KR102685048B1 - HABI-based photoinitiator and its applications that can improve system stability - Google Patents

Abstract

The HABI-based photoinitiator, which can improve system stability and has a structure represented by general formula (I), has a bisimide at four linking positions 2-1', 2-3', 2'-1, and 2'-3. The total mass percentage content of the bisimidazole compound, which includes a dozole compound and has the four linking positions, is more than 92%, and is the sum of the contents of the two linking positions 2-1' and 2'-1 and the two linking positions 2 The ratio of the sum of the contents of -3' and 2'-3 is between 1.5:1 and 2:1. The performance of the photoinitiator can be controlled, and when applied to a photosensitive resin composition, the composition and its dry film have excellent storage stability and do not tend to deteriorate sensitivity and resolution even after long-term storage.
(Ⅰ)

Description

HABI-based photoinitiator and its applications that can improve system stability

The present invention belongs to the field of photocuring technology, and specifically relates to a hexaarylbimidazole-based (HABI) photoinitiator that can improve system stability and its application.

As electronic devices develop in the direction of becoming lighter, thinner, and more compact, the formation of more precise patterns is required, and the pattern line size of printed circuit boards, etc., on which they are mounted is also gradually becoming smaller. In order to manufacture circuit patterns with such narrow spacing at higher yields, a dry film resist with excellent resolution is required, and therefore photosensitive resin compositions with high resolution have become a research issue. As one of the key components of photosensitive resin compositions, photoinitiators that affect the resolution of photosensitive resin compositions are particularly at the core of research.

HABI-based compounds, which have a special chemical structure and can be photo-decomposed under the action of ultraviolet rays to generate polymer free radicals, are a kind of very important photoinitiator in the field of photocuring, especially in the field of free radical polymerization. All conventional HABI photoinitiators on the market are composed of isomers at various different linkage positions. In the application of photosensitive resin compositions, the HABI-based photoinitiators already reported to date only need to apply the isomers they contain directly to the composition without additional requirements for composition. On the one hand, due to differences in production processes, the application performance of HABI-based photoinitiators produced by commercial manufacturers differs greatly, lowering the yield when applied to microcircuits, seriously affecting product quality. On another aspect, conventional Photosensitive resin compositions containing HABI products and their dry films tend to deteriorate in sensitivity and resolution when stored for a long period of time, making it another issue that must be urgently solved due to the easy occurrence of product defects.

In response to the shortcomings of the prior art, the present invention obtains a HABI-based photoinitiator product with improved performance by optimizing the composition and ratio of isomers in the product by controlling variables such as reaction solvent and oxidizing agent during the HABI production process. The performance of the photoinitiator can be controlled, and when applied to a photosensitive resin composition, the composition and its dry film have excellent storage stability and do not tend to deteriorate sensitivity and resolution even after long-term storage.

In order to realize the above-described object, the HABI-based photoinitiator capable of improving system stability having a structure represented by general formula (I) of the present invention has four connection positions 2-1', 2-3', and 2. It includes bisimidazole compounds of '-1, 2'-3, and the total mass percentage content of the bisimidazole compounds having the four linking positions is more than 92%, and the two linking positions 2-1' and 2' The ratio of the sum of contents of -1 (hereinafter abbreviated as connection position 2-1) and the sum of contents of two connection positions 2-3' and 2'-3 (hereinafter abbreviated as connection position 2-3) is 1.5:1. -2:1;

(Ⅰ)

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

Another object of the present invention is to provide a photosensitive resin composition containing the photoinitiator and the application of the composition and its dry film in the manufacturing area of printed circuit boards, protective patterns, conductor patterns, lead frames, semiconductor packaging, etc. It is done.

DETAILED DESCRIPTION OF THE INVENTION

As described above, the present invention relates to a HABI-based photoinitiator capable of improving system stability, a photosensitive resin composition containing the photoinitiator, and application of the composition to a dry film. Below, each of the above aspects is described in more detail.

<HABI photoinitiator>

The HABI-based photoinitiator capable of improving system stability having a structure represented by general formula (I) of the present invention has four connection positions 2-1', 2-3', 2'-1, and 2'-3. It includes a bisimidazole compound, and the total mass percentage content of the bisimidazole compound having the four linking positions is more than 92%, and is the sum of the contents of the two linking positions 2-1' and 2'-1 and the two linking positions. The ratio of the sum of the contents of linking positions 2-3' and 2'-3 is between 1.5:1 and 2:1:

(Ⅰ)

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

Bisimidazole compounds satisfying the four linking positions 2-1', 2-3', 2'-1, and 2'-3 of the structure represented by general formula (I) have the structures specifically listed below. has:

,

2-1’ connection position 2-3’ connection position

,

2’-1 connection position 2’-3 connection position

In general formula (I), the aryl group is preferably a phenyl group.

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

Preferably, the substituent of the aryl group may be halogen, nitro group, cyano group, amino group, hydroxy group, C ₁ -C ₂₀ alkyl group or alkenyl group, C ₁ -C ₈ alkoxy group, where each independent variable ( That is, among each substituent), the methylene group may be selectively substituted with oxygen, sulfur, or imino group.

More preferably, the substituent of the aryl group may be fluorine, chlorine, bromine, nitro group, cyano group, amino group, hydroxy group, C ₁ -C ₁₀ alkyl group or alkenyl group, C ₁ -C ₅ alkoxy group, where, Among each independent variable, the methylene group can be selectively substituted with oxygen, sulfur, or imino group.

Even more 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 improves the discoloration effect during the curing process and the recognition ability of the electronic eye during development (Note: The photosensitive resin layer changes color after exposure, forming a color difference from the unexposed area, thereby forming an electronic eye. perceived by the eye, the present invention can make color differences more clear), thus improving the quality of applied products. Particularly preferably, the halogen substituent is chlorine.

The HABI-based photoinitiator is a type of known photoinitiator in the photoresist field. The production method generally includes oxidative coupling of a triarylimidazole-based compound in the presence of an oxidizing agent, solvent, and phase transfer catalyst, for example US3784557, US4622286, Reference may be made to prior art descriptions such as US4311783, which are hereby incorporated by reference in their entirety.

In order to obtain a HABI-based photoinitiator with improved performance, the present invention optimizes and improves the manufacturing process, as described above. Specifically, the method for producing the HABI-based photoinitiator of the present invention includes the following steps:

(1) Reaction step: Under nitrogen protection, oxidative coupling of the triarylimidazole-based compound in the presence of an oxidizing agent, solvent and phase transfer catalyst, and control through HPLC until the reaction is complete;

(2) Purification step: Wash with pure water to remove inorganic salts, filter and concentrate to obtain the crude product, and then recrystallize and dry to obtain the desired product.

HABI-based compounds are formed by coupling two triarylimidazole compounds (which may be the same or different depending on the substituent of the aryl group). Because the inductive effect of the substituents on the benzene ring reduces the π electron cloud density of the aromatic ring, the inductive effect promotes the distortion of the aromatic ring and causes a shift in the conjugation center of the imidazole ring, resulting in the substitution of the phenyl ring. is placed on a different plane from imidazole (triarylimidazole forms a curved state), and when two triarylimidazole compounds are finally coupled, a different spatial configuration is formed due to the connection of N and C. When expressed, bisimidazole compounds with four linking positions 2-1', 2-3', 2'-1, and 2'-3 are produced.

In order to obtain the HABI-based photoinitiator of the present invention, the oxidizing agent used in the production must have a standard electrode potential (E0) between 0.3-0.9 V, and from the viewpoint of cost, stability, environmental protection, etc. of the oxidizing agent, sodium hypochlorite, One or a combination of two or more of potassium hypochlorite, sodium hypobromite, potassium hypobromite, sodium ferricyanide, and potassium ferricyanide is preferred.

To obtain the HABI-based photoinitiator of the present invention, the solvent used in the preparation has a relative dielectric constant (ε _r ) set to 0-5, and is selected from the group consisting of benzene, toluene, xylene, trimethylbenzene, anisole, and phenetol ( phenetole or ethoxybenzene), etc. are preferred, and toluene is more preferred from the viewpoints of solvent cost, toxicity, recycling, etc.

Dielectric constant (ε) is an important property of a solvent that characterizes its ability to solvate solute molecules and separate ions. A solvent with a high dielectric constant has a greater ion separation ability and a relatively strong solvation ability. The relative permittivity (εr) can be measured using an electrostatic field in the following way: First, measure the capacitance C ₀ when there is a vacuum between the two electrodes of the capacitor, and then use the same distance between the electrodes of the capacitor, but use the same distance between the electrodes. Measure the capacitance _C

.

Here, first, the reaction mechanism of HABI-based compounds will be explained using BCIM as an example: the nitrogen atom of the triarylimidazole molecule becomes negatively charged when it loses the H atom, and the presence of o-chlorophenyl causes the triarylimidazole molecule to have a negative charge of 2. When C at the -position becomes more active, the C atom at the 2-position becomes positively charged due to the charge effect, so the negatively charged N atom attacks the positively charged C atom, and finally, electrons are transferred and BCIM is created. The specific reaction mechanism process is shown as follows:

The reaction of this preparation is a secondary nucleophilic substitution reaction (SN2 reaction). In the SN2 reaction, increasing the degree of solvation after increasing the polarity of the solvent is not favorable for the formation of the SN2 transition state (when the transition state is formed in the SN2 process, the original charge is relatively concentrated in the nucleophile). This is because the charge changes into a relatively dispersed transition state). Meanwhile, hydrogen ions are easily taken from the electron pair donating solvent (e.g. acetone) to generate hydroxyl groups, which affect the reaction by deactivating the positively charged C atom. The inductive effect of lone-pair electrons can accelerate the decomposition of sodium hypochlorite and the production of oxygen, and oxygen can deactivate negatively charged nitrogen atoms to generate nitrogen oxides, and nitrogen oxides can be dissolved in solvents or other By further reacting with the by-product, highly polar by-products are generated in the reaction product, lowering the purity of the obtained reaction product. Therefore, it is preferable to carry out the reaction with a solvent having a relative dielectric constant εr of 0 to 5.

