WO2020108421A1

WO2020108421A1 - Hexaarylbiimidazole hybrid photoinitiator and application

Info

Publication number: WO2020108421A1
Application number: PCT/CN2019/120524
Authority: WO
Inventors: 钱彬
Original assignee: 常州格林感光新材料有限公司
Priority date: 2018-11-30
Filing date: 2019-11-25
Publication date: 2020-06-04
Also published as: JP7264535B2; KR102542920B1; JP2022523892A; CN111258180A; KR20210110815A; CN111258180B

Abstract

A hexaarylbiimidazole hybrid photoinitiator, having a structure as represented by formula (I), and containing a biimidazole compound having four attachment sites, i.e., 1'-2, 2-3', 1-2' and 2'-3. The total mass percentage content of the biimidazole compound having the four attachment positions in the hybrid photoinitiator is above 92%. Ar ₁, Ar ₂, Ar ₃, Ar ₄, Ar ₅, and Ar ₆ in the formula (I) each independently represents a substituted or unsubstituted aryl group. A photosensitive resin composition containing the hexaarylbiimidazole hybrid photoinitiator has good compatibility, excellent photosensitivity, and a small amount of developing waste, and can be widely used in the forms of a dry film and a wet film.

Description

Hexaarylbisimidazole mixed photoinitiator and its application

Technical field

The invention belongs to the technical field of photocuring, and specifically relates to a hexaarylbisimidazole mixed photoinitiator, a photosensitive resin composition containing the photoinitiator, and the application of the photosensitive resin composition.

Background technique

The manufacture of microelectronic circuits such as printed circuit boards, integrated circuits, thin film transistors, semiconductor packages, etc. generally includes the formation of resist patterns using photolithography. In the photolithography method, the photosensitive resin composition layer or laminate coated on the substrate is exposed in combination with a mask having a predetermined pattern, and then developed using a developer with different solubility in the exposed part and the non-exposed part to form a resist The pattern is etched, and then the substrate is plated and/or etched using the resist pattern as a mask to form a desired conductor pattern on the substrate.

With the miniaturization of printed circuit boards on precision electronic equipment, photosensitive resin compositions with high sensitivity, high resolution and resolution have become research hotspots, and as one of the key components of photosensitive resin compositions, light The initiator is required to have high initiation efficiency, good system compatibility and good solubility. Hexaarylbisimidazole compounds (HABI) are a very important type of free radical photoinitiator. Under the action of ultraviolet light, they can be photolyzed to produce macromolecular free radicals, but HABI and its derivatives are normally solid, The solubility is easily poor. The full dissolution and dispersion of the photoinitiator is directly related to its initiation efficiency in the resin system.

In addition to the requirements of solubility and sensitivity, the current research also emphasizes that the photosensitive composition can be developed or processed in an aqueous phase. If the solubility of the components of the photosensitive resin composition in the developing solution is low, insoluble components that are poorly dispersible in the developing solution when the development process is repeated are remarkably increased, and aggregates (sludge) appear. When the development process is continued, the condensate will re-attach to the substrate, which may cause a short circuit and block the piping of the development tank.

Summary of the invention

Aiming at the disadvantages of the existing photosensitive resin composition using HABI and its derivatives as a photoinitiator, when forming a resist pattern, the advantages of high sensitivity, high solubility, and low development waste cannot be combined, the purpose of the present invention is to provide A HABI type mixed photoinitiator.

The hexaarylbisimidazole mixed photoinitiator of the present invention has the structure shown in the general formula (I), which contains four connection positions of 1'-2, 2-3', 1-2' and 2'-3 Of the biimidazole compound, and the total mass percentage of the four connected biimidazole compounds in the mixed photoinitiator is more than 92%,

In the general formula (I), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may be the same or different, and each independently represents a substituted or unsubstituted aryl group. The aryl group refers to any functional group or substituent derived from a simple aromatic ring, for example: phenyl, o-tolyl, 1-naphthyl (or α-naphthyl), 2-naphthyl and the like.

The object of the present invention is also to provide a photosensitive resin composition containing the above-mentioned mixed photoinitiator, and the application of the composition in manufacturing printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.

The photosensitive resin composition containing the above-mentioned hexaarylbisimidazole-based mixed photoinitiator has good compatibility, excellent sensitivity, and a small amount of developing waste, and can be widely used as a dry film and a wet film.

Detailed description of the invention

Based on the purpose of the present invention, each aspect will be described in more detail below.

The terms "sludge" and "developing waste" in this application refer to substances accumulated in the developing solution, which are insoluble in the developing solution and will be redeposited on the developed substrate, thereby reducing the efficiency of the developing solution.

In the general formula (I), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may be the same or different, and each independently represents a substituted or unsubstituted aryl group.

Specifically, the biimidazole compounds satisfying the four connection positions 1'-2, 2-3', 1-2' and 2'-3 of the structure represented by the general formula (I) have the following structures:

The substituted aryl group may be mono-substituted or poly-substituted.

Preferably, the substituent on the aryl group may be halogen, nitro, cyano, amine, hydroxy, C ₁ -C ₂₀ alkyl or alkenyl, C ₁ -C ₈ alkoxy, each of which is independent The methylene group in the variable (ie, each substituent) may be optionally substituted with oxygen, sulfur, and imine groups.

More preferably, the substituent on the aryl group may be fluorine, chlorine, bromine, nitro, cyano, amine, hydroxy, C ₁ -C ₁₀ alkyl or alkenyl, C ₁ -C ₅ alkoxy Group, wherein the methylene group in each independent variable may be optionally substituted by oxygen, sulfur, imine groups.

Further preferably, at least one of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ is an aryl group containing a halogen substituent. The halogen substituent can improve the color change effect during the curing process to enhance the recognition ability of the electronic eye during development (Note: the photosensitive resin layer will change color after exposure, and form a color difference with the unexposed area, which is recognized by the electronic eye. The invention can make the color difference more obvious), thereby improving the quality of the applied products. Particularly preferably, the halogen substituent is chlorine.

The HABI in this application means hexaaryldiimidazole, which is formed by coupling two triarylimidazoles (which may be the same or different, depending on the substituent on the aryl group). Due to the induction effect of the substituents on the aromatic ring, the π electron cloud density of the aromatic ring is reduced, and the induction effect causes the aromatic ring to twist. The conjugate center on the imidazole ring shifts, making the substituted aryl group and imidazole not in the same plane ( The triarylimidazole is in a curved state). When the two imidazoles are finally coupled, the connection of N and C shows different spatial configurations, which has a great impact on the performance of HABI.

In addition to the 1′-2, 2-3′, 1-2′, 2′-3 connection sites mentioned above, HABI photoinitiators also exist 1-4′, 1-5′, 3- 4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1', 5-3', etc. . However, the applicant's research found that HABI can only show the best performance when the four connection sites 1'-2, 2-3', 1-2', 2'-3 exist and the total content accounts for more than 92% of the total HABI. Excellent solubility and sensitivity. The solubility of a single substance at any kind of connection site is far less than the mixture of the present invention, and if the total content of these four kinds of connection sites is less than 92%, the sensitivity tends to become significantly lower.

As the HABI-based mixed photoinitiator of the present invention, a biimidazole compound satisfying four connection positions of 1′-2, 2-3′, 1-2′ and 2′-3 of the structure represented by the general formula (I) is preferably The total mass percentage in the mixed photoinitiator is 95% or more, and it is particularly preferred that the four types of 1'-2, 2-3', 1-2' and 2'-3 satisfy the structure represented by the general formula (I) The connected position is composed of a biimidazole compound.

