CN111747897A - Hexaarylbisimidazole photoinitiator and application thereof - Google Patents

Hexaarylbisimidazole photoinitiator and application thereof Download PDF

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CN111747897A
CN111747897A CN201910248688.8A CN201910248688A CN111747897A CN 111747897 A CN111747897 A CN 111747897A CN 201910248688 A CN201910248688 A CN 201910248688A CN 111747897 A CN111747897 A CN 111747897A
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photosensitive resin
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resin composition
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钱晓春
杨金梁
严春霞
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Changzhou Zhengjie Intelligent Manufacturing Technology Co., Ltd
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Changzhou Green Photosensitive Materials Co ltd
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Priority to PCT/CN2020/081293 priority patent/WO2020200020A1/en
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract

The invention discloses a hexaarylbisimidazole photoinitiator, wherein the molar ratio of red-shifted substituent groups in all substitutable sites is 6-16%. When the photoinitiator is applied to a photosensitive resin composition, the photosensitivity is moderate, the dissolubility is good, the resolution and the developability are excellent, an inverted trapezoid can not appear during development, the hydrophilicity is good, the sludge amount in a developing solution during recycling can be obviously reduced, and the developing solution can be repeatedly and effectively used. The invention also provides a photosensitive resin composition containing the photoinitiator and application of the composition.

Description

Hexaarylbisimidazole photoinitiator and application thereof
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a hexaarylbisimidazole photoinitiator, a photosensitive resin composition containing the photoinitiator and application thereof.
Background
With the miniaturization of precision electronic devices, photosensitive resin compositions have become a focus of research, wherein the effects of photoinitiators on the sensitivity, solubility, hydrophilicity, resolution and developability of photosensitive resin compositions have been the focus of research. The photoinitiator is an essential component of the photosensitive resin composition, and is generally required to have high initiation efficiency, excellent solubility, excellent hydrophilicity, and the like. However, the application finds that not all physicochemical indexes are as high as possible, and for example, as the application becomes finer, the problem of insufficient manufacturing precision and high defective rate is easily caused by too high sensitivity of the photoinitiator.
Hexaarylbisimidazoles are a known class of photoinitiators, and currently, relevant research is mainly focused on: changing substituent groups on the aryl to increase hydrophilicity, thereby reducing development waste; changing the substituent groups on the aryl groups to increase photosensitivity; a color-changing group is added to improve development recognition and the like. The research shows that hexaarylbisimidazole photoinitiator (such as BCIM) with low sensitivity can cause the photosensitive resin composition to have excellent resolution and resolution when used for photoetching with narrower line width, but the amount of sludge in the developing solution is large, thereby influencing the repeated use of the developing solution; the high-sensitivity hexaarylbisimidazole photoinitiator (such as TCDM-HABI) can ensure that when the photosensitive resin composition is used for photoetching with a narrow line width, the bottom is not completely cured, and then an inverted trapezoid appears during development, so that the product does not meet the application requirements. The existing hexaarylbisimidazole photoinitiator in the market has low yield when being applied to a fine line due to unstable components, large difference and large amount of development waste, and seriously influences the product quality and the use feeling of customers.
The applicant further studies the proportion and composition of substituent groups introduced on aryl groups in the hexaarylbisimidazole photoinitiator and the proportion and composition of bathochromic groups in the substituent groups on the basis of the existing hexaarylbisimidazole compounds, and further comprehensively regulates and controls the performances such as sensitivity, solubility, hydrophilicity, resolution, developability and the like, so that the photosensitive resin composition using the photoinitiator has a proper curing rate in application without influencing the development to prepare a required photoetching pattern, and also has the advantage of low development waste, thereby widening the practical application of the hexaarylbisimidazole photoinitiator.
Disclosure of Invention
The invention aims to provide a hexaarylbisimidazole photoinitiator so as to solve the problems that the existing photoinitiator has inverted trapezia and the like when used in a high-precision line, does not meet application requirements, and development waste cannot be effectively reduced. When the photoinitiator is applied to the photosensitive resin composition, the photosensitivity is moderate, the dissolubility is good, the resolution and the developability are excellent, an inverted trapezoid can not appear during development, the hydrophilicity is good, the sludge amount in a developing solution can be obviously reduced during recycling, and the developing solution can be repeatedly and effectively used.
Specifically, the hexaarylbisimidazole photoinitiator is prepared by the following steps:
(1) aromatic aldehyde shown in a general formula (I) and aromatic aldehyde shown in a general formula (II) are subjected to condensation and oxidation reaction to obtain a benzil compound; the benzil compound and aromatic aldehyde shown in a general formula (III) generate a mono-imidazole compound M through cyclization reaction;
(2) the aromatic aldehyde shown in the general formula (IV) and the aromatic aldehyde shown in the general formula (V) are subjected to condensation and oxidation reaction to obtain a benzil compound; the benzil compound and aromatic aldehyde shown in a general formula (VI) generate a mono-imidazole compound N through a cyclization reaction;
(3) the single imidazole compound M and the single imidazole compound N generate a hexaaryl bisimidazole photoinitiator through oxidation reaction;
Figure BDA0002011767650000031
wherein R is1-R30Each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxy, C1-C10Alkyl of (C)1-C10Alkoxy of, or C2-C10And the methylene groups in each group may be optionally substituted by oxygen, sulfur, imino groups;
provided that the red-shifted substituent is introduced into the hexaarylbisimidazole as a photoinduced compoundAll substitutable sites of hair agents, i.e. R1-R30The molar ratio of (A) is 6-16%.
The invention also aims to provide a photosensitive resin composition containing the photoinitiator and application of the composition in manufacturing printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages and the like.
The invention also provides the application of the photosensitive resin composition in the manufacture of a color filter, the color filter and a liquid crystal display module containing the color filter.
Detailed Description
For the purposes of the present invention, the following aspects are described in more detail.
The terms "sludge" and "development waste" in this application refer to materials that accumulate in the developer solution, are insoluble in the developer solution, and can redeposit on the developed substrate, thereby reducing the efficiency of the developer solution.
< hexaarylbisimidazoles photoinitiator >
As described above, the hexaarylbisimidazole photoinitiator of the present invention is prepared by the following steps:
(1) aromatic aldehyde shown in a general formula (I) and aromatic aldehyde shown in a general formula (II) are subjected to condensation and oxidation reaction to obtain a benzil compound; the benzil compound and aromatic aldehyde shown in a general formula (III) generate a mono-imidazole compound M through cyclization reaction;
(2) the aromatic aldehyde shown in the general formula (IV) and the aromatic aldehyde shown in the general formula (V) are subjected to condensation and oxidation reaction to obtain a benzil compound; the benzil compound and aromatic aldehyde shown in a general formula (VI) generate a mono-imidazole compound N through a cyclization reaction;
(3) the single imidazole compound M and the single imidazole compound N generate a hexaaryl bisimidazole photoinitiator through oxidation reaction;
Figure BDA0002011767650000041
wherein R is1-R30Each independent earth surfaceHydrogen, halogen, nitro, cyano, amino, hydroxy, C1-C10Alkyl of (C)1-C10Alkoxy of, or C2-C10And the methylene groups in each group may be optionally substituted by oxygen, sulfur, imino groups;
provided that the red-shifted substituent is at all substitutable sites of the hexaarylbisimidazole photoinitiator, namely R1-R30The molar ratio of (A) is 6-16%.
The red-shift substituent group of the present invention is a group in which a substituent group introduced to an aromatic ring increases the degree of conjugation of a hexaarylbisimidazole structure, thereby causing a shift of an ultraviolet absorption wavelength toward a long wavelength (i.e., causing a red shift phenomenon). Preferably, the bathochromic substituents include chloro, bromo, nitro, cyano, amino, hydroxy, C2-C10Alkenyl of (C)1-C10Wherein the methylene group in each group may be optionally substituted by oxygen, sulfur, or an imine group. Further preferably, the bathochromic substituent is selected from the group consisting of chlorine, bromine, hydroxyl, amine, and C1-C5Alkoxy group of (2).
