] 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.

[0150] 3. Performance Evaluation

[0151] 3.1 Evaluation Method

[0152] <Dry film preparation>

[0153] 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.

[0154] <Substrate Surface Leveling>

[0155] 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].

[0156] Lamination

[0157] 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.

[0158] <Exposure>

[0159] The mask was placed on a polyethylene terephthalate film serving as a support, and then heated by an ultra-high pressure mercury lamp (HMW-201KB, manufactured by ORCMANU FACTURING CO., LTD.) at 60 mJ / cm².2 The irradiation energy exposes the photosensitive layer.

[0160] <Development>

[0161] 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.

[0162] 3.2 Evaluation Content

[0163] (1) Dispersion stability

[0164] 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:

[0165] ○: Uniform surface;

[0166] ●: Undissolved substances precipitate on the surface.

[0167] (2) Photosensitivity

[0168] 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.

[0169] ○: Exposure is 20mJ / cm 2 the following;

[0170] ◎: Exposure is 20mJ / cm 2 -50mJ / cm 2 Excluding end values;

[0171] ●: Exposure intensity is 50mJ / cm 2 above.

[0172] (3) Resolution

[0173] 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.

[0174] ○: Resolution value below 30μm;

[0175] ◎: Resolution values ​​are between 30μm and 50μm, excluding end values;

[0176] ●: Resolution value is above 50μm.

[0177] (4) Anti-corrosion pattern shape

[0178] The shape of the corrosion-resistant pattern was observed using a scanning electron microscope (SEM) (manufactured by Hitachi High Technology Co., Ltd., product name "SU-1500") at an accelerating voltage of 15kV, a magnification of 3000x, and an inclination angle of 60 degrees. The following criteria were used for judgment:

[0179] ○: The shape of the anti-corrosion pattern has not been confirmed to be cut to the bottom, the upper part of the anti-corrosion pattern is missing, and the straightness of the pattern outline is good;

[0180] ●: The shape of the anti-corrosion pattern is confirmed to be cut off to the bottom, the upper part of the anti-corrosion pattern is missing, and the straightness of the pattern outline is poor.

[0181] Table 5

[0182]

[0183]

[0184] The photoinitiator of this invention, when applied to a photosensitive resin composition, enables the composition to produce a complete resist pattern. This pattern exhibits characteristics such as incomplete overcutting, missing portions at the top, and good linearity of the pattern outline. Furthermore, the photosensitive resin composition of this invention demonstrates good dispersion stability, high resolution, and good sensitivity, while also meeting the requirements of the EU Halogen Directive. This photosensitive resin composition can be widely used in both dry and wet film applications in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging. It can also be applied to the manufacture of color filters and liquid crystal display components.

[0185] The applicant declares that the above embodiments illustrate the photoinitiator, photosensitive resin composition, and their applications, but the present invention is not limited to the above embodiments, i.e., it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator, characterized in that, The photoinitiator structure is shown in formula (Ⅰ). Wherein, R represents a straight-chain or branched alkyl group of C3 to C8.

2. The 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator according to claim 1, characterized in that, R is selected from n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl.

3. The 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator according to claim 1 or 2, characterized in that, The photoinitiator is selected from any one of the following compounds:

4. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the following components: (A) The 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator according to any one of claims 1-3; (B) Alkali-soluble polymers; (C) Compounds containing olefinic unsaturated double bonds.

5. The photosensitive resin composition according to claim 4, characterized in that, Based on 100 parts by weight of the total weight of the photosensitive resin composition, the content of the 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator is 1-10 parts by weight. Preferably, the alkali-soluble polymer is selected from one or more combinations of (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethane (meth)acrylate polymers, amide resins, amide epoxy resins, alkyd resins, and phenolic resins.

6. The photosensitive resin composition according to claim 4 or 5, characterized in that, The weight-average molecular weight of the alkali-soluble polymer is 15,000-200,000. Preferably, the acid value of the alkali-soluble polymer is 50-300 mg KOH / g; Preferably, based on 100 parts by weight of the total weight of the photosensitive resin composition, the content of the alkali-soluble polymer is 20-70 parts by weight, more preferably 45-65 parts by weight.

7. The photosensitive resin composition according to any one of claims 4-6, characterized in that, The compounds having olefinic unsaturated double bonds are 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, 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, preferably from one or more combinations of bisphenol A-type (meth)acrylate compounds and (meth)acrylate compounds with intramolecular urethane bonds. Preferably, 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, more preferably 30-50 parts by weight.

8. The photosensitive resin composition according to any one of claims 4-7, characterized in that, The photosensitive resin composition further includes (D) other additives; Preferably, the other additives are selected from at least one of other photoinitiators and / or sensitizers, hydrogen donors, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating aids, or peeling accelerators; Preferably, 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, preferably 0.5-5 parts by weight.

9. A photosensitive resin laminate, characterized in that, The photosensitive resin laminate comprises a photosensitive resin layer formed from the photosensitive resin composition as described in any one of claims 4-8 and a support supporting the photosensitive resin layer.

10. The use of the 2,2'-bis(2-alkoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole photoinitiator according to any one of claims 1-3, or the photosensitive resin composition according to any one of claims 4-8, or the photosensitive resin laminate according to claim 9, in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packages.

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