Representatively, in the prior art, CN1292892A mentions a HABI photoinitiator used in photoresist photopolymerization systems, namely 2,2',5-tris(o-chlorophenyl)-4-( 3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2-diimidazole, commonly referred to as "TCDM-HABI", the document mentions that the use of at least one pro The HABI of water substituents (such as methoxy) can greatly reduce the amount of sludge in the used developer. However, the applicant's research found that a single 2,-2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1 ,2'-diimidazole or 2,-2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1' ,2-Diimidazole has very low solubility in methyl ethyl ketone or PGMEA, for example, 2,-2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) in PGMEA -4',5'-diphenyl-1,2'-diimidazole has a solubility of less than 3%; using these two single HABI photosensitive resin compositions, the amount of sludge in the developer during development is far Far from the expected results. Surprisingly, the 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2' -Diimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-di Imidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole When mixing, the solubility of the mixture in the solvent is greatly improved; and the application of the mixture in the photosensitive resin composition can significantly reduce the amount of sludge in the developer used repeatedly, so that the developer can be repeated multiple times , Effective use.

HABI photoinitiators are a type of photoinitiator known in the photoresist field, and can be prepared by oxidative coupling of triphenylimidazoles or substituted triphenylimidazoles. Specific preparation processes can refer to, for example, US3784557, US4622286, and US4311783 Etc. in the prior art (the entire contents of which are hereby incorporated by reference). On the basis of the existing process, adding a solvent recrystallization process can easily obtain HABI mixed photoinitiators that meet the above composition requirements of the present invention. The solvent may be one or a combination of two or more of toluene, methanol, ethyl acetate, dichloromethane, and water.

The photosensitive resin composition of the present invention generally includes, in addition to the HABI-based mixed photoinitiator, an alkali-soluble polymer; a compound having an ethylenically unsaturated double bond; other photoinitiators and/or sensitizers; And optional additives.

Alkali soluble polymer

The alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition. As the alkali-soluble polymer, as long as it has such characteristics, it can be applied without particular limitation.

Exemplarily, the applicable alkali-soluble polymer may be (meth)acrylic polymer, styrene polymer, epoxy polymer, aliphatic polyurethane (meth)acrylate polymer, aromatic polyurethane (method Group) acrylate polymer, amide resin, amide epoxy resin, alkyd resin, phenol resin, etc.

Further, the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene, etc. at the α-position or in the aromatic Polymerizable styrene derivatives substituted on the ring; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid , Α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid and other (meth) acrylic acid derivatives; Alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ( Diethylaminoethyl methacrylate, 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, diethylamino (meth)acrylate (Meth)acrylates such as ethyl ester, glycidyl (meth)acrylate; maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Maleic acid monoester; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propanoic acid, N-vinyl caprolactam; N-vinyl pyrrolidone, etc. These polymerizable monomers may be used alone or in combination of two or more.

Further, from the viewpoint of alkali developability and adhesion, it is preferable to use a carboxyl group-containing alkali-soluble polymer. The alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth)acrylic acid as a monomer unit, which is introduced into the carboxyl group by using (meth)acrylic acid as a monomer unit; it may further contain (meth)acrylic acid in addition ( A copolymer of alkyl methacrylate as a monomer unit; it may also contain a polymerizable monomer other than (meth)acrylic acid and alkyl (meth)acrylate in addition to (meth)acrylic acid (such as A copolymer having an ethylenically unsaturated group as a monomer component.

Further, the carboxyl group-containing alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers, especially from (meth)acrylate, ethylenically unsaturated carboxylic acid and other (Meth) acrylate polymer made by copolymerization of comonomers. The (meth)acrylate may be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate , Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylic acid Decyl ester, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethyl (meth)acrylate Aminoethyl, (meth)acrylate dimethylaminoethyl, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)acrylate, (meth)acrylic acid Glycidyl ester and so on. These (meth)acrylates may be used alone or in combination of two or more. The ethylenically unsaturated carboxylic acid may be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, with acrylic acid and methacrylic acid being particularly preferred. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. The other copolymerizable monomers may be (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinyl naphthalene, (meth)acrylonitrile, vinyl acetate, vinyl cyclohexane Wait. These other copolymerizable monomers may be used alone or in combination of two or more.

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

In the photosensitive resin composition of the present invention, the weight-average molecular weight of the alkali-soluble polymer is not particularly limited, but in terms of mechanical strength and alkali developability, the weight-average molecular weight is preferably 15,000 to 200,000, and more preferably 30,000 to 150,000, particularly preferably 30000-120000. When the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved, and when the weight average molecular weight is less than 200,000, the development time tends to become shorter, and can maintain other components such as photoinitiator Of compatibility. The weight-average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC), and is obtained by conversion using a standard polystyrene standard curve.

Further, from the viewpoint of good alkali developability, the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, still more preferably 70-250 mgKOH/g, and particularly preferably 100- 250mgKOH/g. When the acid value of the alkali-soluble resin is less than 50 mgKOH/g, it is difficult to ensure a sufficient development speed. When it exceeds 300 mgKOH/g, the adhesion is reduced, pattern short-circuiting is likely to occur, and the storage stability and viscosity of the composition are prone to occur. The problem of rising.

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

The content of the alkali-soluble polymer in the composition is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass based on 100 parts by mass of the total photosensitive resin composition. When the content of the alkali-soluble polymer is 20 parts by mass or more, the durability of the photosensitive resin composition to plating treatment, etching treatment, etc. can be improved, and when the content is 70 parts by mass or less, it is beneficial to improve the photosensitive resin composition Sensitivity.

Compounds with ethylenically unsaturated double bonds

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

The compound having an ethylenically unsaturated double bond is not particularly limited, and a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used. Illustrative examples include: compounds obtained by reacting α,β-unsaturated carboxylic acids with polyols, bisphenol A (meth)acrylate compounds, α,β-unsaturated carboxylic acids and glycidyl groups The compound obtained by the reaction of the compound, a urethane monomer such as a (meth)acrylate compound having a urethane bond in the molecule, nonylphenoxypolyvinyloxyacrylate, γ-chloro-β-hydroxypropyl -Β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, alkyl (meth)acrylate, etc. These compounds may be used alone or in combination of two or more.

Examples of the compound obtained by reacting the above-mentioned α,β-unsaturated carboxylic acid with a polyhydric alcohol include polyethylene glycol di(meth)acrylate having an ethyleneoxy number of 2-14, and the number of propyleneoxy groups being Polypropylene glycol di(meth)acrylate of 2-14, polyethyleneoxy·polypropyleneoxydiol di(methyl) with an ethyleneoxy number of 2-14 and a propyleneoxy number of 2-14 Acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trihydroxy Methylpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate Base) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, tripropylene glycol di (Meth) acrylate, etc. These compounds may be used alone or in combination of two or more. Here, "EO" means ethylene oxide, and the compound modified with EO means a compound having a block structure of an oxyethylene group. "PO" means propylene oxide, and the compound modified with PO means a compound having a block structure of an oxypropylene group.

Examples of the bisphenol A-based (meth)acrylate compound 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, 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane, etc. Examples of the 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane include 2,2-bis(4-((meth)acryloyloxy Diethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-((methyl ) Acryloyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane, 2,2-bis(4- ((Meth)acryloyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyheptethoxy)phenyl)propane, 2,2- Bis(4-((meth)acryloyloxyoctaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy nonaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyundecyloxy) Phenyl)propane, 2,2-bis(4-((meth)acryloyloxydodecyloxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxy Tridecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth Group) acryloyloxy pentaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyhexadecyloxy)phenyl)propane and the like. The number of oxyethylene groups per molecule of the 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane is preferably 4-20, and more preferably 8-15. These compounds may be used alone or in combination of two or more.

As the (meth)acrylate compound having a urethane bond in the molecule, a (meth)acrylic monomer having an OH group at the β position and a diisocyanate compound (isophorone diisocyanate, 2 , 6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tri((meth)acryloyloxytetraethylene glycol isocyanate ) Hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO, PO modified urethane di(meth)acrylic acid Ester etc. These compounds may be used alone or in combination of two or more.