The red-shifted substituent is arranged at all substitutable sites (namely R) of the hexaarylbisimidazole photoinitiator1-R30) The molar ratio of (A) is 6-16%. If the molar ratio of the red-shift substituent is more than 16%, the condition that the surface is completely cured but the inside is not completely cured easily occurs due to overhigh sensitivity exists, so that the narrow line subjected to photoetching can be in an inverted trapezoid shape after being developed, and the prepared product does not meet the application requirement; if the molar ratio of the bathochromic substituent is less than 6%, the sensitivity is low, the curing speed is slow, and the production efficiency is reduced.
The application shows that when the hexaarylbisimidazole photoinitiator is applied to the photosensitive resin composition, the composition has moderate sensitivity, good solubility, excellent resolution and developability, and does not have an inverted trapezoid during development. In addition, the hydrophilic developing solution has better hydrophilicity, and can obviously reduce the amount of sludge in the developing solution during recycling, so that the developing solution can be repeatedly and effectively used.
In the present application, the molar ratio of the bathochromic substituents is calculated as follows:
(1) a mol of an aromatic aldehyde (R) of the formula (I)1-R5The number of the middle red-shifted substituent is A) and b mol of aromatic aldehyde (R) shown in the general formula (II)6-R10The number of the middle red-shift substituent group is B), and (a + B)/2mol of benzil compounds are obtained through condensation and oxidation reactions; the benzil compound is mixed with (a + b)/2mol of aromatic aldehyde (R) shown as a general formula (III)11-R15The number of the middle red-shifted substituent is C) to generate a mono-imidazole compound M through cyclization, wherein the number of the middle red-shifted substituent in M is M;
Figure BDA0002011767650000061
(2) a' mol of an aromatic aldehyde (R) represented by the general formula (IV)16-R20Wherein the number of the bathochromic substituents is A ') and b' mol of the aromatic aldehyde (R) of the formula (V)21-R25The number of the middle red-shift substituent group is B ') to obtain (a ' + B ')/2 mol of benzil compounds through condensation and oxidation reactions; the benzil compound is mixed with (a '+ b')/2 mol of aromatic aldehyde (R) shown in the general formula (VI)26-R30The number of the middle red-shifted substituent groups is C') to generate a mono-imidazole compound N through cyclization, wherein the number of the red-shifted substituent groups in N is N;
Figure BDA0002011767650000062
(3) e mol of the mono-imidazole compound M and f mol of the mono-imidazole compound N are subjected to oxidation reaction to generate the hexaarylbisimidazole photoinitiator, and the red-shifted substituent is positioned at all substitutable sites (namely R) of the hexaarylbisimidazole photoinitiator1-R30) The molar ratio in (1) is p.
Figure BDA0002011767650000063
< photosensitive resin composition >
As described above, the hexaarylbisimidazole-based photoinitiator of the present invention has excellent performance when applied to a photosensitive resin composition. Accordingly, the present invention also provides a photosensitive resin composition comprising the following components:
(A) the hexaarylbisimidazole photoinitiator as described above;
(B) an alkali soluble polymer;
(C) a compound having an ethylenically unsaturated double bond;
(D) a hydrogen donor;
(E) other optional adjuvants.
The components will be described in more detail below.
Hexaarylbisimidazoles photoinitiators (A)
The hexaarylbisimidazole photoinitiators of the present invention do not limit the position of the bisimidazole linkage within the limits of the characteristics as described above. Illustratively, the hexaarylbisimidazole photoinitiator may be selected from or include at least one of the following compounds:
compound 1 (molar percentage of bathochromic substituents 10%):
(1)1mol of benzaldehyde and 1mol of o-chlorobenzaldehyde are subjected to self-condensation and oxidation reaction to obtain 1mol of benzil compounds; the benzil compound and 1mol of o-chlorobenzaldehyde generate a mono-imidazole compound M1 through a ring-forming reaction, and the number of red-shifted substituents in M1 is 2.
(2)2mol of benzaldehyde is subjected to self-condensation and oxidation reaction to obtain 1mol of benzil compound; the benzil compound and 1mol of o-chlorobenzaldehyde generate a mono-imidazole compound N1 through a ring-forming reaction, and the number of red-shifted substituents in N1 is 1.
(3) And (3) oxidizing 1mol of the mono-imidazole compound M1 and 1mol of the mono-imidazole compound N1 to generate the hexaarylbisimidazole photoinitiator, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 10%.
Compound 2 (7.3% in terms of molar ratio of bathochromic substituents):
and (3) generating a hexaarylbisimidazole photoinitiator by oxidizing 1mol of a monoimidazole compound M1 and 9mol of a monoimidazole compound N1, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 7.3%.
Compound 3 (molar ratio of bathochromic substituents 12.7%):
and (3) carrying out oxidation reaction on 9mol of the mono-imidazole compound M1 and 1mol of the mono-imidazole compound N1 to generate the hexaarylbisimidazole photoinitiator, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 12.7%.
Compound 4 (molar ratio of the bathochromic substituent 13.3%):
(1)1mol of p-tolualdehyde and 1mol of o-chlorobenzaldehyde are subjected to condensation and oxidation reaction to obtain 1mol of benzil compound; the benzil compound and 1mol of 2, 4-dichlorobenzaldehyde generate a mono-imidazole compound M2 through a cyclization reaction, and the number of red-shifted substituents in M2 is 3.
(2) And (3) oxidizing 1mol of the mono-imidazole compound M2 and 1mol of the mono-imidazole compound N1 to generate the hexaarylbisimidazole photoinitiator, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 13.3%.
Compound 5 (molar ratio of the bathochromic substituent 15.6%):
and (2) carrying out oxidation reaction on 2mol of the mono-imidazole compound M2 and 1mol of the mono-imidazole compound N1 to generate the hexaarylbisimidazole photoinitiator, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 15.6%.
Compound 6 (6.7% in terms of molar ratio of bathochromic substituents):
(1)1mol of p-tolualdehyde and 1mol of benzaldehyde are subjected to condensation and oxidation reaction to obtain 1mol of benzil compound; the benzil compound and 1mol of o-chlorobenzaldehyde generate a mono-imidazole compound M3 through a ring formation reaction, and the number of red-shifted substituents in M3 is 1.
(2)2mol of the mono-imidazole compound M3 generates a hexaarylbisimidazole photoinitiator through autoxidation reaction, and the molar ratio of the red-shifted substituent group in all substitutable sites of the hexaarylbisimidazole photoinitiator is 6.7%.
The content of the hexaarylbisimidazole-based photoinitiator (a) is 1 to 20 parts by mass, preferably 1 to 10 parts by mass, in 100 parts by mass of the photosensitive resin composition. If the content is too small, the defect of reduced photosensitivity exists; if the content is too large, there is a defect that the photoresist pattern tends to be widened beyond the line width of the photomask.
Alkali soluble Polymer (B)
The alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition. The alkali-soluble polymer is not particularly limited as long as it has such characteristics.
For example, suitable alkali-soluble polymers may be (meth) acrylic polymers, styrene polymers, epoxy polymers, aliphatic urethane (meth) acrylate polymers, aromatic urethane (meth) acrylate polymers, amide resins, amide epoxy resins, alkyd resins, phenolic resins, and the like.
Further, the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include: polymerizable styrene derivatives substituted at the α -position or at the aromatic ring, such as styrene, vinyltoluene, α -methylstyrene, p-ethylstyrene, and p-chlorostyrene; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth) acrylic acid derivatives such as (meth) acrylic acid, α -bromo (meth) acrylic acid, α -chloro (meth) acrylic acid, β -furyl (meth) acrylic acid, and β -styryl (meth) acrylic acid; (meth) acrylate compounds such as alkyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, propanoic acid, N-vinylcaprolactam; n-vinylpyrrolidone and the like. These polymerizable monomers may be used alone or in combination of two or more.