Phase transfer catalysts can help reactants transfer from one phase to another phase where a reaction can occur, thereby accelerating the reaction rate of a heterogeneous system. If there is no phase transfer catalyst, the two phases are separated from each other and the reactants cannot contact each other, so the reaction proceeds slowly. The presence of a phase transfer catalyst enables binding with ions in the aqueous phase (general situation) and promotes the reaction by transferring reactants from the aqueous phase to the organic phase using its affinity for the organic solvent. In the above-described production of the present invention, the phase transfer catalyst used is not particularly limited, but quaternary ammonium salts and cyclic crown ether systems are preferred, and benzyltriethyl ammonium chloride (TEBA), tetrabutyl ammonium bromide (TBAB), tetra Butyl ammonium chloride, Tetrabutylammonium Hydrogen Sulfate, trioctylmethyl ammonium chloride, dodecyltrimethyl ammonium chloride, tetradecyltrimethyl ammonium chloride, 18-crown-6, 15-crown-5, cyclodextrin ), etc.

The reaction temperature is preferably 0-70°C, more preferably 20-70°C. If the reaction temperature is relatively low, the reaction speed is slow, which is disadvantageous in improving production efficiency. If the reaction temperature is too high, on the one hand, it will affect the conversion rate of the reaction, increasing by-products and lowering the purity of the product, and on the other hand, energy consumption will increase, which is not in line with the original intention of lowering production costs.

Satisfactorily, the above-described preparation of the present invention allows control of the composition and ratio of isomers at various linkage positions of the HABI product by controlling process variables such as reaction solvent, oxidizing agent, etc. When the prepared HABI-based photoinitiator is applied to a photosensitive resin composition, the composition and its dry film have excellent storage stability, and there is no tendency for sensitivity and resolution to deteriorate even after long-term storage.

<Photosensitive resin composition>

As described above, when the HABI-based photoinitiator of the present invention is applied to a photosensitive resin composition, it has excellent performance characteristics. Therefore, correspondingly, the present invention is a photosensitive resin composition,

HABI-based photoinitiator (A) as described above;

Alkali soluble polymer (B);

Compound (C) having an ethylenically unsaturated double bond;

hydrogen donor (D);

Other optional adjuvants (E);

A photosensitive resin composition comprising the above components is further provided.

Below, each ingredient is described in more detail.

HABI photoinitiator (A)

The HAB-based mixed photoinitiator of the present invention is selected from or includes the following compounds, illustratively within the limits specified above:

Compound A1:

Compound A2:

Compound A3:

Compound A4:

Compound A5:

.

In the HABI-based photoinitiator of the present invention, for example, Compound A1, Compound A2, etc. can be used individually or in combination of two or more types.

In 100 parts by mass of the photosensitive resin composition, the content of the HABI-based photoinitiator (A) is 1-20 parts by mass, preferably 1-10 parts by mass. If the content is excessively small, there is a defect in that photosensitivity decreases; If the content is excessively high, a defect exists in which the photoresist pattern tends to become wider than the line width of the photomask.

Alkali soluble polymer (B)

The alkali-soluble polymer can impart film forming performance to the photosensitive resin composition. As an alkali-soluble polymer, any polymer having these properties can be applied without particular restrictions.

By way of example, the alkali-soluble polymers applied include (meth)acrylic polymers, styrene-based polymers, epoxy-based polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethane (meth)acrylate polymers, amide-based resins, and amides. It may be an epoxy resin, an alkyd resin, or a phenol resin.

Additionally, alkali-soluble polymers can be obtained through free radical polymerization of polymerizable monomers. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring, such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene; Acrylamide derivatives such as acrylamide and diacetone acrylamide; Ether derivatives of vinyl alcohol such as acrylonitrile and n-butyl vinyl ether; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, and β-styryl (meth)acrylic acid; Alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, Glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-ethylhexyl (meth) (meth)acrylate-based compounds such as acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate; Maleic acid monoesters such as maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, and maleic acid monoisopropyl ester; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propanolic acid, N-vinylcaprolactam; Examples include N-vinylpyrrolidone. These polymerizable monomers can be used individually, or two or more types can be used in combination.

Additionally, considering alkali developability and adhesion, an alkali-soluble polymer containing a carboxyl group is preferably used. The alkali-soluble polymer having a carboxyl group may be an acrylic resin that introduces a carboxyl group using (meth)acrylic acid as a monomer unit and contains (meth)acrylic acid as a monomer unit; It may be a copolymer that further contains alkyl (meth)acrylate as a monomer unit, excluding (meth)acrylic acid; In addition, it may be a copolymer that further includes a polymerizable monomer (for example, a monomer having an ethylenically unsaturated group) other than (meth)acrylic acid and alkyl (meth)acrylate as a monomer component, excluding (meth)acrylic acid.

In addition, alkali-soluble polymers containing carboxyl groups can be obtained through free radical polymerization of polymerizable monomers having carboxyl groups and other polymerizable monomers, especially (meth)acrylates, ethylenically unsaturated carboxylic acids and other copolymerizable monomers. It is a (meth)acrylate-based polymer formed by copolymerization of.

The (meth)acrylate includes 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 ) Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl It may be (meth)acrylate, furfuryl (meth)acrylate, glycidyl (meth)acrylate, etc. These (meth)acrylates can be used individually, or two or more types can be used in combination.

The ethylenically unsaturated carboxylic acid may be acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, or itaconic acid, and is particularly preferably acrylic acid or methacrylic acid. These ethylenically unsaturated carboxylic acids can be used individually, or two or more types can be used in combination.

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

The alkali-soluble polymer can be used individually, or two or more types can be used in combination. Examples of alkali-soluble polymers used in combination of two or more types include two or more alkali-soluble polymers with different copolymerization component compositions, two or more alkali-soluble polymers with different weight average molecular weights, and two or more alkali-soluble polymers with different degrees of dispersion. I can hear it.

In the photosensitive resin composition of the present invention, the weight average molecular weight of the alkali-soluble polymer is not particularly limited and may be suitable for a specific application environment. Considering the mechanical strength and alkali developability comprehensively, the weight average molecular weight is preferably 15,000-200,000, more preferably 30,000-150,000, and particularly preferably 30,000-120,000. If the weight average molecular weight exceeds 15,000, the developer resistance after exposure tends to be further improved, and if the weight average molecular weight is less than 200,000, the development time tends to be shorter, making it compatible with other components such as photoinitiators. You can maintain your temper. The weight average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC) and obtained through conversion using the standard curve of standard polystyrene.

Also, considering the excellent alkali developability, the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, even more preferably 70-250 mgKOH/g, Particularly preferably, it is 100-250 mgKOH/g. If the acid value of the alkali-soluble resin is less than 50 mgKOH/g, it is difficult to secure a sufficient development speed, and if it exceeds 300 mgKOH/g, adhesion is reduced, pattern short-circuiting is likely to occur, storage stability of the composition is reduced, and viscosity is reduced. Problems that arise easily arise.

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 above range, developability is excellent.

In 100 parts by mass of the photosensitive resin composition, the content of the alkali-soluble polymer in the composition is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass. When the content of the alkali-soluble polymer is 20 parts by mass or more, it is possible to ensure improved durability of the photosensitive resin composition for plating, etching, etc., and when the content is 70 parts by mass or less, it is advantageous to increase the sensitivity of the photosensitive resin composition.

Compound (C) having an ethylenically unsaturated double bond

Compounds having ethylenically unsaturated double bonds can promote film formation of the photosensitive resin composition.

The compound having an ethylenically unsaturated double bond is not particularly limited, and any photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used. Illustrative examples include compounds obtained by reacting α,β-unsaturated carboxylic acid and polyol, bisphenol A-based (meth)acrylate compounds, compounds obtained by reacting α,β-unsaturated carboxylic acid and glycidyl-containing compounds, and compounds obtained by reacting α,β-unsaturated carboxylic acid with glycidyl-containing compounds. Urethane monomers such as (meth)acrylate compounds having a urethane bond, nonylphenoxypolyethyleneoxyacrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o- Phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, phthalic acid )-based compounds, alkyl (meth)acrylates, etc. can be given as examples. These compounds can be used individually, or two or more types can be used in combination.

Compounds obtained by reacting the α,β-unsaturated carboxylic acid with polyol include, for example, polyethylene glycol di(meth)acrylate having 2 to 14 ethylene groups, and polypropylene glycol di(meth)acrylate having 2 to 14 propylene groups. ) Acrylate, polyethylene/polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, where the number of ethylene groups is 2-14 and the number of propylene groups is 2-14. Rate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO, 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) Examples include acrylate and tripropylene glycol di(meth)acrylate. These compounds can be used individually, or two or more types can be used in combination. Here, “EO” represents ethylene oxide, and an EO-modified compound refers to a compound having a block structure of an ethylene oxide group; “PO” represents propylene oxide, and a PO-modified compound refers to a compound having a block structure of a propylene oxide group.

Examples of the bisphenol A-based (meth)acrylate compound include 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane, 2,2-bis{4-[( meta)acryloyloxypolypropoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane, 2,2-bis{4-[(meth) Examples include acryloyloxypolyethoxypolypropoxy]phenyl}propane. Examples of the 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane include 2,2-bis{4-[(meth)acryloyloxydiethoxy]phenyl. }Propane, 2,2-bis{4-[(meth)acryloyloxytriethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetraethoxy]phenyl}propane , 2,2-bis{4-[(meth)acryloyloxypentaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexaethoxy]phenyl}propane, 2 ,2-bis{4-[(meth)acryloyloxyheptaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyoctaethoxy]phenyl}propane, 2,2 -bis{4-[(meth)acryloyloxynonaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, 2,2-bis {4-[(meth)acryloyloxyundecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydodecaethoxy]phenyl}propane, 2,2-bis{4 -[(meth)acryloyloxytridecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetradecaethoxy]phenyl}propane, 2,2-bis{4 Examples include -[(meth)acryloyloxypentadecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexadecaethoxy]phenyl}propane, etc. The number of ethylene oxide groups in one molecule of the 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane is preferably 4-20, more preferably 8-15. These compounds can be used individually, or two or more types can be used in combination.

Examples of the (meth)acrylate compound having a urethane bond in the molecule include (meth)acrylate monomers having an OH group at the β position and diisocyanate compounds (isophorone diisocyanate, 2,6-toluene diisocyanate, Addition reactants of (2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.), tris[(meth)acryloyloxytetraethylene glycol isocyanate]hexamethylene isocyanurate, EO modified urethane di(meth) Examples include acrylate, PO modified urethane di(meth)acrylate, EO, and PO modified urethane di(meth)acrylate. These compounds can be used individually, or two or more types can be used in combination.

Examples of the nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, Examples include nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate. These compounds can be used individually, or two or more types can be used in combination.