Examples of the nonylphenoxypolyvinyloxy acrylate include nonylphenoxytetravinyloxy acrylate, nonylphenoxypentavinyloxy acrylate, and nonylphenoxyhexaethylene. Oxyacrylate, nonylphenoxy heptaethyleneoxy acrylate, nonylphenoxy octaethyleneoxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxy decavinyloxy Acrylate, nonylphenoxy undecyloxy acrylate, etc. These compounds may be used alone or in combination of two or more.

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

Examples of the above-mentioned alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, (meth) ) Isobornyl acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-hydroxypropyl ester, benzyl (meth)acrylate, amyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)acrylate, nonyl ethoxylate Phenol (meth)acrylate, propylene glycol polypropylene ether di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, Ethoxylated polytetrahydrofurandiol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, etc. Among them, preferred are methyl (meth)acrylate, ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexaacrylate. These compounds may be used alone or in combination of two or more.

From the viewpoint of improving resolution, plating resistance, and adhesion, the compound having an ethylenically unsaturated double bond is preferably a bisphenol A-based (meth)acrylate compound and a compound having a urethane bond in the molecule ( Meth)acrylate compound. From the viewpoint of improving sensitivity and resolution, a bisphenol A (meth)acrylate compound is preferred. As a commercially available product of a bisphenol A (meth)acrylate compound, there is exemplified 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane (such as Shin Nakamura Chemical Industry Co., Ltd., BPE-200), polyethoxybisphenol A methacrylate (such as Shin Nakamura Chemical Industry Co., Ltd., BPE-5000; Hitachi Chemical Co., Ltd., FA-321M), 2 , 2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane (such as Shin Nakamura Chemical Industry Co., Ltd., BPE-1300), etc.

In 100 parts by mass of the photosensitive resin composition, the content of the compound having an ethylenically unsaturated double bond is preferably 20-50 parts by mass, and more preferably 25-45 parts by mass. When the content of the compound having an ethylenically unsaturated double bond is more than 20 parts by mass, the sensitivity and resolution of the photosensitive resin composition will be further improved; when the content is less than 50 parts by mass, the photosensitive resin composition is easier It is thinned and the durability against etching is further improved.

HABI type mixed photoinitiator

As mentioned above, the HABI hybrid photoinitiator of the present invention has the structure shown in the general formula (I), which contains four connections of 1'-2, 2-3', 1-2' and 2'-3 Bis-imidazole compound, and the total mass percentage of the four-linked bis-imidazole compound in the mixed photoinitiator is 92% or more, preferably 95% or more, and particularly preferably 100%,

Within the range defined by the above characteristics, exemplarily, the HABI-based hybrid photoinitiator of the present invention may be selected from or include:

Compound A1:

Compound A2:

Compound A3:

Compound A4:

Compound A5

Compound A6

Compound A7

Compound A8

Compound A9

In the hexaarylbisimidazole-based mixed photoinitiator of the present invention, compounds such as compound A1 and compound A2 may exist alone, or two or more kinds may be used in combination.

In 100 parts by mass of the photosensitive resin composition, the hexaarylbisimidazole-based mixed photoinitiator of the present invention is preferably 1 to 10 parts by mass. Within this content range, the composition can exhibit good system compatibility and excellent curing performance.

Other photoinitiators and/or sensitizers

The photosensitive resin composition of the present invention may further contain other photoinitiators and/or sensitizers to increase the compatibility, sensitivity, and resolution of the photosensitive resin system through a common/synergistic effect.

The other photoinitiators and/or sensitizers may include (but are not limited to): diimidazoles, pyrazolines, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, Oxime esters, triazines, triphenylamines, coumarins, thioxanthones, acridines and other photoinitiators known to those skilled in the art. These photoinitiators can be used alone or in combination of two or more.

Exemplarily, the bisimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tri(o Chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tri(2-fluoro Phenyl)-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-(o-chlorophenyl)-5-(3,4-dimethoxy Phenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2, 2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)- 4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitro Phenyl)-4-(3,4-dimethoxyphenyl)-5-(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2, 4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2-(2,4- Dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-bis(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2-( 2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4', 5,5'-tetraphenyl-diimidazole, 2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyl-diimidazole and the like. These bisimidazole-based compounds may be used alone or in combination of two or more.

Exemplarily, the pyrazoline compounds include: 1-phenyl-3-(4-tert-butylstyryl)-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3 -Biphenyl-5-(4-tert-butylphenyl) pyrazoline, ethoxylated (9) trimethylol pyrazoline ester, ethoxylated (10) bisphenol A pyrazoline ester And the like. These pyrazoline compounds may be used alone or in combination of two or more.

Exemplarily, the aromatic ketone compounds include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 ,1-dichloroacetophenone, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyl Diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino) benzophenone, 4-p-toluene mercaptobenzophenone, 2 ,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethyl (Amino) benzophenone, acetophenone dimethyl ketal, benzyl dimethyl ketal, α,α'-dimethylbenzoyl ketal, α,α-diethoxyacetophenone , 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone, 2-methyl 1-(4-Methylmercaptophenyl)-2-morpholine 1-acetone, 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-hydroxyl -2-methyl-propionyl)-phenyl]-1,1,3-trimethyl-inden-5-yl}-2-methylacetone; and 2-hydroxy-1-{1-[4- (2-hydroxy-2-methyl-propionyl)-phenyl)-1,3,3-trimethyl-inden-5-yl)-2-methylacetone, 1-(4-isopropylbenzene Yl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)one and the like. These aromatic ketone compounds may be used alone or in combination of two or more.

Exemplarily, the anthraquinone compounds include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl, 1,2,3-trimethylanthracene-9,10-dioctyl fat, 2-ethylanthracene-9,10-bis(4-chlorobutyric acid Methyl ester), 2-(3-((3-ethyloxetan-3-yl)methoxy)-3-oxopropyl)anthracene-9,10-diethyl ester, 9,10 -Dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethylmercapto)anthracene , 9,10-bis (3-hydroxy-1-propylmercapto) anthracene and its analogs. These anthraquinone compounds may be used alone or in combination of two or more.

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

Exemplarily, the oxime ester compounds include: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-(6-(2-methyl Benzoyl)-9-ethylcarbazol-3-yl)-ethane-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazole- 3-yl)-butane-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-propane-1-one-acetic acid Oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-1-cyclohexyl-methane-1-one-oxime acetate, 1-(6- (2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propane-1-one-oxime acetate, 1-(4-phenylthiophenyl)- (3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-di Keto-2-cyclohexylcarboxylic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2 -Dione-2-acetoxime, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione -2-benzoic acid oxime ester, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-o-methylbenzoyl- 9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexyl formate, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentyl Acetone)-1-oxime cyclohexyl formate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2- Dione-2-o-toluic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-(4-Thienyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-oxime acetate, 1-(4-benzoyl diphenyl sulfide)- (3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazol-3-yl)-3-cyclohexyl-propane -1-one-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propane-1-one-oxime acetate, 1- (6-Thienyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanfuranoyl-9-ethylcarbazole -3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-acetoxime, 1-(6-furfuryl Acyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(4-phenylthiophenyl)-(3 -Cyclohexyl)-propane-1,2-dione-2-acetoxime, 1-(6- Furanfuranoyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl )-Propane-1,2-dione-3-benzoic acid oxime ester, 1-(6-thienyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1, 2-dione-2-acetoxime ester, 2-((benzoyloxy)imino)-1-phenylpropane-1-one, 1-phenyl-1,2-propanedione-2- (Oxoacetyl)oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane-1,2-dione-2-acetic acid oxime ester, 1-( 9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane-1-one-oxime acetate, 1-(4-(4-(thiophen-2-formyl) Phenylthio)phenyl)-3-cyclopentylpropane-1,2-dione-2-acetic acid oxime ester, 1-(9,9-dibutyl-2-yl)-3-cyclohexylpropyl Propane-1,2-dione-2-acetoxime, 1-(6-(2-(benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl ) Octane-1,2-dione-2-benzoic acid oxime ester, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl ) Methanone-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propane-1-one-benzoic acid oxime Ester, 1-(7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl)-3-cyclohexylpropane-1,2-dione-2-acetic acid oxime ester, 1-(6-(furan-2-formyl)-9-ethylcarbazol-3-yl)-3-cyclohexylpropane-1,2-dione-2-ethoxycarbonyl oxime ester and similar Thing. These oxime ester compounds may be used alone or in combination of two or more.