Further, from the viewpoint of alkali developability and adhesion, it is preferable to use an alkali-soluble polymer containing a carboxyl group. The alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth) acrylic acid as a monomer unit, which introduces a carboxyl group by using (meth) acrylic acid as a monomer unit; may be a copolymer further comprising, as a monomer unit, an alkyl (meth) acrylate in addition to (meth) acrylic acid; the copolymer may contain, as a monomer component, a polymerizable monomer other than (meth) acrylic acid and alkyl (meth) acrylate (for example, a monomer having an ethylenically unsaturated group) in addition to (meth) acrylic acid.
Further, the carboxyl group-containing alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer, and particularly is a (meth) acrylate polymer obtained by copolymerization of a (meth) acrylate, an ethylenically unsaturated carboxylic acid, and another copolymerizable monomer.
The (meth) acrylic acid ester may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, furfuryl (meth) acrylate, glycidyl (meth) acrylate, or the like. These (meth) acrylates may be used alone or in combination of two or more.
The ethylenically unsaturated carboxylic acid may be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and acrylic acid and methacrylic acid are particularly preferred. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more.
The other copolymerizable monomer may be (meth) acrylamide, n-butyl (meth) acrylate, styrene, vinyl naphthalene, (meth) acrylonitrile, vinyl acetate, vinyl cyclohexane, etc. These other copolymerizable monomers may be used alone or in combination of two or more.
The alkali-soluble polymer may be used alone or in combination of two or more. Examples of the alkali-soluble polymer used in combination of two or more kinds include two or more kinds of alkali-soluble polymers composed of different copolymerization components, two or more kinds of alkali-soluble polymers having different weight average molecular weights, two or more kinds of alkali-soluble polymers having different degrees of dispersion, and the like.
In the photosensitive resin composition of the present invention, the weight average molecular weight of the alkali-soluble polymer is not particularly limited, and it should be adapted to a specific application environment. From the viewpoint of both mechanical strength and alkali developability, the weight average molecular weight is preferably 15000-200000, more preferably 30000-150000, and particularly preferably 30000-120000. When the weight average molecular weight is more than 15000, the developing resistance after exposure tends to be further improved, and when the weight average molecular weight is less than 200000, the developing time tends to be shorter and the compatibility with other components such as a photoinitiator can be maintained. The weight average molecular weight of the alkali-soluble polymer was measured by Gel Permeation Chromatography (GPC) and obtained by conversion using a standard curve of standard polystyrene.
Further, the acid value of the alkali-soluble polymer is preferably from 50 to 300mgKOH/g, more preferably from 50 to 250mgKOH/g, still more preferably from 70 to 250mgKOH/g, and particularly preferably from 100 to 250mgKOH/g, from the viewpoint of satisfactory alkali developability. When the acid value of the alkali-soluble resin is less than 50mgKOH/g, it is difficult to secure a sufficient developing speed, and when it exceeds 300mgKOH/g, the adhesiveness is reduced, a pattern short-circuit is likely to occur, and the problem of lowering of the storage stability of the composition and increase of the viscosity is likely to occur.
The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the alkali-soluble resin is preferably 1.5 to 6.0, particularly preferably 1.8 to 3.7. When the molecular weight distribution is in the range, developability is excellent.
The content of the alkali-soluble polymer in 100 parts by mass of the photosensitive resin composition is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass. When the content of the alkali-soluble polymer is 20 parts by mass or more, the durability of the photosensitive resin composition against plating treatment, etching treatment and the like can be ensured to be improved, and when the content is 70 parts by mass or less, the sensitivity of the photosensitive resin composition is favorably improved.
Compound (C) having an ethylenically unsaturated double bond
The compound having an ethylenically unsaturated double bond can promote film formation of the photosensitive resin composition.
The compound having an ethylenically unsaturated double bond is not particularly limited, and a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used. By way of example, mention may be made of: examples of the urethane monomer include a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol a-based (meth) acrylate compound, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, nonylphenoxy polyethyleneoxy acrylate, γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, phthalic compounds, and alkyl (meth) acrylates. These compounds may be used alone or in combination of two or more.
Examples of the compound obtained by reacting the α, β -unsaturated carboxylic acid with a polyhydric alcohol include: polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, polyethylene-polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, polypropylene glycol, Polyethylene glycol mono (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more. Here, "EO" represents ethylene oxide, and the EO-modified compound means a compound having a block structure of an oxyethylene group. "PO" represents propylene oxide, and a PO-modified compound means a compound having a block structure of an oxypropylene group.
Examples of the bisphenol a (meth) acrylate compound include: 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolypropoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolybutoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane and the like. Examples of the 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane include: 2, 2-bis {4- [ (meth) acryloyloxydiethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytriethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyethtetraethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypentaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyhexaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyheptaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyoctaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxynonaethoxy ] phenyl } propane, 2, 2-bis {4- [ (meth) acryloyloxydodecoxyethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytridecyloxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytetradecyloxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydentadecaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydetaxethoxy ] phenyl } propane and the like. The number of ethylene oxide groups in 1 molecule of the 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane is preferably 4 to 20, more preferably 8 to 15. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylate compound having a urethane bond in the molecule include: an addition reaction product of a (meth) acrylic monomer having an OH group at the β -position and a diisocyanate compound (isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, 1, 6-hexamethylene diisocyanate, etc.), tris [ (meth) acryloxytetraethylene glycol isocyanate ] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the nonylphenoxy polyethyleneoxy acrylate include: nonylphenoxy tetraethoxy acrylate, nonylphenoxy pentaethyleneoxy acrylate, nonylphenoxy hexaethyleneoxy acrylate, nonylphenoxy heptaethyleneoxy acrylate, nonylphenoxy octaethyleneoxy acrylate, nonylphenoxy nonaethyleneoxy acrylate, nonylphenoxy decaethyleneoxy acrylate, nonylphenoxy undecenyloxy acrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the phthalic acid-based compound include: gamma-chloro-beta-hydroxypropyl-beta '- (meth) acryloyloxyethylphthalate, beta-hydroxyalkyl-beta' - (meth) acryloyloxyalkylphthalate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofuranediol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexaacrylate are preferable. These compounds may be used alone or in combination of two or more.
The compound having an ethylenically unsaturated double bond is preferably a bisphenol a (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule, from the viewpoint of improving resolution, plating resistance, and adhesion. From the viewpoint that sensitivity and resolution can be improved, bisphenol a (meth) acrylate compounds are preferable. As commercially available products of bisphenol a-based (meth) acrylate compounds, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane (manufactured by shinkamura chemical industries, ltd., BPE-200), 2-bis {4- [ (meth) acryloyloxypolypropoxy ] phenyl) propane (manufactured by shinkamura chemical industries, ltd., BPE-5000; FA-321M manufactured by Hitachi chemical Co., Ltd.), 2-bis {4- [ (meth) acryloyloxypolybutoxy ] phenyl } propane (New Zhongmura chemical Co., Ltd., BPE-1300), and the like.
The content of the compound having an ethylenically unsaturated double bond is preferably 20 to 50 parts by mass, more preferably 25 to 45 parts by mass, in 100 parts by mass of the photosensitive resin composition. When the content of the compound having an ethylenically unsaturated double bond is 20 parts by mass or more, the sensitivity and resolution of the photosensitive resin composition are further improved; when the content is 50 parts by mass or less, the photosensitive resin composition can be more easily made into a thin film, and the durability against etching treatment can be further improved.
Hydrogen donor (D)
The photosensitive resin composition of the present invention further includes a hydrogen donor in order to improve sensitivity. The double imidazole compounds are cracked after illumination, the generated single imidazole free matrix has larger volume, the steric effect causes smaller activity, and the monomer polymerization is difficult to initiate independently, and if the double imidazole compounds are matched with a hydrogen donor, the single imidazole free radical is easy to capture active hydrogen on the hydrogen donor to generate new active free radical, and further initiates the monomer polymerization.
As long as the hydrogen donor has the above characteristics, there is no particular limitation in specific kinds, and may include (but is not limited to): amine compounds, carboxylic acid compounds, mercapto group-containing organic sulfur compounds, alcohol compounds, and the like. These compounds may be used alone, or in combination of two or more thereof.