Examples of the phthalic acid-based compounds include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β'-(meth)acrylo. Examples include one-oxyalkyl-o-phthalate. These compounds can be used individually, or two or more types can be used in combination.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, and n-butyl (meth)acrylate. ) Acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, iso-bornyl (meth)acrylate, hyde. Roxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl ( Meth)acrylate, pentyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, iso-octyl (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, propylene glycol polypropylene ether di(meth) Acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethoxylated polytetrahydrofuranediol di(meth)acrylate, ethoxylated polypropylene glycol di( Examples include meta)acrylate. Here, methyl (meth)acrylate, ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexaacrylate are preferred. These compounds can be used individually, or two or more types can be used in combination.

The compound having the ethylenically unsaturated double bond is preferably a bisphenol A-based (meth)acrylate compound and a (meth)acrylate compound having a urethane bond in the molecule from the viewpoint of improving resolution, plating resistance, and adhesion, and improves sensitivity and From the viewpoint of improving resolution, bisphenol A-based (meth)acrylate compounds are preferred. Commercially available bisphenol A-based (meth)acrylate compounds include 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane (e.g., Shin Nakamura Chemical Industry Co., Ltd.). , Ltd., BPE-200), 2,2-bis{4-[(meth)acryloyloxypolypropoxy]phenyl}propane (e.g., BPE manufactured by Shin Nakamura Chemical Industry Co., Ltd. -5000; FA-321M manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane (ex. Shin Nakamura Chemical Industry Co.) , Ltd., manufactured by BPE-1300), etc.

In 100 parts by mass of the photosensitive resin composition, the content of the compound (C) having an ethylenically unsaturated double bond is preferably 20 to 50 parts by mass, more preferably 25 to 45 parts by mass. When the content of the compound having an ethylenically unsaturated double bond is 20 parts by mass or more, the sensitivity and resolution of the photosensitive resin composition can be further improved; When the content is 50 parts by mass or less, the photosensitive resin composition becomes easier to thin, and durability against etching treatment is further improved.

hydrogen donor (D)

The photosensitive resin composition of the present invention further includes a hydrogen donor to improve photosensitivity. Bisimidazole compounds are split after light irradiation, and the volume of the monoimidazole radical generated increases and the activity decreases due to the steric hindrance effect, making it difficult to initiate monomer polymerization alone. However, when used in combination with a hydrogen donor, the monoimidazole free radical can easily take the active hydrogen of the hydrogen donor to generate a new active free radical, thereby initiating monomer polymerization.

As long as the hydrogen donor has the above-mentioned characteristics, there is no particular limitation on the specific type, and it may include an amine-based compound, a carboxylic acid-based compound, an organic sulfur compound containing a mercapto group, or an alcohol-based compound (but is not limited thereto). does not). These compounds can be used individually or in combination of two or more types.

Amine-based compounds are not particularly limited and include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl- It may include (but is not limited to) aromatic amine compounds such as p-toluidine, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

The carboxylic acid-based compound is not particularly limited and includes aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, It may include (but is not limited to) chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

Organic sulfur compounds containing a mercapto group are not particularly limited and include 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecylthiol, and ethylene glycol bis (3-mercaptobutyrate). , 1,2-propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethyl Allpropanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate) , propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate) nate), trimethylolpropanetris (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol Bis(3-mercaptoisobutyrate), 1,2-propylene glycol bis(3-mercaptoisobutyrate), diethylene glycol bis(3-mercaptoisobutyrate), butanediolbis(3-mercaptoy) isobutyrate), octanediolbis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol Hexakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2-propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mer Captoisobutyrate), butanediolbis (2-mercaptoisobutyrate), octanediolbis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1,2-propylene glycol bis (4-mercap toisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediolbis (4-mercaptovalerate), octanediolbis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate) captovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), 1,2- Propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediolbis(3-mercaptovalerate), octanediolbis(3-mercaptovalerate), trimethylol Aliphatic secondary polyfunctional thiol compounds such as propanetris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), and dipentaerythritol hexakis (3-mercaptovalerate); Secondary aromatics such as diphthalate (1-mercaptoethyl ester), diphthalate (2-mercaptopropyl ester), diphthalate (3-mercaptobutyl ester), and diphthalate (3-mercaptoisobutyl ester). It may be a multifunctional thiol compound.

Alcohol-based compounds are not particularly limited and include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentanol, n-hexanol, cyclohexanol, ethylene glycol, and 1,2-propylene. It may include glycol, glycerol, benzyl alcohol, phenylethyl alcohol, etc. (but is not limited thereto).

In 100 parts by mass of the photosensitive resin composition, the content of the hydrogen donor (D) may be 0.01-20 parts by mass, preferably 0.01-10 parts by mass. When the content of the hydrogen donor is within the above range, it is advantageous to control the photosensitivity of the photosensitive resin composition.

Other optional supplements (E)

In addition to each component described above, the photosensitive resin composition of the present invention may optionally further contain an appropriate amount of other auxiliaries as needed. Illustratively, the auxiliary agent may include at least one of other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating auxiliaries, peeling accelerators, etc.

The other photoinitiators and/or sensitizers include bisimidazole-based, aromatic ketone-based, anthraquinone-based, benzoin and benzoin alkyl ether-based, oxime ester-based, triazine-based, coumarin-based, thioxanthone-based, and acridine-based. and other photoinitiators known to those skilled in the art, but are not limited thereto.

Illustratively, bisimidazole-based 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(2,4-dichlorophenyl)-4,4',5,5 '-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'- Diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-methoxyphenyl) )-4,4',5,5'-tetraphenyl-diimidazole, 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-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5- (o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) -5,5'-bis(o-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-,2',5-bis(o -Chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetra Includes phenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole and analogs thereof. These bisimidazole-based compounds can be used individually or in combination of two or more types.

Illustratively, aromatic ketone-based compounds include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyl diphenyl 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-toluenemercaptobenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4' -Bis(methyl,ethylamino)benzophenone, acetophenone dimethyl ketal, benzyl dimethyl ketal, α,α'-dimethylbenzil ketal, α,α'-diethoxy Acetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-p-hydroxyethyletherphenylpropanone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholine 1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl) 1-butanone, phenylbis(2,4 ,6-trimethylbenzoyl)phosphine oxide, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-1-{3-[4-(2-hydroxy-2-methyl-propionyl) )-phenyl]-1,1,3-trimethyl-inden-5-yl}-2-methylpropanone, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propylene) oneyl)-phenyl]-1,3,3-trimethyl-inden-5-yl}-2-methylpropanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone and analogs thereof. These aromatic ketone compounds can be used individually or in combination of two or more types.

Illustratively, anthraquinone-based compounds include 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene- 9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-di(methyl 4-chlorobutyrate), 2-{3-[( 3-ethyloxetan-3-yl)methoxy]-3-oxopropyl)anthracene-9,10-diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethyl anthracene, 9 , 10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethylthio)anthracene, 9,10-bis(3-hydroxy-1-propylthio)anthracene and their analogues. do. These anthraquinone-based compounds can be used individually or in combination of two or more types.

Exemplarily, benzoin and benzoin alkyl ether-based compounds include benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and analogs thereof. These benzoin and benzoin alkyl ether compounds can be used individually or in combination of two or more types.

Illustratively, the oxime ester-based compound is 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-oximebenzoate (1-(4-phenylthiophenyl)-n-octane-1, 2-dione-2-benzoic acid oxime ester), 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-ethane-1-one-oxime acetate, 1-[6-( 2-methylbenzoyl)-9-ethylcarbazol-3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-propane -1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-cyclohexyl-methan-1-one-oxime acetate, 1-[6- (2-methylbenzoyl)-9-ethylcarbazol-3-yl]-(3-cyclopentyl)-propan-1-one-oximeacetate, 1-(4-phenylthiophenyl)-(3-cyclopentyl) -Propane-1,2-dione-2-oximebenzoate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-oximecyclohexylcarboxylate, 1 -[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-o-methyl Benzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-oximebenzoate, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentyl Propanone)-1-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentylpropanone)-1-oximecyclohexylcarboxylate, 1- (4-benzoyldiphenyl sulfide)-3-cyclopentylpropanone)-1-oximecyclohexylcarboxylate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3- Cyclopentyl)-propane-1,2-dione-2-oxime o-methylbenzoate (1-(6-orthomethylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione -2-orthomethylbenzoic acid oxime ester), 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-oximecyclohexylcarboxylate, 1-(4-thenoyl -Diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-oxime acetate (1-(4-thiopheneformyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one -acetic acid oxime ester), 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazole -3-yl)-3-cyclohexyl-propan-1-one-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propane-1- On-oxime acetate, 1-(6-thenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexylpropanone)-1-oxime acetate, 1-(6-furanfuroyl-9-ethyl Carbazol-3-yl)-(3-cyclopentylpropanone)-1-oxime acetate (1-(6-furanfuroyl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime acetate), 1,4-diphenylpropane-1,3-dione-2-oxime acetate, 1-(6-furoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2 -Dione-2-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1-(6-furanfuroyl-9-ethyl Carbazol-3-yl)-(3-cyclohexylpropanone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-3-oxime Benzoate, 1-(6-thenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 2-[(benzoyloxy) already [n]-1-phenylpropan-1-one, 1-phenyl-1,2-propanedione-2-(oxoacetyl)oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane -1,2-dione-2-oxime acetate, 1-(9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propan-1-one-oxime acetate, 1-{ 4-[4-(thiophen-2-formyl)phenylthio]phenyl}-3-cyclopentylpropane-1,2-dione-2-oxime acetate, 1-[9,9-dibutyl-2-yl ]-3-Cyclohexylpropylpropane-1,2-dione-2-oxime acetate, 1-[6-(2-(benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl] Octane-1,2-dione-2-oxime benzoate, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-oxime acetate, 1- [6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-3-cyclopentyl-propan-1-one-oximebenzoate, 1-[7-(2-methylbenzoyl)-9, 9-dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-oxime acetate, 1-[6-(furan-2-formyl)-9-ethylcarbazole-3 -yl]-3-cyclohexylpropane-1,2-dione-2-ethoxyformyloxime ester and analogs thereof may be included. These oxime ester compounds can be used individually or in combination of two or more types.