Exemplarily, triazine compounds include: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4- Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazine -6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s- Triazin-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}ethyl Ester, 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(tri Chloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl ]Phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(tris Chloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1 ,3,-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like. These triazine compounds may be used alone or in combination of two or more.

Exemplarily, the triphenylamine compounds include: N,N-bis-[4-(2-styryl-1-yl)-phenyl]-N,N-bis(2-ethyl-6methylbenzene Group)-1,1-bisphenyl-4,4-diamine, N,N-bis-[4-(2-styryl-1-yl)-4′-methylphenyl]-N, N-bis(2-ethyl-6methylphenyl)-1,1-bisphenyl-4,4-diamine and the like. These triphenylamine compounds may be used alone or in combination of two or more.

Exemplarily, the coumarin compounds include: 3,3'-carbonylbis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin, 3,3'-carbonyl Bis(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 its analogues. These coumarin compounds may be used alone or in combination of two or more.

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

Exemplarily, acridine compounds include: 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methylphenyl acridine, 9-o-chlorophenyl acridine, 9-o-fluorine [4-(9-acridinyl)phenoxy]acetate of phenylacridine, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether cyclohexane ether (ie PAD107, Produced by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3 -Chlorophenyl) acridine, 1,7-bis(9-acridine) heptane, 1,5-bis(9-acridinepentane), 1,3-bis(9-acridine) propane and their Analogs. These acridine compounds may be used alone or in combination of two or more.

Preferably, in 100 parts by mass of the photosensitive resin composition, the content of the other photoinitiator and/or sensitizer is not more than 8 parts by mass.

Additives

In addition to the above-mentioned components, the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other auxiliary agents as needed. Illustratively, the auxiliary agent may be dyes such as malachite green, tribromophenyl sulfone, colorless crystal violet and other light color developers, pigments, fillers, plasticizers, stabilizers, coating aids, peeling accelerators, etc. .

As the above-mentioned dyes, pigments, and photochromic agents, exemplarily, tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, fluorane Phthalocyanines such as dyes, toluenesulfonic acid monohydrate, basic magenta, phthalocyanine green and phthalocyanine blue, auramine, by-product magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock Green, Diamond Green, Basic Blue 20, Brilliant Green, Eosin, Ethyl Violet, Erythrosine Sodium B, Methyl Green, Phenolphthalein, Alizarin Red S, Thymol Phenolphthalein, Methyl Violet 2B, Quinadine Red, Rose Bengal Agar, Mitaniel Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenyl Flucarbazone, 2,7-Dichlorofluorescein, Pan-Methyl Red , Congo red, Benzo red purple 4B, α-naphthyl red, phenacetin, methyl violet, Victoria pure blue BOH, rhodamine 6G, diphenylamine, dibenzylaniline, triphenylamine, di Ethylaniline, diphenyl-p-phenylene diamine, p-toluidine, benzotriazole, methamphetamine, 4,4'-biphenyldiamine, o-chloroaniline, white crystal violet , White malachite green, white aniline, white methyl violet, azo and other organic pigments, titanium dioxide and other inorganic pigments. In consideration of having a good contrast, it is preferable to use tris(4-dimethylaminophenyl)methane (ie, leuco crystal violet, LCV). These dyes, pigments and photochromic agents may be used alone or in combination of two or more.

As the filler, for example, fillers such as silica, alumina, talc, calcium carbonate, and barium sulfate (excluding the above-mentioned inorganic pigments) may be used. The filler may be used alone or in combination of two or more.

As the above-mentioned plasticizer, for example, it may be: phthalate such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, etc. Glycol esters such as acid esters, triethylene glycol diacetate, tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide, triphenyl phosphate, Trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, tricresyl phosphate, 2-naphthyl Diphenyl phosphate, tolyl bis 2,6-xylyl phosphate, aromatic condensed phosphate, tri(chloropropyl) phosphate, tri(tribromo neopentyl) phosphate, halogen-containing condensed phosphate , Triethylene glycol dicaprylate, triethylene glycol bis(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris(2-ethyl phosphate Ethyl ester), Brij 30 [C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₄ OH], Brij 35 [C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₂₀ OH], etc. The plasticizer may be used alone or in combination of two or more.

As the above stabilizer, exemplarily, it may be: hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide, 1 -Phenyl-3-pyrazolidone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, tert-butylcatechol, 1,2,3-pyrogallol, copper resinate, naphthalene Amine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloroquinone. The stabilizer may be used alone or in combination of two or more.

As the coating aid, from the viewpoint of safety and versatility, it may be: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate , Ethyl lactate, cyclohexanone, γ-butyrolactone, dichloromethane, etc. The coating aid may be used alone or in combination of two or more.

Examples of the above-mentioned peeling accelerator include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, methyl, propyl, heptyl, octyl, decyl, and dodecane Alkylbenzene sulfonic acid, etc. The peeling accelerator may be used alone or in combination of two or more.

Preferably, in 100 parts by mass of the photosensitive resin composition, the content of the auxiliary agent is not more than 10 parts by mass.

The photosensitive resin composition of the present invention can be prepared as a dry film, that is, a photosensitive resin laminate, and is used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages through different processes in different The desired pattern is formed on the substrate.

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

Dry film applications

The photosensitive resin laminate which is a dry film of the present invention includes a photosensitive resin layer formed of a photosensitive resin composition and a support that supports the photosensitive resin layer.

Generally, the production of a dry film includes: coating a photosensitive resin composition on a support and drying to form a photosensitive resin layer; optionally, attaching a cover film (protective layer) as needed. Preferably, the drying conditions are 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 more preferably 15-30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation is not good, and if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be poor.

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

The coating of the photosensitive resin composition is not particularly limited, and for example, a spray coating method, a drum coating method, a spin coating method, a slit coating method, a compression coating method, a curtain coating method, and a dye coating can be used Conventional methods such as cloth method, line coating method, blade coating method, roll coating method, blade coating method, spray coating method, dip coating method, etc.

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

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

(2) Exposure step: Expose the photosensitive resin layer in the photosensitive resin laminate, and irradiate active light in the form of an image to photocur the exposed portion;

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

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

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

Further, the present invention provides the application of the above dry film in manufacturing a protective pattern, including the above-mentioned lamination step, exposure step and development step, the difference is that in the lamination step, the photosensitive resin laminate can be laminated on various materials On the substrate.

Further, the present invention provides the application of the above dry film in manufacturing a conductor pattern, including the above-mentioned lamination step, exposure step, development step, and conductor pattern formation step, except that in the lamination step, the photosensitive resin laminate is laminated on the metal Board or metal-coated insulating board.

Further, the present invention provides the application of the above dry film in manufacturing a frame wire, including the above-mentioned lamination step, exposure step, development step, and conductor pattern forming step, except that the photosensitive resin laminate is laminated in the lamination step On the metal plate, the part not covered by the protection pattern is etched in the conductor pattern forming process.

Further, the present invention provides the application of the above dry film in the manufacture of semiconductor packages, including the above-mentioned lamination step, exposure step, development step, and conductor pattern forming step, the difference is that in the lamination step, the photosensitive resin laminate is laminated on On a wafer with a large-scale integrated circuit, the part not covered by the protection pattern is plated in the conductor pattern forming process.

Wet film applications

The photosensitive resin composition of the present invention can be directly applied on a substrate by a wet film method, and is used for the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.

Without limitation, the photosensitive resin composition can be applied on the substrate by conventional methods such as roll coating, blade coating, spray coating, and dip coating, and dried to form the photosensitive resin layer.