The amine compound is not particularly limited, and may include (but is not limited to): aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone and the like.
The carboxylic acid-based compound is not particularly limited, and may include (but is not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.
The mercapto group-containing organosulfur compound is not particularly limited and may include (but is not limited to): 2-Mercaptobenzothiazole (MBO), 2-Mercaptobenzimidazole (MBI), dodecylmercaptan, ethylene glycol bis (3-mercaptobutyrate), 1, 2-propanediol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), Trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), 1, 2-propanediol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexa (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1, 2-propanediol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), Butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1, 2-propanediol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), 1, 2-propanediol bis (3-mercaptovalerate), Aliphatic secondary polyfunctional thiol compounds such as diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), and the like; aromatic secondary polyfunctional thiol compounds such as bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, bis (3-mercaptoisobutyl) phthalate and the like.
The alcohol compound is not particularly limited, and may include (but is not limited to): methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, 1, 2-propanediol, 1,2, 3-propanetriol, benzyl alcohol, phenethyl alcohol, etc.
The content of the hydrogen donor (D) may be 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight, in 100 parts by weight of the photosensitive resin composition. When the content of the hydrogen donor is within the above range, it is advantageous to control the sensitivity of the photosensitive resin composition.
Other optional auxiliary agents (E)
In addition to the above components, the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other auxiliary agents as needed. Illustratively, the auxiliary may include at least one of other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photo-colorants, fillers, plasticizers, stabilizers, coating aids, release promoters, and the like.
The other photoinitiators and/or sensitizers may include (but are not limited to): bisimidazoles, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, triazines, coumarins, thioxanthones, acridines and other photoinitiators known to those skilled in the art.
Exemplary bisimidazoles include: 2,2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-1, 1 ' -diimidazole, 2 ', 5-tris (2-fluorophenyl) -4- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-diimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-fluorophenyl) -4- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4 ', 5 ' -diphenyl-diimidazole, 2 ' -bis (2-fluorophenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-methoxyphenyl) -4,4 ', 5,5 ' -tetraphenyl-diimidazole, 2 ' -bis (2-chloro-5-nitrophenyl) -4,4 ' -bis (3, 4-dimethoxyphenyl) -5,5 ' -bis (o-chlorophenyl) -diimidazole, 2 ' -bis (2-chloro-5-nitrophenyl) -4- (3, 4-dimethoxyphenyl) -5- (o-chlorophenyl) -4 ', 5 ' -diphenyl-diimidazole, 2,2 '-bis (2, 4-dichlorophenyl) -4, 4' -bis (3, 4-dimethoxyphenyl) -5,5 '-bis (o-chlorophenyl) -diimidazole, 2- (2, 4-dichlorophenyl) -4- (3, 4-dimethoxyphenyl) -2', 5-bis (o-chlorophenyl) -4 ', 5' -diphenyl-diimidazole, 2- (2, 4-dichlorophenyl) -2 '- (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-diimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4 ', 5, 5' -tetraphenyl-diimidazole and the like. These bisimidazoles may be used alone or in combination of two or more.
Exemplary aromatic ketones include: acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4 '-methylbenzophenone sulfide, 4-benzoyl-4' -ethyldiphenyl sulfide, 4-benzoyl-4 '-propyldiphenyl sulfide, 4' -bis (diethylamino) benzophenone, 4-p-tolylmercapto benzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone, 4 '-bis (dimethylamino) benzophenone, 4' -bis (methyl, ethylamino) benzophenone, acetophenone dimethyl ketal, benzophenone derivatives, and mixtures thereof, Benzil dimethyl ketal,. alpha. '-dimethylbenzyl ketal,. alpha.' -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl etherylphenylacetone, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-butanone, phenylbis (2,4, 6-trimethylbenzoyl) oxyphosphine, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2-hydroxy-1- {3- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,1, 3-trimethyl-inden-5-yl } -2-methyl acetone, 2-hydroxy-1- {1- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,3, 3-trimethyl-inden-5-yl } -2-methyl acetone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) one, and the like. These aromatic ketone compounds may be used alone or in combination of two or more.
Exemplary anthraquinones include: 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone-9, 10-diethyl ester, 1,2, 3-trimethylanthracene-9, 10-dioctyl ester, 2-ethylanthrane-9, 10-bis (methyl chlorobutyrate), 2- {3- [ (3-ethyloxetan-3-yl) methoxy ] -3-oxopropyl } anthracene-9, 10-diethyl ester, 9, 10-dibutoxyanthracene, 9, 10-diethoxy-2-ethylanthrane, 9, 10-bis (3-chloropropoxy) anthracene, 9, 10-bis (2-hydroxyethylmercapto) anthracene, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone, 10-, 9, 10-bis (3-hydroxy-1-propylmercapto) anthracene and the like. These anthraquinone compounds may be used alone or in combination of two or more.
Exemplary benzoin and benzoin alkyl ether compounds include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and the like. These benzoin and benzoin alkyl ether compounds may be used alone or in combination of two or more.
Exemplary oxime ester compounds may include: 1- (4-phenylthiophenyl) -n-octane-1, 2-dione-2-benzoxy-ate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -ethane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -butane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -propane-1-one-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -1-cyclohexyl-methane- 1-keto-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentyl) -propane-1-one-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime benzoate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime benzoate, 1- (4-benzoyldiphenyl sulfide) - (3-cyclopentylacetone) -1-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) - (3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (4-benzoyldiphenyl sulfide) -3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (6-o-methylbenzoyl-9-ethylcarbazole-3-yl) -one-oxime (3-cyclopentyl) -propane-1, 2-dione-2-o-methylbenzoic acid oxime ester, 1- (4-thiophenylphenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- (4-thenoyl-diphenylsulfide-4' -yl) -3-cyclopentyl-propane-1-one-acetic acid oxime ester, 1- (4-benzoyldiphenylsulfide) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-nitro-9-ethylcarbazol-3-yl) -3-cyclohexyl-propane-1-one-acetic acid oxime ester, and salts thereof, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (6-furfurylcarbazol-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime acetate, 1, 4-diphenylpropane-1, 3-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-3-oxime benzoate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, oxime, 2- [ (benzoyloxy) imino ] -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- (thiophene-2-formyl) phenylthiophenyl ] phenyl } -3-cyclopentylpropan-1, 2-dione-2-oxime acetate, and pharmaceutically acceptable salts thereof, 1- [9, 9-dibutyl-2-yl ] -3-cyclohexylpropylpropane-1, 2-dione-2-oxime acetate, 1- [6- (2-benzoyloxyimino) -3-cyclohexylpropyl-9-ethylcarbazol-3-yl ] octane-1, 2-dione-2-oxime benzoate, 1- (7-nitro-9, 9-diallylfluoren-2-yl) -1- (2-methylphenyl) methanone-oxime acetate, 1- [6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl ] -3-cyclopentyl-propane-1-one-oxime benzoate, methyl acetate, ethyl acetate, 1- [7- (2-methylbenzoyl) -9, 9-dibutylfluoren-2-yl ] -3-cyclohexylpropane-1, 2-dione-2-oxime acetate, 1- [6- (furan-2-formyl) -9-ethylcarbazol-3-yl ] -3-cyclohexylpropane-1, 2-dione-2-carbethoxyoxime ester, and the like. These oxime ester compounds may be used alone or in combination of two or more.
Exemplary triazines include: 2- (4-ethylbiphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-methyleneoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 1,1,1,3,3, 3-hexafluoroisopropyl-3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate, ethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, methyl-ethyl-2, 4-bis (trichloromethyl) -s-triazin, 2-ethoxyethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, cyclohexyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, 3- { chloro-4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanamide, benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, and the like, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2, 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1, 3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like. These triazine compounds may be used alone or in combination of two or more.
Exemplary coumarins include: 3,3 '-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3' -carbonylbis (7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3- (2-benzothiazole) -7- (diethylamino) coumarin, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one [7- (diethylamino) -4-methylcoumarin ], 3-benzoyl-7-methoxycoumarin, and the like. These coumarins may be used alone or in combination of two or more.