Illustratively, the triazine-based compound is 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}prop Cypionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-ethoxyethyl-2-{4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6- yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenyl thio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylamino phenyl)-1,3,-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and analogs thereof. These triazine compounds can be used individually or in combination of two or more types.

Illustratively, coumarin-based compounds include 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis(7-methoxy coumarin), 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 analogs thereof. These coumarin-based compounds can be used individually or in combination of two or more types.

Illustratively, thioxanthone-based compounds include thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Santhone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone and analogs. These thioxanthone-based compounds can be used individually or in combination of two or more types.

Illustratively, acridine-based compounds include 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluo Lophenylacridine, 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acrydine Includes dine, 1,7-bis(9-acridine)heptane, 1,5-bis(9-acridinepentane), 1,3-bis(9-acridine)propane and analogs thereof. These acridine-based compounds can be used individually or in combination of two or more types.

The organic solvent just needs to be capable of dissolving each of the above-mentioned components. For example, it may be a glycol ether-based solvent, an alcohol-based solvent, an ester-based solvent, a ketone-based solvent, an amide-based solvent, a chlorine-containing solvent, etc., and in particular, a colorant, It is desirable to select the alkali-soluble polymer by considering factors such as solubility, applicability, and safety. Preferably, the organic solvent is ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutanol (3 -methyl-3-methoxybutanol), butylcarbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate ( Ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lac Tate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentane on), isophorone (3,5,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4- It may be methylaminolactam or NMP), methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, etc. These solvents can be used individually or in combination of two or more types.

Exemplarily, dyes, pigments, and photochromic agents include tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, fluoran dye, tosylate monohydrate, and basic fuchsin ( basic fuchsin), phthalocyanines such as phthalocyanine green and phthalocyanine blue, auramine base, pararosaniline, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green, basic blue 20 (basic blue 20), brilliant green, eosin, ethyl violet, erythrosin sodium salt B, methyl green, phenolphthalein, alizarin red S , thymol phthalein, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymolsulfonephthalein, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, methyl red, Congo red, benzopurpurine 4B, α-naphthyl red, phenacetin, methyl violet, Victoria Pure Blue BOH, rhodamine 6G, diphenylamine, di Benzylaniline, triphenylamine, diethylaniline, di-p-phenylenediamine, p-toluidine, benzotriazole, methylbenzotriazole, 4,4'-biphenyldiamine, o- Organic pigments such as chloroaniline, leuco crystal violet, white malachite green, leuco aniline, white methyl violet, azo, and inorganic pigments such as titanium dioxide It can be. Considering the excellent contrast, tris(4-dimethylaminophenyl)methane (i.e., leuco crystal violet, LCV) is preferably used. These dyes, pigments, and photochromic agents can be used alone, or by mixing two or more types. You can also use it.

Exemplarily, fillers include fillers such as silica, aluminum oxide, talc, calcium carbonate, and barium sulfate (the inorganic pigments are not included). Fillers can be used individually, or two or more types can be mixed.

Illustratively, the plasticizer is phthalic acid ester such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate, ethylene glycol ester such as triethylene glycol diacetate and tetraethylene glycol diacetate, p-toluenesulfonamide, and benzene. Sulfonamides such as sulfonamide and n-butylbenzenesulfonamide, triphenyl phosphate ester, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tritolyl phosphate, trixylenyl phosphate, tolyl diphenyl phosphate, Trixylenyl phosphate, 2-naphthyldiphenyl phosphate, tolyl-bis2,6-xylenyl phosphate, aromatic condensed phosphate ester, tris(chloropropyl)phosphate, tris(tribromoneopentyl)phosphate, halogen-containing condensation Phosphate ester, triethylene glycol dicaprylate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate suberate), tris(2-ethylethyl) phosphate), 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. Plasticizers can be used individually, or two or more types can be mixed.

Illustratively, the stabilizer is hydroquinone, 1,4,4-trimethyl-diazobicyclo (3.2.2) -non-2-en-2,3-dioxide (1,4,4-Trimethyl-diazobicyclo (3.2.2) )-non-2-ene-2,3-dioxide), 1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, tert-butylcatechol, pyrogallol ), copper resinate, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, Includes dinitrobenzene, p-toluquinone, and chloranil. Stabilizers can be used individually, or two or more types can be mixed.

Illustratively, coating aids include acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, and cyclohexanone. , γ-butyrolactone, dichloromethane, etc. Coating aids can be used individually, or two or more types can be mixed.

Exemplarily, peeling accelerators include benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, and alkylbenzenesulfonic acids such as methyl, propyl, heptyl, octyl, decyl, and dodecyl. The peeling accelerator can be used individually, or two or more types can be mixed.

<Dry film and wet film application>

The photosensitive resin composition of the present invention can be manufactured as a dry film, that is, a photosensitive resin laminate, and is applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging, and can be used to manufacture printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging. Form the necessary patterns for other substrates.

The photosensitive resin composition of the present invention can also be applied to the corresponding substrate at each corresponding manufacturing step through a wet film coater, that is, as a wet film, printed circuit board, protective pattern, conductor pattern, lead frame, Applied to the manufacturing of semiconductor packaging, it forms the necessary patterns on different substrates through different processes.

Application of dry film

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

Typically, the production of a dry film includes the steps of applying a photosensitive resin composition to a support and drying it to form a photosensitive resin layer; Optionally, a step of adhering a cover film (protective layer) is included as needed. Preferably, the drying conditions are 0.5-15 min at 60-100°C. The thickness of the photosensitive resin layer is preferably 5 to 95 μm, more preferably 10 to 50 μm, and even more preferably 15 to 30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation may be poor, and if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be inferior.

As a support, specific examples include various types of plastic films, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polyalkyl methacrylate, and methacrylate copolymer. (methacrylate copolymer), polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, vinyl chloride-vinylacetate copolymer, polytetrafluoroethylene, polytrifluoroethylene and its analogues. Additionally, composite materials composed of two or more materials can also be used. Preferably, polyethylene terephthalate, which has excellent light transparency, is used. The thickness of the support is preferably 5-150 μm, more preferably 10-50 μm.

Coating of the photosensitive resin composition is not particularly limited, and includes, for example, spray coating, drum coating, spin coating, slit coating, extrusion coating, Curtain coating, die coating, wire bar coating, knife coating, roller coating, doctorblade coating, spray coating, dip coating. Conventional methods such as dip coating can be used.

The invention also provides for applications of the dry film in the manufacture of printed circuit boards, including:

(1) Lamination process: The photosensitive resin laminate is laminated to a copper clad laminate or a flexible substrate;

(2) Exposure process: The photosensitive resin layer of the photosensitive resin laminate is exposed and actinic rays are irradiated in a pattern to photocure the exposed portion;

(3) Development process: The non-exposed portion of the photosensitive resin layer is removed with a developer to form a protective pattern;

(4) Conductor pattern formation process: The portion of the surface of the copper clad laminate or flexible substrate that is not covered by the protective pattern is etched or plated.

(5) Peeling process: The protective pattern is peeled from the copper clad laminate or flexible substrate.

Additionally, the present invention provides for the application of the dry film in manufacturing a protective pattern including the lamination process, exposure process, and development process as described above. The only difference is that in the lamination process, the photosensitive resin laminate can be laminated to substrates made of various different materials.

In addition, the present invention provides application of the dry film in conductor pattern manufacturing including the lamination process, exposure process, development process, and conductor pattern formation process as described above. The only difference is that in the lamination process, the photosensitive resin laminate is laminated to a metal plate or metal-coated insulating plate.

Additionally, the present invention provides for the application of the dry film in lead frame manufacturing including the lamination process, exposure process, development process, and conductor pattern formation process as described above. The only difference is that in the lamination process, the photosensitive resin laminate is laminated to a metal plate, and in the conductor pattern formation process, etching is performed on the portion not covered by the protection pattern.

Additionally, the present invention provides for the application of the dry film in semiconductor packaging manufacturing including the lamination process, exposure process, development process, and conductor pattern formation process as described above. The only difference is that in the lamination process, a photosensitive resin laminate is laminated to a wafer equipped with a large-scale integrated circuit, and in the conductor pattern formation process, plating is performed on the portion not covered by the protection pattern.

Application of wet film

The photosensitive resin composition of the present invention can be used by directly applying it to a substrate using a wet film method for use in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging.

Without limitation, the photosensitive resin composition can be applied to the substrate using a conventional method such as roller coating, doctor blade coating, spray coating, or dip coating, and after drying, a photosensitive resin layer is formed.

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

Examples of exposure in the exposure process include mask exposure (a method of irradiating actinic light in a pattern with a negative or positive mask pattern of a wiring pattern), projection exposure, and laser direct imaging. ) A method of irradiating actinic rays in a pattern shape through a direct drawing exposure method such as exposure method or digital light processing exposure method can also be used. Light sources of actinic rays include known light sources, such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure indicator lamps, high-pressure indicator lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, and semiconductor lasers. A light source that effectively emits ultraviolet rays, such as a gallium nitride-based blue-violet laser, can be used. In addition, a light source that effectively emits visible light, such as a photographic floodlight lamp or fluorescent lamp, can be used. The type of actinic light source used in the photosensitive resin composition of the present invention is not particularly limited, and the exposure amount is preferably 10-1000 mJ/cm ² .

In the development process, the non-exposed portion of the photosensitive resin layer is removed using a developer. If a support exists in the photosensitive resin layer, the support can first be removed using an automatic peeler, etc., and then the unexposed portion is removed using a developer such as an aqueous alkaline solution, an aqueous developer, or an organic solvent. Examples of alkaline aqueous solutions include 0.1-5 mass% sodium carbonate solution, 0.1-5 mass% potassium carbonate solution, and 0.1-5 mass% sodium hydroxide solution, and the pH value is preferably 9-11. Additional surfactants, antifoaming agents, organic solvents, etc. can be added to the alkaline aqueous solution. The developing method may be a conventional method such as dipping, spraying, or brushing.

In the etching process, the resist pattern (i.e., protection pattern) formed on the substrate is used as a mask to remove the uncovered conductor layer of the circuit formation substrate by etching to form a conductor pattern. The etching process can be selected depending on the conductor layer to be removed. For example, examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution.

In the plating process, copper plating and soldering are performed on the insulating plate of the uncovered circuit forming board using the resist pattern formed on the board as a mask. After plating, the resist pattern is removed to form a conductor pattern. The plating treatment method may be electroplating treatment or electroless plating treatment, and electroless plating treatment is preferable. Electroless plating treatments include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watts bath (nickel sulfate-nickel chloride) plating, and sulfamic acid plating. Examples include nickel plating such as Acid) nickel plating, and gold plating such as hard gold plating and soft gold plating.