After the photosensitive resin layer is formed on the substrate, subsequent processes such as an exposure process, a development process, a conductor pattern forming process, and a peeling process can all be performed with reference to the application method of the dry film.

Process steps

In the exposure process, the exposure may include a mask exposure method (a method in which a negative or positive mask pattern of a wiring pattern irradiates active light in the form of an image), a projection exposure method, or a direct imaging exposure method using laser, digital optics The method of direct drawing exposure, such as the processing exposure method, irradiates the active light in the form of an image. As the light source of active light, a well-known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure indicator lamp, a high-pressure indicator lamp, a gas laser such as a xenon lamp, an argon laser, a solid laser such as a YAG laser, a semiconductor laser, and gallium nitride can be used It is a blue-violet laser and other light sources that effectively emit ultraviolet light. In addition, a light source that efficiently emits visible light such as a floodlight for photography or a fluorescent lamp can also be used.

The photosensitive resin composition of the present invention is not particularly limited to the type of light source of active light, and the exposure amount is preferably 10-1000 mJ/cm ² .

In the development step, the unexposed portion of the photosensitive resin layer is removed with a developer. When the support is present on the photosensitive resin layer, the support can be removed by an automatic peeler, etc., and then the unexposed portion can be removed using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Examples of the alkaline aqueous solution may be 0.1-5 mass% sodium carbonate solution, 0.1-5 mass% potassium carbonate solution, 0.1-5 mass% sodium hydroxide solution, etc. The pH value is preferably 9-11. Surfactants, defoamers, organic solvents, etc. can also be added to the alkaline aqueous solution. The development method may be conventional methods such as dipping, spraying, and brushing.

In the etching process, using the resist pattern (ie, the protection pattern) formed on the substrate as a mask, the conductor layer of the uncovered circuit-forming substrate is etched away to form a conductor pattern. The etching method can be selected according to the conductor layer to be removed. For example, examples of the etching solution include copper oxide solution, iron oxide solution, alkali etching solution, hydrogen peroxide-based etching solution, and the like.

In the plating process, using the resist pattern formed on the substrate as a mask, copper, solder, or the like is plated on the insulating plate of the uncovered circuit-forming substrate. After the plating process, the resist pattern is removed to form a conductor pattern. As a method of the plating treatment, either electroplating treatment or electroless plating treatment may be used, and electroless plating treatment is preferable. Examples of the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, high-throw solder plating and other solder plating, and watt bath (nickel sulfate-chloride) Nickel) plating and nickel sulfamate plating and other nickel plating, hard gold plating and soft gold plating and other gold plating.

The resist pattern can be removed by an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step. As an example of a strong alkaline aqueous solution, for example, a 1-10% by mass sodium hydroxide aqueous solution can be used.

BRIEF DESCRIPTION

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

Figure 2 is the structure spectrum of T1 obtained by single crystal diffraction

Figure 3 is a comparison of the sensitivity test results of compounds a1, a2, a3, a8, a9, a10

detailed description

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

1. Hexaarylbisimidazole mixed photoinitiator

1.1 Preparation of hexaarylbisimidazole mixed photoinitiator a1

Under the protection of nitrogen, put 31.8g 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1), 51.3g 2,5-di(o-chlorophenyl)- into a 1L four-necked flask 4-(4,5-dimethoxyphenyl)-imidazole (M2), 4.2g 30% liquid alkali, 4.0g tetrabutylammonium bromide and 300g toluene, heated and stirred, and added dropwise at 60-65℃ 85g of sodium hypochlorite (11% aqueous solution), after the dropwise addition, the reaction was kept warm, and the samples were collected and controlled by HPLC, until both M1 and M2 were less than 1%, the reaction was complete, and the heat preservation was ended.

After the holding reaction was completed, it was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. Add 70g of methanol to the material obtained by distillation, heat and stir until it is dissolved, and then add the droplets of solution to the recrystallization solution made up of 30g of methanol and 50g of pure water. After drying, 79.1 g of product a1 was obtained.

The product was analyzed using high performance liquid chromatography.

Figure 1 is a high performance liquid chromatogram of product a1. The analysis result shows that the total content of the product peaks of the four connection sites of 1'-2, 2-3', 1-2' and 2'-3 is 92.5%.

The product a1 is a mixture obtained from two different monoimidazoles (ie, M1, M2) by pair-wise coupling and mutual coupling, including T1, T2, and T3. In order to accurately verify the structural composition of the product, the components a1-1, a1-2 and a1-3 were verified and analyzed.

By means of monoimidazole self-coupling, column chromatography, chromatographic separation and other means, pure T1, T2 and T3 were obtained, respectively, and the structure was confirmed.

T1 has only one peak in the liquid phase, but two peak shapes are obtained by single crystal diffraction, see Figure 2. According to the structural characteristics, it can be determined that the main product of the coupling of two monoimidazoles is a mixture of N containing hydrogen on one imidazole and C on the 2-position of the other imidazole, thus indicating that the structure of T1 is The 1-2' and 2'-3 connection positions mentioned above.

The imidazole used to synthesize T1 is M1, which belongs to symmetric imidazole, so the 1-2' and 2'-3 obtained by coupling are of similar polarity, and the liquid phase is difficult to separate. And because of the structural symmetry of M1, the structure of the product obtained by its own coupling is 1-2' and 1'-2, and 2'-3 and 3-2' are the same, so the main structure of T1 is 1- The products of the two connecting positions of 2'and 3-2' have the structural formulas as shown below, respectively T1-1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-diimidazole and T1-2: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole;

Similarly, the separated pure T2 was analyzed, the main structure was four connected products, and the structure was confirmed by LCMS. Mass spectrometry analysis obtained 849 and 850 molecular fragment peaks with the aid of software attached to the instrument. The molecular weight of the product was 848, which was consistent with T+1 and T+2, proving that these four products have similar structures and the same molecular weight. The monoimidazole M2 synthesized by T2 belongs to asymmetric monoimidazole. There are two configurations of M2, M2-1 and M2-2, as shown below:

T2 is synthesized by asymmetric monoimidazole coupling. In theory, there are eight main structures connected by 1-2 and 2-3 connecting sites, but for the self-coupled monoimidazole, the structure of 1-2' is the same as 1'-2. , The structure of 2'-3 and 3-2' is also the same, so for T2, there are actually four main structures connected by 1-2 and 2-3 connection sites, and their compositions are:

T2-1: 2,2',5,5'-tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole, T2 -2: 2,2',4,5'-tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole, T2- 3: 2,2',5,5'-tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole, T2-4 : 2,2',4,5'-tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole, the structure is shown below :

T3 is formed by coupling M1 and M2 two by two. The main structure of the pure T3 separated in the liquid phase is the product with four kinds of connection positions. The structure of the products with four kinds of connection positions is confirmed by LCMS. Mass spectrometry analysis obtained molecular fragment peaks of 755 and 756 with the software attached to the instrument. The molecular weight of the product was 754, which was consistent with T+1 and T+2, proving that these four products have similar structures and the same molecular weight. T3 is formed by connecting symmetrical imidazole M1 and asymmetrical imidazole M2 two by two. There are four main structures connected by 1-2 and 2-3 connection sites, which are composed of:

T3-1: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-di Imidazole, T3-2: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3 -Diimidazole, T3-3: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2, 3'-diimidazole, T3-4: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl- 1',2-Diimidazole, the structural formula is as follows:

Based on the above experimental analysis, it is determined that the product a1 is composed of T1 (T1-1, T1-2), T2 (T2-1, T2-2, T2-3, T2-4) and T3 (T3-1, T3-2, T3-3, T3-4) combined, in which the content of the biimidazole compound composed of four connecting positions 1'-2, 2-3', 1-2' and 2'-3 in a1 is 92.5% .

1.2 Preparation of a2-a10

A2-a10 were prepared separately, and the conditions of each product are shown in Table 1 below.