Exemplary thioxanthone compounds include: thioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone, and the like. These thioxanthone compounds may be used alone or in combination of two or more.
Exemplary acridine compounds include: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluorophenylacridine, 1, 7-bis (9-acridinyl) heptane, 9-ethylaccridine, 9- (4-bromophenyl) acridine, 9- (3-chlorophenyl) acridine, 1, 7-bis (9-acridine) heptane, 1, 5-bis (9-acridinopentane), 1, 3-bis (9-acridine) propane and the like. These acridine compounds may be used alone or in combination of two or more.
The organic solvent may be any solvent capable of dissolving the above components, and may be, for example, a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, a chlorine-containing solvent, and the like, and is preferably selected in consideration of the solubility, coatability, safety, and the like of the colorant and the alkali-soluble polymer. Preferably, the organic solvent may be ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, n-butyl acetate, Ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5, 5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2, 6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol, ethanol, isopropanol, N-propanol, isobutanol, N-butanol, and the like. These solvents may be used alone, or two or more thereof may be used in combination.
Illustratively, dyes, pigments, and photo developers include: tris (4-dimethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, fluoran dye, toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine-green and phthalocyanine-blue and other phthalocyanine systems, auramine base, parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, chrysin green, basic blue 20, brilliant green, eosin, ethyl violet, dittanium sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinadine red, rhodol sodium agar, mirderlein, thymolsulfonphthalein, xylenol blue, methyl orange, tangerine IV, diphenylene flow carbazone, 2, 7-dichlorofluorescein, carmellose red, congo red, wool violet 4B, alpha-naphthylred, phenacetin, methyl violet, victoria pure blue, rhodamine 6G, BOH, Organic pigments such as diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-phenylenediamine, p-toluidine, benzotriazole, tolyltriazole, 4' -diaminobenzidine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl violet, azo pigments and inorganic pigments such as titanium dioxide. In view of good contrast, tris (4-dimethylaminophenyl) methane (i.e. leuco crystal violet, LCV) is preferably used. These dyes, pigments and optical developers may be used singly or in combination of two or more.
Exemplary fillers include: fillers (not including the inorganic pigments) such as silica, alumina, talc, calcium carbonate, and barium sulfate. The filler may be used alone or in combination of two or more.
Exemplary plasticizers include: phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate, ethylene glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, p-toluenesulfonamide and benzenesulfonylSulfonamides such as amines and n-butylbenzenesulfonamide, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tolyldiphenyl phosphate, trixylyl phosphate, 2-naphthyldiphenyl phosphate, tolylbis-2, 6-xylyl phosphate, aromatic condensed phosphate, tris (chloropropyl) phosphate, tris (tribromoneopentyl) phosphate, halogen-containing condensed phosphate, triethylene glycol dioctoate, triethylene glycol di (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl octanedioate, tris (2-ethylethyl phosphate), Brij30[ C ] C12H25(OCH2CH2)4OH]And Brij35[ C ]12H25(OCH2CH2)20OH]And the like. The plasticizer may be used alone or in combination of two or more.
Illustratively, the stabilizers include: hydroquinone, 1,4, 4-trimethyl-diazobicyclo (3.2.2) -non-2-ene-2, 3-dioxide, 1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl-and aryl-substituted hydroquinones and quinones, t-butyl catechol, 1,2, 3-benzenetrisol, copper resinate, naphthylamine, β -naphthol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone, chloranil and the like. The stabilizer may be used alone or in combination of two or more.
Exemplary coating aids include: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methylene chloride, and the like. The coating aids may be used singly or in combination.
Exemplary release promoters include: benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, alkyl benzene sulfonic acid such as methyl, propyl, heptyl, octyl, decyl, dodecyl and the like. The peeling accelerator may be used alone or in combination of two or more.
< Dry film and Wet film applications >
The photosensitive resin composition can be prepared into a dry film, namely a photosensitive resin laminated body, and is applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires and semiconductor packages, and required patterns are formed on different substrates through different procedures.
The photosensitive resin composition of the present invention can be applied to a substrate corresponding to each of the respective manufacturing steps by a wet film coater, that is, applied as a wet film to manufacture of a printed circuit board, a protective pattern, a conductor pattern, a lead wire, and a semiconductor package, and a desired pattern is formed on a different substrate through different processes.
Dry film applications
The dry film, namely, the photosensitive resin laminate of the present invention comprises: a photosensitive resin layer formed by the photosensitive resin composition and a support for supporting the photosensitive resin layer.
Generally, the fabrication of dry films includes: coating the photosensitive resin composition on a support, and drying to form a photosensitive resin layer; optionally, a cover film (protective layer) is attached as necessary. Preferably, the drying condition is 60-100 deg.C for 0.5-15 min. The thickness of the photosensitive resin layer is preferably 5 to 95 μm, more preferably 10 to 50 μm, and still more preferably 15 to 30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation property is not good, and if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be poor.
As the support, specific examples may be various types of plastic films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polyalkylmethacrylate, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, ethylene chloro-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, and the like. In addition, a composite material composed of two or more materials may also be used. Preferably, polyethylene terephthalate having excellent light transmittance is used. The thickness of the support is preferably 5 to 150. mu.m, more preferably 10 to 50 μm.
The photosensitive resin composition is not particularly limited, and can be applied by a conventional method such as spray coating, roll coating, spin coating, slit coating, compression coating, curtain coating, dye coating, line coating, blade coating, roll coating, blade coating, spray coating, and dip coating.
Further, the present invention provides an application of the above dry film in manufacturing a printed circuit board, comprising:
(1) a laminating step: laminating the photosensitive resin laminate on a copper-clad laminate or a flexible substrate;
(2) an exposure step: exposing the photosensitive resin layer in the photosensitive resin laminate to light and irradiating the exposed portion with active light in an image-like manner to perform photocuring;
(3) a developing process: removing the unexposed portion of the photosensitive resin layer with a developing solution to form a protective pattern;
(4) a conductor pattern forming step: etching or plating the part of the surface of the copper-clad laminated plate or the flexible substrate, which is not covered by the protection pattern;
(5) a stripping procedure: and peeling the protective pattern from the copper-clad laminate or the flexible substrate.
Further, the present invention provides the use of the above dry film in the manufacture of a protective pattern, comprising the laminating process, the exposing process and the developing process as described above, except that: the photosensitive resin laminate in the laminating step may be laminated on various substrates made of different materials.
Further, the present invention provides an application of the dry film in the production of a conductor pattern, comprising the above-mentioned laminating process, exposing process, developing process and conductor pattern forming process, except that: the photosensitive resin laminate is laminated on a metal plate or a metal-coated insulating plate in the laminating step.
Further, the present invention provides an application of the above dry film in manufacturing a lead frame wire, comprising the above-mentioned laminating process, exposing process, developing process, and conductor pattern forming process, except that: in the laminating step, the photosensitive resin laminate is laminated on the metal plate, and in the conductor pattern forming step, a portion not covered with the protective pattern is etched.
Further, the present invention provides an application of the above dry film in manufacturing a semiconductor package, comprising the above-mentioned laminating process, exposing process, developing process, and conductor pattern forming process, except that: in the laminating step, the photosensitive resin laminate is laminated on a wafer having a large-scale integrated circuit, and in the conductor pattern forming step, a portion not covered with the protective pattern is plated.
Wet film applications
The photosensitive resin composition of the present invention can be used by directly coating on a substrate in a wet film manner, and is used for the production of printed wiring boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
Without limitation, the photosensitive resin composition may be coated on the substrate by a conventional method such as roll coating, knife coating, spray coating, dip coating, etc., and dried to form the photosensitive resin layer.
After the photosensitive resin layer is formed on the substrate, subsequent processes such as an exposure process, a development process, a conductor pattern formation process, and a peeling process can be performed in a manner referred to dry film application.