Removal of the resist pattern may be performed by peeling with an aqueous solution that is more basic than the alkaline aqueous solution used in the development step. As an example of a strongly alkaline aqueous solution, for example, a 1-10% by mass aqueous sodium hydroxide solution can be used.

Figure 1 is a structural composition spectrum of TCTM2 obtained by single crystal diffraction.
Figure 2 is a high performance liquid chromatography (HPLC) graph of product a1.
Figure 3 compares the photosensitivity tests of TCTM 1, TCTM 2, TCTM 3, and TCTM 4.
Figure 4 is a high-performance liquid chromatography graph of product b1.
Figure 5 is a structural composition spectrum of b1 obtained by single crystal diffraction.

Below, the present invention is described in more detail through examples, but this should not be considered as limiting the scope of protection of the present invention.

1. Preparation of HABI-based photoinitiator

1.1 Preparation of HABI photoinitiator a1

Under nitrogen protection, 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole (TAI, 2,5-Bis(o-chlorophenyl)- Add 30.6 g of 4-(3,4-dimethoxyphenyl)-imidazole), 1.0 g of 30% liquefied caustic soda, 0.5 g of tetrabutylammonium bromide, and 300 g of toluene, heat and stir, and dissolve when the internal temperature is 60°C. 25 g of sodium chlorate (11% aqueous solution) was added dropwise. After completion of the dropwise addition, the reaction was performed while maintaining the temperature, and sampling was controlled through HPLC until the reaction was completed with TAI of less than 1%, and the temperature retention was terminated. After completion of the warming reaction, the mixture was washed four times with 100 g of pure water, the aqueous layer was extracted once with 100 g of toluene, and the organic layer was distilled under reduced pressure. 40 g of methanol was added to the material obtained by distillation, heated and stirred, and then a solution of 20 g of methanol and 200 g of pure water was added dropwise to the system, and after completion of the dropwise addition, filtration, washing, and baking were performed to obtain 26.5 g of product a1.

Since product a1 is produced by homo-coupling of asymmetric monoimidazole, product a1 is a bisimidazole compound composed of four linking positions 2-1', 2-3', 2'-1, and 2'-3. , the compositions are respectively as follows: TCTM 1: 2,2',5,5'-tetra(o-chlorophenyl)-4',4-bis(3,4-dimethoxyphenyl)-3,2' -Diimidazole (2,2',5,5'-Tetra(o-chlorophenyl)-4',4-bis(3,4-dimethoxyphenyl)-3,2'-diimidazole), TCTM 2: 2,2 ',5,5'-tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole (2,2',5,5'- Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), TCTM 3: 2,2',5,5'-tetra(o-chlorophenyl)- 4',4-bis(3,4-dimethoxyphenyl)-2,1'-diimidazole (2,2',5,5'-Tetra(o-chlorophenyl)-4',4-bis(3 ,4-dimethoxyphenyl)-2,1'-diimidazole), TCTM 4: 2,2',5,5'-tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) -2,3'-diimidazole (2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), structure is displayed as follows:

The structure of product a1 was confirmed using LCMS, and the four products TCTM 1, TCTM 2, TCTM 3, and TCTM 4 all contained molecular fragment peaks of 847 and 848 through mass spectrometry using software provided in the equipment. It was confirmed that the molecular weight of product a1 was 848, which matched T+1 and T+2. This indicates that the four products have the same molecular weight and similar structures.

In order to accurately verify the structural composition of the product, pure TCTM 1, TCTM 2, TCTM 3, and TCTM 4 were obtained through methods such as homo-coupling of monoimidazole, column chromatography, and chromatographic separation, respectively. Figure 1 is a structural composition spectrum of TCTM2 obtained by single crystal diffraction.

Product a1 was analyzed using high-performance liquid chromatography, and the analysis results show that the total peak content of the products at the four linkage positions TCTM 1, TCTM 2, TCTM 3, and TCTM 4 is 96.6%. Figure 2 is a high-performance liquid chromatography graph of product a1.

Judging from the HPLC chromatogram and three-dimensional structure angle of product a1, TCTM 4 has large steric hindrance and is difficult to produce, and its content in product a1 is 0.1%; Comparing TCTM 3 and TCTM 1, TCTM 3 has small steric hindrance, the content in product a1 of TCTM 3 is 34.2%, and the content in product a1 of TCTM 1 is 17.1%; TCTM 2 has the smallest steric hindrance among the four linking positions, and its single crystal composition has already been confirmed, so the content of TCTM 2 in product a1 is 45.2%.

1.2 Light sensitivity test

According to the composition shown in Table 1, photosensitive resin compositions of Samples 1-4 were prepared and tested for photosensitivity. The unit of capacity for each substance in the table is g.

ingredient Sample One 2 3 4 TMPTA 7.10770 7.10773 7.10776 7.10774 NPG 0.00180 0.00181 0.00187 0.00183 PGMEA 2.84310 2.84314 2.84315 2.84312 TCTM1 0.02367 TCTM2 0.02362 TCTM3 0.02369 TCTM4 0.02371

In Table 1, trimethylolpropane triacrylate (TMPTA) was purchased from Tianjin Beilian Fine Chemicals Development Co., Ltd., N-phenylglycine (NPG) was purchased from Shenzhen Pengshunxing Technology Co., Ltd., and propylene Glycolmethyl ether acetate (PGMEA) was purchased from Jinan Huifengda Chemical Co., Ltd.

Samples were prepared according to the above-mentioned composition, mixed uniformly, 1.0 mg of the sample was applied evenly to the bottom of the crucible, and then placed in the stove of a differential scanning calorimeter (model name: DSC8000, manufacturer: PerkinElmer) for testing. carried out. The peak value represents the maximum heat release amount (mw/mg), and the greater the heat release, the higher the photosensitivity; The slope indicates the curing speed, and the smaller the slope, the higher the photosensitivity.

The results are as shown in Figure 3, and the photosensitivity test results are as follows: TCTM 4>TCTM 1>TCTM 3>TCTM 2.

Among the four bisimidazole compounds at linking positions 2-1', 2-3', 2'-1, and 2'-3, TCTM 2 has the smallest steric hindrance, the highest content in product a1, but the lowest photosensitivity; TCTM 1 and TCTM 3 have medium content in product a1 and medium photosensitivity; TCTM 4 has the lowest content in product a1 but has the highest photosensitivity. The reason is that, according to molecular collision theory, the presence of steric hindrance reduces the probability of collision between molecules, and this makes it easier to produce compounds with less steric hindrance. TCTM 2, which has the smallest steric hindrance, has the highest content in product a1, but TCTM 2 has a stable structure, so it needs to absorb more heat to be decomposed, and its binding energy is large. On the contrary, TCTM 4, which has the greatest steric hindrance, has the lowest content in product a1, but TCTM 4 has an unstable structure, so it requires less heat to be absorbed for decomposition, and its binding energy is small. In other words, hexaarylbisimidazole compounds with high steric hindrance are decomposed more easily and exhibit higher photosensitivity because the energy required for decomposition is low after light irradiation.

The test results show that the composition ratio of the bisimidazole compounds at the four linking positions 2-1', 2-3', 2'-1, and 2'-3 included in the HABI photoinitiator ultimately depends on the photosensitivity of the photoinitiator. There is enough proof that it has a big impact.

1.3 Preparation of HABI photoinitiator a2-a45

a2-a45 was manufactured with reference to the manufacturing process of a1, and the solvent, oxidizing agent, phase transfer catalyst, and reaction temperature used were as shown in Table 2 below, and other process variables were maintained without change.

number menstruum oxidizing agent phase transition catalyst reaction temperature type ε _r type E ₀ a1 toluene 2.4 sodium hypochlorite 0.89V TBAB 60℃ a2 benzene 2.3 sodium hypochlorite 0.89V TBAB 60℃ a3 xylene 2.4 sodium hypochlorite 0.89V TBAB 60℃ a4 Anisol 4.3 sodium hypochlorite 0.89V TBAB 60℃ a5 Ethyl acetate 6.0 sodium hypochlorite 0.89V TBAB 60℃ a6 Dichloroethane 10.4 sodium hypochlorite 0.89V TBAB 60℃ a7 Acetonitrile 37.5 sodium hypochlorite 0.89V TBAB 60℃ a8 DMF 36.7 sodium hypochlorite 0.89V TBAB 60℃ a9 toluene 2.4 sodium hypochlorite 0.89V TBAB 0℃ a10 toluene 2.4 sodium hypochlorite 0.89V TBAB 20℃ a11 toluene 2.4 sodium hypochlorite 0.89V TBAB 40℃ a12 toluene 2.4 sodium hypochlorite 0.89V TBAB 70℃ a13 toluene 2.4 sodium hypochlorite 0.89V TBAB 80℃ a14 toluene 2.4 sodium hypochlorite 0.89V TBAB 100℃ a15 toluene 2.4 sodium hypochlorite 0.89V 18-Crown-6 60℃ a16 toluene 2.4 Sodium hypobromite 0.76V TBAB 60℃ a17 benzene 2.3 Sodium hypobromite 0.76V TBAB 60℃ a18 xylene 2.4 Sodium hypobromite 0.76V TBAB 60℃ a19 Anisol 4.3 Sodium hypobromite 0.76V TBAB 60℃ a20 Ethyl acetate 6.0 Sodium hypobromite 0.76V TBAB 60℃ a21 Dichloroethane 10.4 Sodium hypobromite 0.76V TBAB 60℃ a22 Acetonitrile 37.5 Sodium hypobromite 0.76V TBAB 60℃ a23 DMF 36.7 Sodium hypobromite 0.76V TBAB 60℃ a24 toluene 2.4 Sodium hypobromite 0.76V TBAB 0℃ a25 toluene 2.4 Sodium hypobromite 0.76V TBAB 20℃ a26 toluene 2.4 Sodium hypobromite 0.76V TBAB 40℃ a27 toluene 2.4 Sodium hypobromite 0.76V TBAB 70℃ a28 toluene 2.4 Sodium hypobromite 0.76V TBAB 80℃ a29 toluene 2.4 Sodium hypobromite 0.76V TBAB 100℃ a30 toluene 2.4 Sodium hypobromite 0.76V 18-Crown-6 60℃ a31 toluene 2.4 Potassium ferricyanide 0.36V TBAB 60℃ a32 benzene 2.3 Potassium ferricyanide 0.36V TBAB 60℃ a33 xylene 2.4 Potassium ferricyanide 0.36V TBAB 60℃ a34 Anisol 4.3 Potassium ferricyanide 0.36V TBAB 60℃ a35 Ethyl acetate 6.0 Potassium ferricyanide 0.36V TBAB 60℃ a36 Dichloroethane 10.4 Potassium ferricyanide 0.36V TBAB 60℃ a37 Acetonitrile 37.5 Potassium ferricyanide 0.36V TBAB 60℃ a38 DMF 36.7 Potassium ferricyanide 0.36V TBAB 60℃ a39 toluene 2.4 Potassium ferricyanide 0.36V TBAB 0℃ a40 toluene 2.4 Potassium ferricyanide 0.36V TBAB 20℃ a41 toluene 2.4 Potassium ferricyanide 0.36V TBAB 40℃ a42 toluene 2.4 Potassium ferricyanide 0.36V TBAB 70℃ a43 toluene 2.4 Potassium ferricyanide 0.36V TBAB 80℃ a44 toluene 2.4 Potassium ferricyanide 0.36V TBAB 100℃ a45 toluene 2.4 Potassium ferricyanide 0.36V 18-Crown-6 60℃