Table 1

It can be seen from the solubility data in the above table that the solubility of pure HABI (a6 and a7) with a single structure is very poor, and even if it is mixed with other HABI (a4 and a5), the solubility cannot be improved. The initiator must have the structure of the same substituent and there are four kinds of linking sites simultaneously to achieve the optimal solubility shown in the present invention.

1.3 Sensitivity test

Due to the poor solubility when using pure T2-3 or T3-4, it is difficult to perform sensitivity test, so only the sensitivity data of a1, a2, a3, a8, a9, a10 were tested.

Referring to the formulation shown in Table 2, the photosensitive resin compositions of Comparative Examples 1-6 were prepared for sensitivity test, and the unit of dosage of each substance in the table was g.

Table 2

In Table 1 above, TMPTA was purchased from Tianjin Beilian Fine Chemical Development Co., Ltd., NPG was purchased from Shenzhen Pengshunxing Technology Co., Ltd., and PGMEA was purchased from Jinan Huifengda Chemical Co., Ltd.

Prepare the sample according to the above formula. After mixing, take 1.0 mg of the sample and lay it flat on the bottom of the crucible, and then put it into the furnace body of the differential scanning calorimeter (model: DSC8000, manufacturer: PerkinElmer) for testing.

The peak value represents the maximum heat dissipation, mw/mg, the greater the heat dissipation, the higher the sensitivity. The slope represents the curing rate, the smaller the slope, the higher the sensitivity.

The results are shown in Figure 3. The sensitivity test results are: a10 (76.1%) <a9 (83.0%) ≈ a8 (88.5%) <a1 (92.5%) ≈ a2 (95.6%) ≈ a3 (98.3). This further confirms that the total mass of the biimidazole compound composed of four connection sites of 1'-2, 2-3', 1-2' and 2'-3 in the mixed photoinitiator has a certain effect on the sensitivity, when When the content is higher than 92%, the sensitivity is improved.

1.4 Preparation of a11

Under nitrogen protection, put 50g 2-(4-chlorophenyl)-5-(6-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole into a 1L four-necked flask ( M3), 51g 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole (M2), 5.6g 30% liquid alkali, 4.0g tetrabutylammonium bromide And 300g of toluene, heated and stirred, and 90g of sodium hypochlorite (11% aqueous solution) was added dropwise at 60-65°C. After the end of the addition, the reaction was kept warm, and the sample was controlled by HPLC until both M2 and M3 were less than 1%, the reaction was complete To end the insulation.

After the holding reaction was completed, it was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. Add 70g of methanol to the material obtained by distillation, heat and stir until the solution is clear, then add the solution clear droplets to the recrystallization solution composed of 30g methanol and 50g pure water, rinse and drain after the end of the addition , Baking material, to obtain 98g of product a11.

The analysis result shows that the total content of the product peaks of the four connection sites of 1'-2, 2-3', 1-2' and 2'-3 is 92.5%.

The product a11 is a mixture obtained from two different monoimidazoles (ie, M2 and M3) by pairwise coupling and mutual coupling, including T2, T4 and T5. In order to accurately verify the structure of the product, the components T2, T4 and T5 were analyzed and verified.

By means of monoimidazole self coupling, column chromatography, chromatographic separation and other means, T2, T4 and T5 were obtained respectively, and the structure was confirmed separately.

T2 has the same structure as compound a1.

T4 is formed by the coupling of asymmetric monoimidazole M3 itself, there are four main structures connected by 1-2 and 2-3 connection sites, and their composition is:

T4-1: 2,2'-bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)- 2,3'-Diimidazole, T4-2: 2,2'-bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4- Dimethoxyphenyl)-1,2'-diimidazole, T4-3: 2,2'-bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4 '-Bis(3,4-dimethoxyphenyl)-1,2'-diimidazole, T4-4: 2,2'-bis(4-chlorophenyl)-4',5-bis(o Chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole, the structural formula is as follows:

The structure was confirmed by LCMS, and the four structural spectra were consistent. Mass spectrometry analysis obtained the peaks of 849 and 850 molecular fragments with the software attached to the instrument. The molecular weight of the product is 848, which is in agreement with T+1 and T+2. It proves that these four product peaks have similar structures and the same molecular weight.

T5 is formed by the coupling of asymmetric M2 and asymmetric M3, and there are four main structures connected by 1-2 and 2-3 connection sites. Their composition is:

T5-1: 2-(4-chlorophenyl)-2', 5,5'-tri(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2 ,3'-diimidazole, T5-2: 2'-(4-chlorophenyl)-2,5,5'-tri(o-chlorophenyl)-4,4'-bis(3,4-dimethyl Oxyphenyl)-1,2'-diimidazole, T5-3: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis (3,4-dimethoxyphenyl)-2',3-diimidazole, T5-4: 2'-(4-chlorophenyl)-2,5,5'-tri(o-chlorophenyl) -4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole, the structural formula is as follows:

Based on the above experimental analysis, it is determined that the product a11 is composed of T2 (T2-1, T2-2, T2-3, T2-4), T4 (T4-1, T4-2, T4-3, T4-4) and T5 ( T5-1, T5-2, T5-3, T5-4), which consists of biimidazole compounds composed of four connecting positions 1'-2, 2-3', 1-2' and 2'-3 The content in a11 is 92.5%.

A12-a20 were prepared separately, and the conditions of each product are shown in Table 3 below.

table 3

The solubility data in the table above further shows that the solubility of pure HABI (a16 and a17) with a single structure is very poor, and even if it is mixed with other HABI (a14 and a15), the solubility cannot be improved. It is necessary for the structure of the same substituent to have four kinds of connection sites at the same time in order to achieve the optimal solubility shown in the present invention.

1.5 Preparation of a21

Under nitrogen protection, put 35g 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1), 39g2-(2,4-dichlorophenyl)-4 into a 1L four-necked flask, 5-Diphenyl-imidazole (M4), 5.6g 30% liquid alkali, 4.0g tetrabutylammonium bromide and 250g toluene, heated and stirred, and 87g sodium hypochlorite was added dropwise at 60-65°C, and kept warm after the dropwise addition The reaction was sampled and controlled by HPLC until both M1 and M4 were less than 1%. The reaction was complete and the heat preservation was completed.

After the heat retention reaction was completed, it was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. Add 60g of methanol to the material obtained by distillation, heat and stir until it is dissolved, and then add the droplets of solution to the recrystallization solution made up of 30g of methanol and 50g of pure water. After the dropwise addition, rinse and drain. , Baking material, to obtain 66g of product a21.

The analysis result showed that the total content of the product peaks of the four connection sites of 1'-2, 2-3', 1-2' and 2'-3 was 92.1%.

The product a21 is a mixture obtained from two different symmetrical monoimidazoles (ie, M1, M4) by pairwise self-coupling and mutual coupling, including T1, T6, and T7. In order to accurately verify the structure of the product, the components T1, T6 and T7 were verified and analyzed.

By means of monoimidazole self coupling, column chromatography, chromatographic separation and other means, T1, T6 and T7 were obtained respectively, and the structure was confirmed separately.

T1 has the same structure as compound a1.

T6 has two structures, but there is only one peak in the liquid phase, and its structural composition is similar to that of T1. T6 is obtained by self-coupling of symmetric imidazole, so the polarities of 1-2' and 2'-3 obtained by coupling are similar , The liquid phase is difficult to separate, the structural formula is as follows, respectively T6-1: 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-diimidazole and T6-2: 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole;

The separated T6 was analyzed, and the structure was confirmed by LCMS. Mass spectrometry analysis obtained 729 and 730 molecular fragment peaks with the software attached to the instrument. The molecular weight of the product was 728, which was in agreement with T+1 and T+2, proving that these two products have similar peak structures and the same molecular weight.