In the exposure step, exposure may be performed by a mask exposure method (a method of irradiating actinic rays in an image form through a negative or positive mask pattern of a wiring pattern) or a projection exposure method, or may be performed by a method of irradiating actinic rays in an image form through a direct writing exposure method such as a laser direct imaging exposure method or a digital optical processing exposure method. As the light source of the active light, known light sources, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure lamp, a high pressure lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser, a gallium nitride-based blue-violet laser, and the like, which efficiently emit ultraviolet rays, can be used. Further, a light source that efficiently emits visible light, such as a floodlight for photography or a fluorescent lamp, may be used. The photosensitive resin composition of the present invention is not particularly limited with respect to the type of light source of the active light, and the exposure dose is preferably 10 to 1000mJ/cm2。
In the developing step, the unexposed portion of the photosensitive resin layer is removed with a developing solution. When the support is present on the photosensitive resin layer, the support can be removed by an automatic stripper or the like, and then the unexposed portion can be removed by using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Examples of the alkaline aqueous solution may be a 0.1 to 5 mass% sodium carbonate solution, a 0.1 to 5 mass% potassium carbonate solution, a 0.1 to 5 mass% sodium hydroxide solution, etc., and the pH is preferably 9 to 11. The alkaline aqueous solution may further contain a surfactant, a defoaming agent, an organic solvent, and the like. The developing method may be a conventional method such as dipping, spraying, brushing, etc.
In the etching treatment, the conductor layer of the circuit-forming substrate which is not covered is etched and removed using the resist pattern (i.e., the protective pattern) formed on the substrate as a mask, thereby forming a conductor pattern. The method of the etching process may be selected according to the conductor layer to be removed. Examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkaline etching solution, and a hydrogen peroxide etching solution.
In the plating treatment, copper, solder, or the like is plated on the insulating plate of the circuit-forming substrate that is not covered, using the resist pattern formed on the substrate as a mask. After the plating treatment, the resist pattern is removed to form a conductor pattern. The plating treatment may be electroplating treatment or electroless plating treatment, and is preferably electroless plating treatment. Examples of the electroless plating treatment include: copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-uniformity solder (high-through) plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and gold plating such as hard gold plating and soft gold plating.
The resist pattern can be removed by an aqueous solution having a stronger basicity than the basic aqueous solution used in the developing step. As an example of the strongly alkaline aqueous solution, for example, a1 to 10 mass% aqueous solution of sodium hydroxide can be used.
< color Filter and method for producing the same >
The invention also relates to application of the photosensitive resin composition in manufacturing a color filter, the color filter and a liquid crystal display module containing the color filter.
A color filter made of the photosensitive resin composition comprises: and a colored pattern formed on the support using the photosensitive resin composition.
Techniques for preparing RGB, BM, photo spacers, etc. by photo-curing and photolithography processes using the photosensitive resin composition are well known to those skilled in the art. Generally comprising the steps of: a step of applying a photosensitive resin composition to a support to form a photosensitive resin layer (referred to simply as "forming step"); a step of exposing the photosensitive resin layer through a mask (referred to simply as "exposure step"); and a step of developing the exposed photosensitive resin layer to form a colored pattern (referred to simply as "developing step").
Specifically, the photosensitive resin composition of the present invention is applied directly or via another layer onto a support (substrate) to form a photosensitive resin layer; exposing through a predetermined mask pattern to cure only the coating film irradiated with light; the color filter of the present invention is manufactured by forming a patterned film composed of pixels of each color (3 or 4 colors) by developing with a developer.
Next, each step in the production method of the present invention will be explained.
Formation process
The photosensitive resin layer forming step is to apply the photosensitive resin composition of the present invention on a support to form a photosensitive resin layer.
Examples of suitable supports include soda lime glass, alkali-free glass, pyrex (pyrex) glass, quartz glass, and plastic substrates used for liquid crystal display devices and the like, supports obtained by attaching a transparent conductive film to the supports, photoelectric conversion device substrates used for image sensors and the like, such as silicon substrates and the like, Complementary Metal Oxide Semiconductor (CMOS), and the like. The substrate may be formed with a black matrix (black matrix) for isolating each pixel.
In addition, a lower coating layer may be provided on the support as needed to improve adhesion to an upper layer, prevent diffusion of a substance, or planarize the substrate surface.
As a method for applying the photosensitive resin composition of the present invention to a support, various application methods such as slit coating, an ink jet method, spin coating, roll coating, and a screen printing method can be applied.
The coating thickness of the photosensitive resin composition is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm.
The drying temperature of the photosensitive resin composition coated on the support is 70-110 ℃, and the drying time is 2-4 minutes.
Exposure Process
The exposure step is to expose the photosensitive resin layer formed in the photosensitive resin layer forming step through a mask to cure only the coating film portion irradiated with light.
The exposure is preferably performed by irradiation with radiation, and as radiation usable for the exposure, ultraviolet rays such as g-rays and i-rays are particularly preferably used, and a high-pressure mercury lamp is more preferably used. The irradiation intensity is preferably 5-1500mJ/cm2More preferably 10 to 500mJ/cm2。
Developing process
After the exposure step, an alkaline development treatment (development step) is performed to dissolve the unexposed portion in an alkaline aqueous solution in the exposure step. Thereby, only the photo-cured portion remains.
The developing temperature is usually 20 to 30 ℃ and the developing time is 20 to 90 seconds.
In the production method of the present invention, after the photosensitive resin layer forming step, the exposure step, and the development step are performed, a post-curing step of further curing the formed colored pattern by heating and/or exposure may be added as necessary.
The photosensitive resin layer forming step, the exposure step, and the development step (and the post-curing step added as necessary) are repeated in accordance with the desired number of tones, whereby a color filter having a desired tone composition can be produced.
Drawings
FIG. 1 is a high performance liquid chromatography of compound a 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
1. Preparation of hexaarylbisimidazole photoinitiator
1.1 hexaarylbisimidazole photoinitiators a1
1.1.1 preparation of Monoimidazole Compound a1-3
66g of vitamin B1, 195g of pure water and 195g of ethanol were placed in a 1L four-necked flask, stirred, cooled in an ice bath to an internal temperature of 0 to 10 ℃ and 99g of a 10% aqueous NaOH solution was added dropwise thereto over about 20 minutes, at which time the pH was 8 to 9. Then, a mixed solution of 75g of benzaldehyde (0.7mol) and 99g of o-chlorobenzaldehyde (0.7mol) is added dropwise, after the dropwise addition is completed within about 40 minutes, the temperature is raised to an internal temperature of 65 ℃ for reaction under a condition that the pH is controlled to be 8-9 by additionally adding 10% NaOH aqueous solution. And (4) controlling the concentration of benzaldehyde and o-chlorobenzaldehyde to be less than 1% in sampling HPLC, finishing heat preservation, and removing a water layer. Washed once with 200g of pure water and then with 100mL of 10% NaHSO3The aqueous solution was washed once and finally twice with 200g of pure water to obtain 156g of brown liquid a 1-1.
300g of glacial acetic acid, 0.8g of copper acetate and 157g of ammonium nitrate were placed in a 1L four-necked flask, and after stirring and raising the temperature to an internal temperature of 100 ℃ and then 156g of the brown liquid a1-1 obtained by the above reaction was dissolved in 150g of glacial acetic acid, the resulting solution was added dropwise to the reaction system over about 30 minutes. Sampling HPLC, controlling a1-1 to be less than 1%, and ending the heat preservation. After removal of glacial acetic acid by atmospheric distillation, the reaction mixture was washed once with 200mL of 10% aqueous NaOH solution and twice with 200g of pure water to give 134g of a brown liquid a 1-2.
Figure BDA0002011767650000321
The structure of a1-2 is confirmed by LCMS, mass spectrometry obtains 211 and 212 molecular fragment peaks by means of instrument attached software, the molecular weight of a1-2a is 210, and the product matches with T +1 and T + 2; the 245 and 246 molecular fragment peaks are obtained, the molecular weight of the product a1-2b is 244, and the product a1-2 is consistent with T +1 and T + 2; the 279 and 280 molecular fragment peaks were obtained, and the product a1-2c had a molecular weight of 278, consistent with T +1 and T + 2. LCMS proves that the brown liquid a1-2 consists of three components of a1-2a, a1-2b and a1-2 c.