The products a1-a45 were analyzed by HPLC, and the results are shown in Table 3 below.

code TCTM1 TCTM2 TCTM3 TCTM4 4 connection positions
total content Ratio of 2-1 connection position and 2-3 connection position a1 17.1% 45.2% 34.2% 0.5% 97.0% 1.8:1 a2 17.4% 45.4% 34.0% 0.5% 97.3% 1.8:1 a3 17.5% 45.4% 34.3% 0.4% 97.6% 1.8:1 a4 17.2% 45.9% 33.8% 0.7% 97.6% 1.8:1 a5 TAI remaining 88%, TCTM creation 10%. no product - a6 26.8% 34.6% 27.2% 0.4% 89.0% 2.2:1 a7 33.3% 26.6% 25.1% 2.1% 87.1% 2.2:1 a8 24.7% 33.8% 22.4% 2.9% 83.8% 2.3:1 a9 14.3% 46.9% 35.1% 0.6% 96.9% 1.7:1 a10 15.6% 46.3% 34.9% 0.5% 97.3% 1.7:1 a11 16.5% 44.7% 35.4% 0.5% 97.1% 1.7:1 a12 17.7% 40.6% 36.9% 1.0% 96.2% 1.5:1 a13 17.8% 36.6% 37.7% 1.2% 93.3% 1.4:1 a14 TAI remaining 88%, TCTM generated 6%. no product - a15 17.2% 45.1% 34.1% 0.5% 96.9% 1.8:1 a16 16.8% 48.1% 32.1% 0.6% 97.6% 2.0:1 a17 17.0% 48.3% 31.9% 0.5% 97.7% 2.0:1 a18 16.9% 48.0% 31.3% 0.6% 96.8% 2.0:1 a19 17.0% 47.9% 32.3% 0.5% 97.7% 2.0:1 a20 TAI remaining 75%, TCTM creation 16%. no product - a21 26.2% 30.6% 25.2% 0.2% 82.2% 2.2:1 a22 TAI remaining 61%, TCTM generated 30%. no product - a23 TAI remaining 73%, TCTM generated 15%. no product - a24 17.0% 47.3% 32.8% 0.5% 97.6% 1.9:1 a25 16.9% 47.0% 32.3% 0.5% 96.7% 1.9:1 a26 17.0% 46.9% 33.3% 0.5% 97.7% 1.9:1 a27 17.3% 42.2% 36.9% 0.8% 97.2% 1.6:1 a28 17.8% 38.0% 38.2% 1.0% 95.0% 1.4:1 a29 18.0% 29.4% 43.4% 1.1% 93.3% 1.1:1 a30 16.9% 48.0% 32.2% 0.5% 97.6% 2.0:1 a31 18.1% 45.7% 32.9% 0.2% 96.9% 1.9:1 a32 18.0% 45.9% 32.9% 0.3% 97.1% 1.9:1 a33 18.1% 45.6% 33.0% 0.2% 96.9% 1.9:1 a34 17.9% 45.9% 32.9% 0.4% 97.1% 1.9:1 a35 No TAI reaction, no TCTM formation. no product - a36 25.6% 34.1% 26.2% 0.2% 86.1% 2.3:1 a37 TAI remaining 30%, TCTM creation 40%. no product - a38 TAI remaining 60%, TCTM generation 15%. no product - a39 16.8% 46.1% 33.9% 0.3% 97.1% 1.8:1 a40 16.9% 45.9% 33.5% 0.5% 96.8% 1.8:1 a41 16.9% 45.6% 33.7% 0.4% 96.6% 1.8:1 a42 17.8% 42.3% 37.2% 0.3% 97.6% 1.6:1 a43 18.3% 37.4% 41.0% 0.2% 96.9% 1.4:1 a44 18.9% 34.1% 43.1% 0.3% 96.4% 1.2:1 a45 18.0% 45.6% 32.8% 0.3% 96.7% 1.9:1

1.4 Preparation of HABI photoinitiator b1

Under nitrogen protection, 20.7 g of 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (INC, 2-(o-chlorophenyl)-4,5-diphenyl-imidazole) was added to a 1L four-necked flask. 1.0 g of 30% liquefied caustic soda, 0.5 g of tetrabutylammonium bromide, and 300 g of toluene were added, heated and stirred, and 25 g of sodium hypochlorite (11% aqueous solution) was added dropwise when the internal temperature was 60°C. After completion of the dropwise addition, the reaction was performed while maintaining the temperature, sampling was controlled through HPLC until the reaction was completed with INC of less than 1%, and the temperature retention was terminated. After completion of the warming reaction, the water layer was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 100 g of toluene. The organic layer was distilled under reduced pressure until about 30 g of toluene remained, the temperature was cooled to about 25°C, and then filtered. Washing and baking yielded 18.8 g of product b1.

Product b1 is produced by homo-coupling of symmetric monoimidazole (INC), so the polarities of 2'-1 and 2'-3 obtained by coupling are similar, and liquid phase separation is difficult; Due to the structural symmetry of INC, among the structures of the products obtained by homo-coupling, the structures of 2'-1 and 2-1' are the same, and the structures of 2'-3 and 2-3' are also the same. Therefore, product b1 is a bisimidazole compound consisting of two linking positions 2'-1 and 2'-3, and its composition is respectively as follows: BCIM 1: 2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-diimidazole (2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2 '-diimidazol); BCIM 2: 2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole (2,2'-Bis(o-chlorophenyl)- 4,4',5,5'-tetraphenyl-2',3-diimidazol), and the structure is shown as follows:

The structure of product b1 was confirmed using LCMS, and the molecular fragment peaks of 659 and 660 were obtained from mass spectrometry using software provided in the equipment, and the molecular weight of product b1 was 648, T+1 and T+2. It met.

Product b1 was analyzed using high-performance liquid chromatography, and the analysis results showed that product b1 had only one peak in the liquid phase and had a total content of 99.5%. Figure 4 is a high-performance liquid chromatography graph of product b1.

Product b1 has only one peak in the liquid phase, but two spatial configurations are obtained through single crystal diffraction (as shown in FIG. 5).

1.5 Preparation of HABI photoinitiator b2-b45

b2-b45 was manufactured with reference to the manufacturing process of b1, and the solvent, oxidizing agent, phase transfer catalyst, and reaction temperature used were as shown in Table 4 below, and other process variables were maintained without change.

The total content of the four linkage positions in product b1-b45 is listed in Table 4.

code menstruum oxidizing agent phase transition catalyst reaction temperature Total content of 4 linkage positions type ε _r type E ₀ b1 toluene 2.4 sodium hypochlorite 0.89V TBAB 60℃ 99.5% b2 benzene 2.3 sodium hypochlorite 0.89V TBAB 60℃ 99.3% b3 xylene 2.4 sodium hypochlorite 0.89V TBAB 60℃ 99.6% b4 Anisol 4.3 sodium hypochlorite 0.89V TBAB 60℃ 99.4% b5 Ethyl acetate 6.0 sodium hypochlorite 0.89V TBAB 60℃ No product b6 Dichloroethane 10.4 sodium hypochlorite 0.89V TBAB 60℃ 88.4% b7 Acetonitrile 37.5 sodium hypochlorite 0.89V TBAB 60℃ 90.1% b8 DMF 36.7 sodium hypochlorite 0.89V TBAB 60℃ 85.4% b9 toluene 2.4 sodium hypochlorite 0.89V TBAB 0℃ 99.7% b10 toluene 2.4 sodium hypochlorite 0.89V TBAB 20℃ 99.4% b11 toluene 2.4 sodium hypochlorite 0.89V TBAB 40℃ 99.6% b12 toluene 2.4 sodium hypochlorite 0.89V TBAB 70℃ 99.4% b13 toluene 2.4 sodium hypochlorite 0.89V TBAB 80℃ 94.5% b14 toluene 2.4 sodium hypochlorite 0.89V TBAB 100℃ no product b15 toluene 2.4 sodium hypochlorite 0.89V 18-Crown-6 60℃ 99.6% b16 toluene 2.4 Sodium hypobromite 0.76V TBAB 60℃ 99.5% b17 benzene 2.3 Sodium hypobromite 0.76V TBAB 60℃ 99.6% b18 xylene 2.4 Sodium hypobromite 0.76V TBAB 60℃ 99.4% b19 Anisol 4.3 Sodium hypobromite 0.76V TBAB 60℃ 99.4% b20 Ethyl acetate 6.0 Sodium hypobromite 0.76V TBAB 60℃ no product b21 Dichloroethane 10.4 Sodium hypobromite 0.76V TBAB 60℃ 86.4% b22 Acetonitrile 37.5 Sodium hypobromite 0.76V TBAB 60℃ no product b23 DMF 36.7 Sodium hypobromite 0.76V TBAB 60℃ no product b24 toluene 2.4 Sodium hypobromite 0.76V TBAB 0℃ 99.6% b25 toluene 2.4 Sodium hypobromite 0.76V TBAB 20℃ 99.5% b26 toluene 2.4 Sodium hypobromite 0.76V TBAB 40℃ 99.6% b27 toluene 2.4 Sodium hypobromite 0.76V TBAB 70℃ 99.4% b28 toluene 2.4 Sodium hypobromite 0.76V TBAB 80℃ 95.7% b29 toluene 2.4 Sodium hypobromite 0.76V TBAB 100℃ 91.7% b30 toluene 2.4 Sodium hypobromite 0.76V 18-Crown-6 60℃ 99.6% b31 toluene 2.4 Potassium ferricyanide 0.36V TBAB 60℃ 99.7% b32 benzene 2.3 Potassium ferricyanide 0.36V TBAB 60℃ 99.6% b33 xylene 2.4 Potassium ferricyanide 0.36V TBAB 60℃ 99.5% b34 Anisol 4.3 Potassium ferricyanide 0.36V TBAB 60℃ 99.6% b35 Ethyl acetate 6.0 Potassium ferricyanide 0.36V TBAB 60℃ no product b36 Dichloroethane 10.4 Potassium ferricyanide 0.36V TBAB 60℃ 86.4% b37 Acetonitrile 37.5 Potassium ferricyanide 0.36V TBAB 60℃ no product b38 DMF 36.7 Potassium ferricyanide 0.36V TBAB 60℃ no product b39 toluene 2.4 Potassium ferricyanide 0.36V TBAB 0℃ 99.6% b40 toluene 2.4 Potassium ferricyanide 0.36V TBAB 20℃ 99.7% b41 toluene 2.4 Potassium ferricyanide 0.36V TBAB 40℃ 99.6% b42 toluene 2.4 Potassium ferricyanide 0.36V TBAB 70℃ 99.5% b43 toluene 2.4 Potassium ferricyanide 0.36V TBAB 80℃ 99.5% b44 toluene 2.4 Potassium ferricyanide 0.36V TBAB 100℃ 99.6% b45 toluene 2.4 Potassium ferricyanide 0.36V 18-Crown-6 60℃ 99.3%