T7 is formed by coupling symmetrical M1 and symmetrical M4 two by two. There are four main structures connected by 1-2 and 2-3 connection sites, whose composition are:

T7-1: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,3'-diimidazole, T7 -2: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1',2-diimidazole, T7- 3: 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, T7-4 : 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole, the structural formula is shown below :

The separated T7 was analyzed, and the structure was confirmed by LCMS. Mass spectrometry analysis obtained 695 and 696 molecular fragment peaks with the aid of software attached to the instrument. The molecular weight of the product is 694, which is in agreement with T+1 and T+2, proving that the four products have similar peak structures and the same molecular weight.

Based on the above experimental analysis, it is determined that the product a21 is composed of T1 (T1-1, T1-2), T6 (T6-1, T6-2) and T7 (T7-1, T7-2, T7-3, T7-4) It is a combination, in which the content of the biimidazole compound composed of four connecting positions of 1'-2, 2-3', 1-2' and 2'-3 in a21 is 92.1%.

A22-a30 were prepared separately, and the conditions of each product are shown in Table 4 below.

Table 4

The solubility data in the table above further shows that the solubility of pure HABI (a26 and a27) with a single structure is very poor, and even if it is mixed with other HABI (a24 and a25), the solubility cannot be improved. The HABI-type mixed photoinitiators described in the present invention It is necessary for the structure of the same substituent to have four kinds of connection sites at the same time in order to achieve the optimal solubility shown in the present invention.

1.5 Preparation of a31

Under nitrogen protection, put 35g 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1), 44g2-(o-chlorophenyl)-4,5-di( 2-naphthyl)-imidazole (M5), 5.6g of 30% liquid alkali, 4.0g of tetrabutylammonium bromide and 300g of toluene, heating and stirring, and adding 97g of sodium hypochlorite dropwise at 60-65°C, keeping warm after the dropwise addition The reaction was sampled and controlled by HPLC until both M1 and M5 were less than 1%. The reaction was complete and the heat preservation was completed.

After the holding reaction was completed, it was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. Add 60g of methanol to the material obtained by distillation, heat and stir until it is dissolved, and then add the droplets of solution to the recrystallization solution made up of 30g of methanol and 50g of pure water. After the dropwise addition, rinse and drain. , Baking material, to obtain 76g of product a31.

The analysis result shows that the total content of the product peaks of the four connection sites of 1'-2, 2-3', 1-2' and 2'-3 is 92.7%.

The product a31 is a mixture obtained from two different symmetrical monoimidazoles (ie, M1, M5) through pairwise self-coupling and mutual coupling, including T1, T8, and T9. In order to accurately verify the structure of the product, the components T1, T8 and T9 were verified and analyzed.

By means of monoimidazole self coupling, column chromatography, chromatographic separation and other means, T1, T8 and T9 were obtained respectively, and the structure was confirmed separately.

T1 has the same structure as compound a1.

T8 has two structures, but there is only one peak in the liquid phase, and its structural composition is similar to that of T1. T8 is obtained by self-coupling of symmetric imidazole (M5), so the 1-2' and 2'-3 obtained by coupling The polarities are similar, and the liquid phase is difficult to separate. The structural formulas are as follows: T8-1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(2-naphthyl )-1,2'-diimidazole and T8-2: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(2-naphthyl)-2',3- Diimidazole

The separated T8 was analyzed, and the structure was confirmed by LCMS. Mass spectrometry analysis obtained the molecular fragment peaks of 860 and 861 with the software attached to the instrument. The molecular weight of the product was 859, which was in agreement with T+1 and T+2, proving that the two products had similar peak structures and the same molecular weight.

T9 is formed by coupling symmetrical M1 and symmetrical M5 two by two. There are four main structures connected by 1-2 and 2-3 connection sites, and their composition is:

T9-1: 2,2'-bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1,2'-diimidazole, T9-2: 2,2'-bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2',3-diimidazole, T9-3: 2,2' -Bis(o-chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-1',2-diimidazole, T9-4: 2,2'-bis(o Chlorophenyl)-4,5-bis(2-naphthyl)-4'5'-diphenyl-2,3'-diimidazole, the structural formula is as follows:

The separated T9 was analyzed, and the structure was confirmed by LCMS. The mass spectrometry analysis obtained the molecular fragment peaks of 760 and 761 with the software attached to the instrument. The molecular weight of the product was 759, which was consistent with T+1 and T+2, which proved that the four products had similar peak structures and the same molecular weight.

Based on the above experimental analysis, it is determined that the product a31 is composed of T1 (T1-1, T1-2), T8 (T8-1, T8-2) and T9 (T9-1, T9-2, T9-3, T9-4) It is a combination, in which the content of the biimidazole compound composed of four connecting positions of 1'-2, 2-3', 1-2' and 2'-3 in a21 is 92.7%.

A32-a40 were prepared separately, and the conditions of each product are shown in Table 5 below.

table 5

The solubility data in the above table further shows that the solubility of pure HABI (a36 and a37) with a single structure is very poor, and even if it is mixed with other HABI (a34 and a35), the solubility cannot be improved. The HABI-type mixed photoinitiators described in the present invention It is necessary for the structure of the same substituent to have four kinds of connection sites at the same time in order to achieve the optimal solubility shown in the present invention.

2. Preparation of photosensitive resin composition

Referring to the formulations shown in Tables 5-7, the components are mixed uniformly to prepare a photosensitive resin composition. Unless otherwise specified, the parts shown in the table are parts by mass.

Table 6

Table 7

Table 8

Table 9

The meaning of each component code in Table 6-9 is shown in Table 10.

Table 10

In Table 10, the preparation of alkali soluble polymer C1: Under a nitrogen atmosphere, a flask equipped with a stirrer, reflux cooler, thermometer and dropping funnel was charged with methyl cellosolve and toluene at a mass ratio of 3:2 500g of the prepared mixed solvent is stirred and heated to 80°C. A solution was prepared by mixing 100g of methacrylic acid, 200g of ethyl methacrylate, 100g of ethyl acrylate, 100g of styrene, and 0.8g of azobisisobutyronitrile, which was then slowly added dropwise to the flask for 4 hours After the dropwise addition, the reaction was continued for 2 hours. Next, 100 g of a mixed solvent (the composition is the same as above) in which 1.2 g of azobisisobutyronitrile was dissolved was dropped into the flask, and the dropping time was 10 minutes. After the dropwise addition, the reaction was further performed at 80° C. for 3 hours, and the temperature was raised to The reaction was continued at 90°C for 2 hours. After the reaction, the alkali soluble polymer C1 was obtained by filtration, and the weight average molecular weight was about 80,000.

3. Performance evaluation

3.1 Evaluation method

Taking the dry film application method as an example, each application performance of the photosensitive resin compositions shown in the above examples and comparative examples was tested.

The photosensitive resin composition was sufficiently stirred, and it was evenly coated on the surface of a 25 μm thick polyethylene terephthalate film as a support using a bar coater, and dried in a dryer at 95° C. for 5 minutes. A photosensitive resin layer with a thickness of 40 μm was formed, and then a 15 μm-thick polyethylene film as a protective layer was laminated on the surface of the photosensitive resin layer where no polyethylene terephthalate film was laminated to obtain a dry film.

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

The polyethylene film protective layer was peeled off from the dry film, and then using a hot roll laminator (AL-70 manufactured by Asahi Kasei Co., Ltd.), it was laminated on a copper clad preheated to 60°C at a roll temperature of 105°C. Laminate. The gas pressure is 0.35 MPa, and the lamination speed is 1.5 m/min.

The mask was placed on a polyethylene terephthalate film as a support, and exposed by an ultra-high pressure mercury lamp (HMW-201KB manufactured by ORCMANUFACTURINGCO., LTD.).

The polyethylene terephthalate film was peeled off, and a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. was sprayed on the photosensitive resin layer using an alkali developing machine (developer for dry film manufactured by FujiKiko Co., Ltd.) Above, the unexposed portion of the photosensitive resin layer is dissolved and removed in a time twice as long as the minimum development time. The minimum development time is the shortest time required to completely dissolve the photosensitive resin layer of the unexposed portion.