134g of brown liquid a1-2, 75g of o-chlorobenzaldehyde (0.7mol), 118g of ammonium acetate and 500g of glacial acetic acid were put into a 1L four-necked flask, stirred, heated to an internal temperature of 115 ℃ and reacted for 3 hours while maintaining the temperature. And (3) after controlling a1-2 and o-chlorobenzaldehyde to be less than 1% in sampling HPLC, distilling glacial acetic acid at normal pressure, cooling the residual glacial acetic acid of about 50g to the internal temperature of 100 ℃, slowly dropwise adding 200g of pure water for about 40 minutes, removing a water layer while the glacial acetic acid is hot, and adjusting the pH to 7-8 by using a 10% NaOH aqueous solution. With 100mL of 10% NaHSO3The aqueous solution was washed once and finally twice with 200g of pure water to give a brown oily liquid. The brown oily liquid was dissolved off with 50mL of methanol and then added dropwise to 500mL of purified water, and after completion of the addition, stirring was continued for 30 minutes, followed by suction filtration to give 350g of a yellow solid a 1-3.
Figure BDA0002011767650000322
The structure of a1-3 is confirmed by LCMS, mass spectrometry obtains 311 and 312 molecular fragment peaks by means of instrument attached software, the molecular weight of a1-3a is 330, and the product is matched with T +1 and T + 2; the fragment peaks of 365 and 366 molecules are obtained, the molecular weight of the product a1-3b is 364, and the product is consistent with T +1 and T + 2; the fragment peaks of 399 and 400 molecules were obtained, and the molecular weight of product a1-3c was 398, consistent with T +1 and T + 2. LCMS proves that the brown liquid a1-3 is composed of three components of a1-3a, a1-3b and a1-3 c.
The number of red-shifted substituents in a1-3 is 2 (where a is 0.7, B is 0.7, a is 0, B is 1, and C is 1) calculated according to the formula above.
Figure BDA0002011767650000331
1.1.2 preparation of the Monoimidazole Compound INC
INC was prepared according to the preparation process of a1-3, with the difference that: 2mol of benzaldehyde is subjected to self-condensation and oxidation reaction to obtain 1mol of benzil compound; the benzil compound and 1mol of o-chlorobenzaldehyde generate a mono-imidazole compound INC through cyclization. The INC structure was confirmed using LCMS and mass spectrometry with the aid of the instrument accompanying software gave molecular fragment peaks 311 and 312, with product INC having a molecular weight of 330, consistent with T +1 and T + 2.
Figure BDA0002011767650000332
The number of red-shifted substituents in INC is 1 (where a ' ═ 1, B ' ═ 1, a ' ═ 0, B ' ═ 0, and C ' ═ 1), calculated according to the formula above.
Figure BDA0002011767650000333
1.1.3 preparation of hexaarylbisimidazole photoinitiators a1
Under the protection of nitrogen, 13.0g of yellow solid a1-3(0.036mol), 11.9g of 2- (o-chlorophenyl) -4, 5-diphenyl-Imidazole (INC) (0.036mol), 0.5g of 30% liquid alkali, 0.5g of tetrabutylammonium bromide and 100g of toluene are put into a 500mL four-neck flask, heated and stirred, 40g of sodium hypochlorite (11% aqueous solution) is added dropwise at an internal temperature of 60-65 ℃, the reaction is kept warm after the addition, samples are taken and are controlled by HPLC until a1-3 and INC are both less than 1%, the reaction is complete, and the heat preservation is finished. After completion of the incubation reaction, the reaction mixture was washed four times with 50g of pure water, and then the aqueous layer was extracted once with 20g of toluene, and the organic layer was distilled under reduced pressure. And adding 20g of methanol into the material obtained by distillation, heating and stirring until the solution is clear, then dropwise adding the clear solution into a solution prepared from 20g of methanol and 200g of pure water, and filtering, leaching and drying after the dropwise adding is finished to obtain 23.4g of a product a 1.
The product a1 was analyzed by high performance liquid chromatography, and as shown in FIG. 1, the total content of bisimidazole in the product a1 was 94.5%.
The solubility of product a1 in butanone was 23.1%.
The molar ratio of the red-shifted substituents of the product a1 in all substitutable sites of the hexaarylbisimidazole photoinitiators was calculated according to the above formula to be 10.0% (where e ═ 0.036, f ═ 0.036, m ═ 2, and n ═ 1).
Figure BDA0002011767650000341
1.2 hexaarylbisimidazole photoinitiators a2
Referring to the preparation process of a1, 0.0072mol of a1-3 is reacted with 0.0648mol of INC, and other parameters and conditions are not changed to obtain a2 product. The product a2 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a2 was 93.6%.
The solubility of product a2 in butanone was 19.8%.
The molar ratio of the red-shifted substituents of the product a2 in all substitutable sites of the hexaarylbisimidazole photoinitiator was 7.3% (where e ═ 0.0072, f ═ 0.0648, m ═ 2, and n ═ 1), calculated according to the formula above.
1.3 hexaarylbisimidazole photoinitiators a3
Referring to the preparation process of a1, 0.0648mol of a1-3 and 0.0072mol of INC are used for reaction, and other parameter conditions are unchanged to obtain a3 product. The product a3 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a3 was 94.9%.
The solubility of product a3 in butanone was 25.2%.
The molar ratio of the red-shifted substituents of the product a3 in all substitutable sites of the hexaarylbisimidazole photoinitiator was calculated to be 12.7% (where e ═ 0.0648, f ═ 0.0072, m ═ 2, and n ═ 1) according to the above formula.
1.4 hexaarylbisimidazole photoinitiators a4
The preparation process referred to a1-3 prepares a4-1, except that: 1mol of p-tolualdehyde and 1mol of o-chlorobenzaldehyde are subjected to condensation and oxidation reaction to obtain 1mol of benzil compound; the benzil compound and 1mol of 2, 4-dichlorobenzaldehyde generate a mono-imidazole compound a4-1 through a cyclization reaction.
The number of red-shifted substituents in a4-1 is 3 (where a is 1, B is 1, a is 0, B is 1, and C is 2) calculated according to the above formula.
Figure BDA0002011767650000351
Referring to the preparation process of a1, 0.036mol of a4-1 is used for reacting with 0.036mol of INC, and other parameter conditions are not changed to obtain a 4. The product a4 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a4 was 93.9%.
The solubility of product a4 in butanone was 35.7%.
The molar ratio of the red-shifted substituents of the product a4 in all substitutable sites of the hexaarylbisimidazole photoinitiators was calculated to be 13.3% (where e ═ 0.036, f ═ 0.036, m ═ 3, and n ═ 1) according to the above formula.
1.5 hexaarylbisimidazole photoinitiators a5
Referring to the preparation process of a1, 0.048mol of a4-1 is reacted with 0.024mol of INC, and other parameter conditions are unchanged to obtain a 5. The product a5 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a5 was 95.2%.
The solubility of product a5 in butanone was 43.4%.
The molar proportion of the product a5 of red-shifted substituents in all substitutable sites of hexaarylbisimidazole photoinitiators was 15.6% (where e ═ 0.048, f ═ 0.024, m ═ 3, and n ═ 1), calculated according to the formula above.
1.6 hexaarylbisimidazole photoinitiators a6
The preparation process referred to a1-3 prepares a6-1, except that: 1mol of p-tolualdehyde and 1mol of benzaldehyde are subjected to condensation and oxidation reaction to obtain 1mol of benzil compound; the benzil compound and 1mol of o-chlorobenzaldehyde generate a mono-imidazole compound a6-1 through cyclization.
The number of red-shifted substituents in a6-1 is 1 (where a is 1, B is 1, a is 0, B is 0, and C is 1) calculated according to the above formula.
Figure BDA0002011767650000361
Referring to the preparation process of a1, 0.04mol of a6-1 reaction is used, and other parameter conditions are not changed to obtain a 6. The product a6 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a6 was 93.4%.