1.6 Light sensitivity test

According to the composition shown in Table 5, a photosensitive resin composition was prepared and tested for photosensitivity. The unit of capacity for each substance in the table is g.

ingredient mass 60 mass% toluene/methylcellosolve (mass ratio 6/4) of alkali-soluble polymer [methacrylic acid/methyl methacrylate/styrene copolymer (mass ratio 25/30/25, acid value 163 mgKOH/g, weight average molecular weight 90000) solution] 7.9 PGMEA 11.0 DPHA 1.0 LCV 0.25 NPG 0.01 HABI series photoinitiator (a1-a45, b1-b45) 0.1

In Table 5, dipentaerythritol hexaacrylate (DPHA) was purchased from Tianjin Beilian Fine Chemicals Development Co., Ltd., and leuco crystal violet (LCV) was purchased from Changzhou Tronly New Electronic Materials Co., Ltd. , N-phenylglycine (NPG) was purchased from Shenzhen Pengshunxing Technology Co., Ltd., and propylene glycol methyl ether acetate (PGMEA) was purchased from Jinan Huifengda Chemical Co., Ltd.

The photosensitive resin composition was sufficiently stirred, and the composition was uniformly applied to the surface of a 25 μm thick polyethylene terephthalate thin film as a support using a bar coater, and dried in a dryer at 95°C for 5 minutes to form a photosensitive resin layer. Exposure was performed with a Stouffer 21 step tablet, and the photosensitive layer was exposed to irradiation energy of 60 mJ/cm ² through an exposure machine equipped with a high-pressure mercury lamp (manufactured by ORC Manufacturing Co., Ltd., product name: EXM-1201). After exposure, to perform development, a 1% by mass aqueous solution of sodium carbonate at 30°C was sprayed to develop, using a time twice the minimum development time, and the unexposed portion was removed. Thereafter, the photosensitivity of the photosensitive resin composition was evaluated by measuring the lattice number of the step tablet of the formed photocurable film. The photosensitivity is expressed by the number of grids of the step tablet, and the higher the grid number of the step tablet, the higher the photosensitivity. The results are shown in Table 6.

Sample a1 a2 a3 a4 a6 a7 a8 a9 a10 a11 Light sensitivity (grid) 10 10 10 10 7.5 8 7.5 10 10 10 Sample a12 a13 a15 a16 a17 a18 a19 a21 a24 a25 Light sensitivity (grid) 10 9 10 10 10 10 10 7.5 10 10 Sample a26 a27 a28 a29 a30 a31 a32 a33 a34 a36 Light sensitivity (grid) 10 10 10 8 10 10 10 10 10 7.5 Sample a39 a40 a41 a42 a43 a44 a45 Light sensitivity (grid) 10 10 10 10 10 8 10 Sample b1 b2 b3 b4 b6 b7 b8 b9 b10 b11 Light sensitivity (grid) 5 5 5 5 3 4 3 5 5 5 Sample b12 b13 b15 b16 b17 b18 b19 b21 b24 b25 Light sensitivity (grid) 5 4 5 5 5 5 5 3 5 5 Sample b26 b27 b28 b29 b30 b31 b32 b33 b34 b36 Light sensitivity (grid) 5 5 5 4 5 5 5 5 5 3 Sample b39 b40 b41 b42 b43 b44 b45 Light sensitivity (grid) 5 5 5 5 5 4 5

The photosensitivity test results of product b1-b45 and product a1-a45 show a tendency to basically match.

Based on the above experimental results, the hexaarylbisimidazole compound obtained through oxidation of an oxidizing agent with a standard electrode potential of 0.3-0.9V in a solvent with a relative dielectric constant of 0-5 at 0-70℃, has four connection positions 2 The composition of the bisimidazole compound consisting of -1', 2-3', 2'-1, and 2'-3 is stable, and the ratio of linking positions 2-1 and 2-3 is between 1.5:1 and 2:1. and has relatively little effect on the photosensitivity of the photoinitiator. Otherwise, problems such as low purity and low sensitivity may exist, which may affect the application of the HABI-based photoinitiator in the photosensitive resin composition.

2. Preparation of photosensitive resin composition

According to the composition shown in Tables 7 and 8, each component was mixed uniformly to prepare a photosensitive resin composition. Unless otherwise specified, all numbers shown in Tables 7 and 8 are parts by mass.

code Example One 2 3 4 5 6 7 8 9 10 11 12 a1 2 a2 2 a3 2 a4 2 b1 2 b2 2 b3 2 b4 2 b9 2 b10 2 b11 2 b12 2 B 59 59 59 59 59 59 59 59 59 59 59 59 C1 16 16 16 16 16 16 16 16 16 16 16 16 C2 20 20 20 20 20 20 20 20 20 20 20 20 D 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E1 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 E2 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 E3 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E4 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 E5 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 E6 30 30 30 30 30 30 30 30 30 30 30 30 E7 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 E8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 E9 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8

code Example Comparative example 13 14 15 16 One 2 3 4 5 6 7 8 b15 2 b27 2 b41 2 b42 2 a13 2 a28 2 a44 2 b13 2 b28 2 b29 2 b43 2 b44 2 B 59 59 59 59 59 59 59 59 59 59 59 59 C1 16 16 16 16 16 16 16 16 16 16 16 16 C2 20 20 20 20 20 20 20 20 20 20 20 20 D 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E1 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 E2 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 E3 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E4 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 E5 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 0.17 E6 30 30 30 30 30 30 30 30 30 30 30 30 E7 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 E8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 E9 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8

The meaning represented by each component in Tables 7 and 8 is as shown in Table 9.

ingredient code specific composition Alkali soluble polymer B self-production Compounds with ethylenically unsaturated double bonds C1 FA-321M: EO modified bisphenol A dimethacrylate, average amount of EO added is 10 mol (Hitachi Chemical Industry Co., Ltd.) C2 APG400: Polypropylene glycol diacrylate, the average number of structural units of propylene oxide is 7 (Shin Nakamura Chemical Industry Co., Ltd.) hydrogen donor D N-phenylglycine (Hubei Jusheng Technology Co., Ltd.) supplements E1 Malachite Green (Hangzhou Hairui Chemical Co., Ltd.) E2 Leuco Crystal Violet (Hangzhou Hairui Chemical Co., Ltd.) E3 5-Carboxyl-1,2,3-benzotriazole (Alpha Chemical Co., Ltd.) E4 2,6-di-tert-butyl-p-cresol (Hangzhou Hairui Chemical Co., Ltd.) E5 Polyoxypropylene oxyethylene glycerol ether (Haisen Chemical Co., Ltd.) E6 acetone E7 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (Changzhou Tronly New Electronic Materials Co., Ltd.) E8 9-Phenylacridine (Changzhou Tronly New Electronic Materials Co.,Ltd.) E9 9,10-bis(3-chloropropoxy)anthracene (Changzhou Tronly New Electronic Materials Co., Ltd.)

The preparation of alkali-soluble polymer B is as follows: Under a nitrogen atmosphere, 500 g of a mixed solvent of methyl cellosolve and toluene (mass ratio 3:2) is added to a flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel. After stirring and heating to 80°C, 100g of methacrylic acid, 200g of ethyl methacrylate, 100g of ethyl acrylate, 100g of styrene, and azobisisobutyronitrile. The solution obtained by mixing 0.8 g of (Azobisisobutyronitrile) was slowly added dropwise to the flask over a dropping time of 4 hours, and after the dropwise addition was completed, the reaction was continued for 2 hours. Next, 100 g of a mixed solvent (composition same as above) containing 1.2 g of azobisisobutyronitrile dissolved in the flask was added dropwise over 10 minutes. After the dropwise addition was completed, the reaction was continued at 80°C for 3 hours, and then again at 90°C. The temperature was raised to and the reaction was continued for 2 hours. After completion of the reaction, it was filtered to obtain alkali-soluble polymer B with an acid value of 196 mgKOH/g and a weight average molecular weight of about 80,000.

3. Performance evaluation

3.1 Evaluation method

<Manufacture of dry film>

The photosensitive resin composition was sufficiently stirred, applied uniformly to the surface of the 25μm thick polyethylene terephthalate thin film as a support using a bar coater, and dried in a dryer at 95°C for 5 minutes to form a photosensitive resin layer with a thickness of 40μm. did. Next, a dry film was obtained by attaching a polyethylene thin film with a thickness of 15 μm as a protective layer to the surface of the photosensitive resin layer on which the polyethylene terephthalate thin film was not laminated.

<Substrate surface flattening>

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 buff roller polished (Scotch-Brite (registered trademark) HD#600 manufactured by 3M, 2 passes). ) was performed.