3.2 Evaluation content

(1) Compatibility

The photosensitive resin composition was sufficiently stirred, and the composition was uniformly coated on the surface of a 25 μm-thick polyethylene terephthalate film as a support using a bar coater. Dry in a dryer at 95°C for 5 min to form a photosensitive resin layer. Then the surface of the photosensitive resin layer was visually inspected and graded as follows:

◇: Even surface;

◆: Undissolved matter is deposited on the surface.

(2) Sensitivity

The photosensitive resin layer was exposed for 15 minutes using a 21-stage stepped exposure meter manufactured by Stouffer with a 21-stage brightness change from transparent to black to evaluate its sensitivity. After the exposure, development is carried out at twice the minimum development time, and according to the exposure amount of the stepped exposure table with the resist film completely remaining being 8, the following classification is performed:

○: The exposure is 20mJ/cm ² or less;

◎: The exposure is 20mJ/cm ² -50mJ/cm ² , excluding the end value;

●: The exposure is 50mJ/cm ² or more.

(3) Resolution

After exposure and development using a photomask having a wiring pattern of Line/Space=10:10-150:150 (unit: μm), the resolution of the dry film was measured. The resolution is the minimum value of the pattern after the unexposed portion is cleaned out of the resist pattern formed by development after exposure.

○: Resolution value is below 30μm;

◎: The resolution value is 30μm-50μm, excluding the end value;

●: The resolution value is above 50μm.

(4) Hydrophilicity

The hydrophilicity was evaluated by the amount of precipitation after the photosensitive resin layer was dissolved.

The photosensitive resin composition was sufficiently stirred, and applied uniformly on the surface of a 25 μm-thick polyethylene terephthalate film as a support using a bar coater. Dry in a dryer at 95°C for 4 minutes to form a photosensitive resin layer with a layer thickness of approximately 30.5 μm and a layer weight of approximately 3.2 g.

Dissolve 20g of sodium carbonate in 2L of water, add 1.5ml of P1uronic RPG3110 (BASF, Mt. Olive, NJ, this reagent is polyoxyethylene and polyoxypropylene copolymer plasticizer) to prepare a developer. Put the above-mentioned film with photosensitive resin layer into 100g developer solution, let the sample stand until the resin layer is dissolved, and the amount of precipitation is determined according to the following grade:

0=precipitation amount is less than 0.005g;

1 = A small amount of finely dispersed light yellow matter with a precipitation amount between 0.005-0.01g;

5=Medium amount of light yellow substance (usually fine), the amount of precipitation is between 0.05-0.08g;

10=There are a large number of light yellow substances in the solid layer (usually in the form of flakes), and the amount of precipitation is above 0.1 g.

(5) developability

After development, the photoresist pattern was observed by a scanning electron microscope (SEM) to evaluate developability.

The developability is evaluated according to the following criteria:

□: No residue was observed in the unexposed part;

△: A small amount of residue was observed in the unexposed part, but the amount of residue was acceptable;

×: A clear residue was observed in the unexposed part.

3.3 Evaluation results

The evaluation results are shown in Table 11.

The HABI mixed photoinitiator of the present invention has excellent compatibility when applied to a photosensitive resin composition. The composition has high sensitivity, good resolution and developability, and has excellent hydrophilicity, making the developer It can be reused, and there will be no clogging of the filter by developing garbage. Compared with the photosensitive resin composition of Comparative Examples 1-28, the comprehensive application performance advantage of the present invention is remarkable.

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, changes, modifications, substitutions, combinations, etc. that do not depart from the spirit and principles of the present invention The simplifications should all be equivalent replacement methods, which are all included in the protection scope of the present invention.

Claims

A hexaarylbisimidazole mixed photoinitiator with a structure as shown in the general formula (I), which contains four connection positions of 1'-2, 2-3', 1-2' and 2'-3 A double imidazole compound, and the total mass percentage of the double imidazole compound composed of these four connection positions in the hexaarylbisimidazole mixed photoinitiator is more than 92%,

In the general formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group.
The hexaarylbisimidazole-based mixed photoinitiator according to claim 1, characterized in that it satisfies 1'-2, 2-3', 1-2' and 2'- of the structure represented by the general formula (I) 3 Four kinds of biimidazole compounds at the linking position have the following structure:
The hexaarylbisimidazole mixed photoinitiator according to claim 1 or 2, wherein the substituents on the aryl group are halogen, nitro, cyano, amine, hydroxyl, C 1 -C 20 Alkyl or alkenyl, C 1 -C 8 alkoxy, wherein the methylene in each independent variable may be optionally substituted with oxygen, sulfur, imino.
The hexaarylbisimidazole mixed photoinitiator according to any one of claims 1-3, wherein the substituents on the aryl group are fluorine, chlorine, bromine, nitro, cyano, amine, Hydroxyl group, C 1 -C 10 alkyl group or alkenyl group, C 1 -C 5 alkoxy group, wherein the methylene group in each independent variable may be optionally substituted by oxygen, sulfur, imine group.
The hexaarylbisimidazole mixed photoinitiator according to any one of claims 1 to 4 , wherein at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and Ar 6 contains The aryl group of the halogen substituent.
The hexaarylbisimidazole mixed photoinitiator according to claim 5, wherein the halogen substituent is chlorine.
The hexaarylbisimidazole mixed photoinitiator according to any one of claims 1-6, characterized in that it satisfies 1'-2, 2-3', 1- that satisfy the structure represented by the general formula (I) The total mass percentage content of the 4′ and 2′-3 biimidazole compounds in the mixed photoinitiator is more than 95%.
The hexaarylbisimidazole-based mixed photoinitiator according to any one of claims 1 to 7, characterized in that: 1'-2, 2-3', 1 satisfying the structure represented by the general formula (I) -2'and 2'-3 four imidazole compounds connected position.
A photosensitive resin composition containing the hexaarylbisimidazole mixed photoinitiator according to any one of claims 1-9.
The photosensitive resin composition according to claim 9, further comprising: an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, other photoinitiators and/or sensitizers, and optional auxiliary agents.
The photosensitive resin composition according to claim 10, wherein the alkali-soluble polymer is selected from (meth)acrylic polymer, styrene polymer, epoxy polymer, and aliphatic polyurethane (Meth)acrylate polymer, aromatic urethane (meth)acrylate polymer, amide resin, amide epoxy resin, alkyd resin, and phenol resin.
The photosensitive resin composition according to claim 10 or 11, wherein the alkali-soluble polymer is an alkali-soluble polymer containing a carboxyl group.
The photosensitive resin composition according to claim 12, wherein the carboxyl group-containing alkali-soluble polymer is formed by copolymerizing (meth)acrylate, ethylenically unsaturated carboxylic acid, and other copolymerizable monomers (Meth)acrylate polymer.
The photosensitive resin composition according to claim 10, wherein the compound having an ethylenically unsaturated double bond is a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule.
The photosensitive resin composition according to claim 10 or 14, wherein the compound having an ethylenically unsaturated double bond is selected from bisphenol A (meth)acrylate compounds and has a urethane bond in the molecule (Meth)acrylate compound.
The photosensitive resin composition according to claim 10, wherein the other photoinitiator and/or sensitizer is selected from the group consisting of diimidazoles, pyrazolines, aromatic ketones, anthraquinones, and benzene At least one of benzoin and benzoin alkyl ethers, oxime esters, triazines, triphenylamines, coumarins, thioxanthones, and acridine photoinitiators.
The photosensitive resin composition according to claim 10, wherein the auxiliary agent is selected from the group consisting of dyes, photochromic agents, pigments, fillers, plasticizers, stabilizers, coating aids, and peeling accelerators At least one of them.
A photosensitive resin laminate comprising: the photosensitive resin layer formed of the photosensitive resin composition according to any one of claims 9-17; and a support for supporting the photosensitive resin layer.
Use of the photosensitive resin laminate according to claim 18 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.
Use of the photosensitive resin composition according to any one of claims 9 to 17 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.