<Lamination>

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

<Exposure>

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

<Phenomena>

The polyethylene terephthalate thin film was peeled off, a 1% by mass Na ₂ CO ₃ aqueous solution at 30°C was sprayed on the photosensitive resin layer using an alkaline developer (developer for dry films manufactured by FujiKiko Co., Ltd.), and the minimum development time was 2. The unexposed portion of the photosensitive resin layer was dissolved and removed using a doubling of the time. The minimum time required to completely dissolve the photosensitive resin layer in the non-exposed area is the minimum development time.

3.2 Evaluation contents

(1) Storage stability

The photosensitive resin compositions of the examples and comparative examples were stored in a dark place at 20°C for 2 weeks, and the rate of increase in viscosity (thickness) was tested after 2 weeks. The evaluation criteria are as described below.

○ : Thickening rate 0-100%；

△: Thickening rate 100-200%；

×: Thickening ratio of 200% or more or gelation.

(2) Sensitivity

The dry film made from the photosensitive resin composition of the above examples and comparative examples was stored in a dark place at 23°C and 50% humidity for 5 hours, and then the photosensitive resin layer laminated on the copper clad laminate was placed on a Stouffer 21 step tablet (stepwise exposure ruler). ) and developed. The sensitivity of the photosensitive resin composition was evaluated by measuring the lattice number of the step tablet of the photocurable film formed on the copper clad laminate. Sensitivity is expressed by the number of grids of the step tablet, and the higher the grid number of the step tablet, the higher the photosensitivity.

(3) Sensitivity maintenance time

Dry films prepared from the photosensitive resin compositions of the examples and comparative examples were stored in a dark place at 23°C and 50% humidity for 2 weeks, and then their sensitivity was evaluated using the same method as the sensitivity test.

(4) Resolution

Exposure and development were performed using a photo mask with a wiring pattern of Line/Space = 10:10 - 150:150 (unit: μm), and then the resolution of the dry film was measured. Resolution is the minimum value of the pattern after cleanly removing the non-exposed portion of the resist pattern formed by developing after exposure. The evaluation criteria are as described below.

○: Resolution value is 30μm or less.

◎: Resolution value is 30μm - 50μm, not including endpoint.

●: Resolution value is 50μm or more.

(4) Resolution maintenance time

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

3.3 Evaluation results

The evaluation results are shown in Table 10.

Storage stability
(%) Sensitivity
(grid) Sensitivity maintenance time
(grid) resolution
(μm) Resolution maintenance time (μm) Example 1 25/○ 10 10 25/○ 25/○ Example 2 28/○ 10 10 24/○ 24/○ Example 3 23/○ 10 10 24/○ 24/○ Example 4 29/○ 10 10 25/○ 25/○ Example 5 22/○ 5 5 24/○ 24/○ Example 6 24/○ 5 5 25/○ 25/○ Example 7 26/○ 5 5 25/○ 25/○ Example 8 30/○ 5 5 26/○ 26/○ Example 9 19/○ 5 5 24/○ 24/○ Example 10 22/○ 5 5 25/○ 25/○ Example 11 25/○ 5 5 25/○ 25/○ Example 12 35/○ 5 5 26/○ 26/○ Example 13 23/○ 5 5 25/○ 25/○ Example 14 33/○ 5 5 26/○ 26/○ Example 15 28/○ 5 5 24/○ 24/○ Example 16 32/○ 5 5 26/○ 26/○ Comparative Example 1 142/△ 8.5 7 27/○ 33/◎ Comparative example 2 171/△ 9 7.5 27/○ 33/◎ Comparative Example 3 132/△ 9 8 28/○ 34/◎ Comparative example 4 163/△ 4.5 3.5 27/○ 33/◎ Comparative Example 5 138/△ 4.5 3.5 28/○ 32/◎ Comparative Example 6 172/△ 4 2.5 28/○ 34/◎ Comparative example 7 129/△ 4.5 3.5 27/○ 32/◎ Comparative example 8 140/△ 4 3 28/○ 31/◎

When the HABI-based photoinitiator of the present invention is applied to a photosensitive resin composition, the composition and its dry film have excellent storage stability, and there is no tendency for sensitivity and resolution to decrease even after long-term storage. The photosensitive resin composition can be widely applied in the manufacturing area of printed circuit boards, protective patterns, conductor patterns, lead frames, and semiconductor packaging using dry film and wet film methods. .

The above-described embodiments are preferred embodiments of the present invention, but the implementation method of the present invention is not limited to the above-described embodiments. All other changes, modifications, substitutions, combinations and simplifications made within the spirit and principles of the present invention are included within the protection scope of the present invention in the form of equivalent substitution.

Claims (20)

In the HABI-based photoinitiator that can improve system stability having a structure represented by general formula (I),
The HABI-based photoinitiator includes bisimidazole compounds at four linking positions 2-1', 2-3', 2'-1, and 2'-3, and the total of bisimidazole compounds having the four linking positions The mass percentage content is more than 92%, and the ratio of the sum of the contents of the two connecting positions 2-1' and 2'-1 and the sum of the contents of the two connecting positions 2-3' and 2'-3 is 1.5:1-2: HABI-based photoinitiator, characterized in that it is between 1;
(Ⅰ)
In general formula (I), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may be the same or different from each other, and each independently represents a substituted or unsubstituted aryl group, but Ar ₁ and Ar ₄ is the same aryl group, Ar ₂ and Ar ₅ are the same aryl group, Ar ₃ and Ar ₆ are the same aryl group, except for cases where Ar ₁ , Ar ₂ , Ar ₄ and Ar ₅ are all the same aryl group.
According to clause 1,
In general formula (I), the HABI-based photoinitiator is characterized in that the aryl group is a phenyl group.
According to claim 1 or 2,
The substituents of the aryl group are halogen, nitro, cyano, amino, hydroxy, C ₁ -C ₂₀ alkyl or alkenyl, C ₁ -C ₈ alkoxy, and among each independent variable, the methylene group is oxygen, sulfur, methylene, A HABI-based photoinitiator characterized in that it can be selectively substituted with a no group.
According to clause 3,
The substituents of the aryl group are fluorine, chlorine, bromine, nitro group, cyano group, amino group, hydroxy group, C ₁ -C ₁₀ alkyl or alkenyl group, C ₁ -C ₅ alkoxy group, and among each independent variable, the methylene group is oxygen A HABI-based photoinitiator characterized in that it can be selectively substituted with , sulfur, and imino groups.
According to clause 3,
Ar ₁ and Ar ₄ ; Ar ₂ and Ar ₅ ; and Ar ₃ and Ar ₆ ; at least one of
A HABI-based photoinitiator, characterized in that it is an aryl group containing a halogen substituent or an aryl group containing chlorine.
In the method for producing the HABI-based photoinitiator according to claim 1,
(1) Reaction step: Under nitrogen protection, oxidative coupling of a triarylimidazole-based compound in the presence of an oxidizing agent, solvent, and phase transfer catalyst, and controlling through HPLC until the reaction is completed;
(2) Purification step: washing with pure water to remove inorganic salts, filtering and concentrating to obtain a crude product, and then recrystallizing and drying to obtain the desired product.
A method for producing a HABI-based photoinitiator, comprising:
According to clause 6,
The standard electrode potential (E0) of the oxidizing agent is between 0.3-0.9V, or
A method for producing a HABI-based photoinitiator, wherein the oxidizing agent is one or a combination of two or more of sodium hypochlorite, potassium hypochlorite, sodium hypobromite, potassium hypobromite, sodium ferricyanide, and potassium ferricyanide.
According to clause 6,
Preparation of a HABI-based photoinitiator, characterized in that the relative dielectric constant (ε _r ) of the solvent is 0-5, and the solvent is selected from benzene, toluene, xylene, trimethylbenzene, anisole, and phenetole. method.
According to clause 6,
The phase transfer catalyst is selected from quaternary ammonium salts and cyclic crown ether systems,
The phase transfer catalyst is benzyltriethyl ammonium chloride (TEBA), tetrabutyl ammonium bromide (TBAB), tetrabutyl ammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethyl ammonium chloride, dodecyltrimethyl ammonium chloride, A method for producing a HABI-based photoinitiator, characterized in that it is one or a combination of two or more of tetradecyltrimethyl ammonium chloride, 18-crown-6, 15-crown-5, and cyclodextrin.
According to clause 6,
A method for producing a HABI-based photoinitiator, characterized in that the reaction temperature is 0-70°C, or 20-70°C.
HABI-based photoinitiator (A) according to claim 1;
Alkali soluble polymer (B);
Compound (C) having an ethylenically unsaturated double bond;
hydrogen donor (D);
Other optional adjuvants (E);
A photosensitive resin composition comprising:
According to clause 11,
The alkali-soluble polymer includes (meth)acrylic polymer, styrene-based polymer, epoxy-based polymer, aliphatic polyurethane (meth)acrylate polymer, aromatic polyurethane (meth)acrylate polymer, amide-based resin, amide-epoxy-based resin, and alkyd. A photosensitive resin composition selected from resins and phenolic resins.
According to clause 12,
A photosensitive resin composition, characterized in that the alkali-soluble polymer is a (meth)acrylate-based polymer formed by copolymerization of (meth)acrylate, ethylenically unsaturated carboxylic acid, and other copolymerizable monomers.
According to any one of claims 11 to 13,
A photosensitive resin composition, characterized in that the acid value of the alkali-soluble polymer is 50-300 mgKOH/g, or 50-250 mgKOH/g, or 70-250 mgKOH/g, or 100-250 mgKOH/g.
According to clause 11,
A photosensitive resin composition, wherein the compound having an ethylenically unsaturated double bond is a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule.
According to clause 15,
A photosensitive resin composition, wherein the compound having an ethylenically unsaturated double bond is selected from bisphenol A-based (meth)acrylate compounds and (meth)acrylate compounds having a urethane bond in the molecule.
According to claim 11,
A photosensitive resin composition, characterized in that the hydrogen donor is one type or a combination of two or more types selected from amine-based compounds, carboxylic acid-based compounds, organic sulfur compounds containing a mercapto group, and alcohol-based compounds.
According to clause 11,
The auxiliary agent includes at least one of other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating auxiliaries, and peeling accelerators. Photosensitive resin composition.
A photosensitive resin laminate comprising a photosensitive resin layer formed from the photosensitive resin composition according to claim 11, 12, or 13, and a support for supporting the photosensitive resin layer.
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