The solubility of product a6 in butanone was 25.1%.
The molar ratio of the red-shifted substituents of the product a6 in all substitutable sites of the hexaarylbisimidazole photoinitiators was 6.7% (where e ═ 0.02, f ═ 0.02, m ═ 1, and n ═ 1), calculated according to the formula above.
1.7 hexaarylbisimidazole photoinitiators a7 (comparative example)
Referring to the preparation process of a1, 0.0648mol of a4-1 and 0.0072mol of INC are used for reaction, and other parameters are unchanged to obtain a7 product. The product a7 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a7 was 94.1%.
The solubility of product a7 in butanone was 48.1%.
The molar ratio of the red-shifted substituents of the product a7 in all substitutable sites of the hexaarylbisimidazole photoinitiator was 18.7% (where e ═ 0.0648, f ═ 0.0072, m ═ 3, and n ═ 1), as calculated according to the formula above.
1.7 hexaarylbisimidazole photoinitiators a8, a9 and a10 (comparative examples)
a8 is BCIM (single structure HABI) produced by Changzhou Strong Electron New materials Ltd, wherein the molar ratio of the red-shifted substituent in all substitutable sites of hexaarylbisimidazole photoinitiators is 6.7%.
a9 is TR-HABI-104 (single structure HABI) manufactured by Hezhou Strong Electron New materials Ltd, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 13.3%.
Figure BDA0002011767650000381
a10 is TCDM (hybrid HABI) produced by Hezhou Strong Electron New materials Ltd, wherein the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 16.7%.
Figure BDA0002011767650000382
2. Preparation of photosensitive resin composition
The photosensitive resin compositions were obtained by uniformly mixing the respective components with reference to the formulation shown in Table 1-2-1. Unless otherwise specified, the parts shown in Table 1-2-1 are parts by mass.
TABLE 1-2-1
Figure BDA0002011767650000383
Figure BDA0002011767650000391
The symbols of the respective components in Table 1-2-1 indicate the meanings as shown in Table 1-2-2.
Tables 1-2
Figure BDA0002011767650000392
Figure BDA0002011767650000401
Preparation of alkali-soluble Polymer B: 500g of a mixed solvent of methyl cellosolve and toluene (mass ratio: 3:2) was added to a flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere, and after stirring and heating to 80 ℃, a solution prepared by mixing 100g of methacrylic acid, 200g of ethyl methacrylate, 100g of ethyl acrylate, 100g of styrene and 0.8g of azobisisobutyronitrile was slowly dropped into the flask for 4 hours, and the reaction was continued for 2 hours after the completion of the dropping. Then, 100g of a mixed solvent (composition as above) in which 1.2g of azobisisobutyronitrile was dissolved was dropped into the flask for 10 minutes, and after completion of the dropping, the reaction was further carried out at 80 ℃ for 3 hours, and the temperature was raised to 90 ℃ to continue the reaction for 2 hours. After completion of the reaction, the reaction mixture was filtered to obtain an alkali-soluble polymer B having an acid value of 196mgKOH/g and a weight-average molecular weight of about 80000.
The photosensitive resin compositions were obtained by uniformly mixing the respective components with reference to the formulations shown in tables 1-2-3. Unless otherwise specified, the parts shown in the table are parts by mass.
Tables 1-2-3
Figure BDA0002011767650000411
Figure BDA0002011767650000421
Wherein, the meanings of each component in tables 1-2-3 are shown in tables 1-2-4.
Tables 1-2-4
Figure BDA0002011767650000422
3. Evaluation of Performance
3.1 light sensitivity
A photosensitive resin composition was coated on a glass substrate by a spin coater, and then dried at 100 ℃ for 5 minutes to remove the solvent to form a coating film having a thickness of 10 μm, the coating process was carried out either once or in multiple portions to obtain the coating film having the above thickness, the substrate with the coating film was cooled to room temperature, and the substrate was subjected to an exposure of 50mJ/cm at a wavelength of 365nm through a mask 20 μm in a longitudinal direction of 20 μm × and a transverse direction of 20 μm by an i-line reduction projection exposure apparatus2The coating film was irradiated. After the irradiation, the coating film was developed at 23 ℃ for 60 seconds using a developing solution (trade name: CD-2000, 60%, manufactured by Fuji film electronics). Then, the image was rinsed with running water for 20 seconds, and then spray-dried to obtain a pattern image. Image formation was confirmed by an optical microscope. The pixel pattern obtained has a large width, and is therefore highly sensitive and thus preferable.
The width of the obtained pixel pattern is determined by the following criteria:
o: more than 35 μm;
very good: 20 μm or more and less than 35 μm;
●: less than 20 μm.
3.2 resolution
After exposure development was performed using a photomask having a wiring pattern of Line/Space of 10:10 to 150:150 (unit: μm), the resolution was measured. The resolution is the minimum value of the pattern from which unexposed portions are removed in the resist pattern formed by development after exposure, and is graded as follows:
o: the resolution value is below 30 μm;
very good: the resolution value is 30-50 μm, not including the end value;
●: the resolution value is above 50 μm.
3.3 developability
After development, the photoresist pattern was observed by a Scanning Electron Microscope (SEM) to evaluate developability. The developability was evaluated according to the following criteria:
□: no residue was observed in the unexposed parts;
and (delta): a small amount of residue was observed in the unexposed parts, but the residual amount was acceptable;
x: a clear residue was observed in the unexposed parts.
3.4 resist Pattern shapes
The shape of the resist pattern was observed with a Scanning Electron Microscope (SEM) (product name "SU-1500" manufactured by hitachi high & new technologies, ltd.) at an acceleration voltage of 15kV, a magnification of 3000 times, and an inclination angle of 60 degrees, and was judged according to the following criteria:
□: undercut and absence of the upper part of the resist pattern were not observed in the shape of the resist pattern, and the linearity of the pattern profile was good;
and (delta): undercutting, loss of the upper portion of the resist pattern, and poor linearity of the pattern profile were observed in the resist pattern shape.
3.5 hydrophilicity
Hydrophilicity was evaluated by the amount of precipitation after dissolution of the photosensitive resin layer. The photosensitive resin composition was sufficiently stirred and uniformly applied to the surface of a 25 μm-thick polyethylene terephthalate film as a support by using a bar coater. The resultant was dried at 95 ℃ for 4min in a dryer to form a photosensitive resin layer having a layer thickness of about 30.5 μm and a layer weight of about 3.2 g. A developer was prepared by dissolving 20g of sodium carbonate in 2L of water and adding 1.5ml of P1uronic RPG3110(BASF, Mt. Olive, NJ, this agent is a polyoxyethylene and polyoxypropylene copolymer plasticizer). The film with the photosensitive resin layer was put into 100g of a developing solution, and the sample was left to stand until the resin layer was dissolved, and the amount of the precipitate was determined in the following order:
0 ═ amount of precipitate less than 0.005 g;
1, a small amount of finely dispersed light yellow substance, and the precipitation amount is between 0.005 and 0.01 g;
5 to medium light yellow (usually finer) and precipitation between 0.05 and 0.08 g;
when the precipitate is 10 g, a large amount of solid layer light yellow (usually in a flake form) is precipitated, and the precipitate amount is more than 0.1 g.
The evaluation results are shown in Table 2-1.
TABLE 2-1
Evaluation item Sensitivity of light Resolution ratio Developability Resist pattern shape Hydrophilicity
Example 1 ◎ ○ □ □ Level 0
Example 2 ◎ ○ □ □ Level 0
Example 3 ◎ ○ □ □ Level 0
Example 4 ◎ ○ □ □ Level 0
Example 5 ◎ ○ □ □ Level 0
Example 6 ◎ ○ □ □ Level 0
Example 7 ◎ ○ □ □ Level 0
Example 8 ◎ ○ □ □ Level 0
Example 9 ◎ ○ □ □ Level 0
Example 10 ◎ ○ □ □ Level 0
Example 11 ◎ ○ □ □ Level 0
Example 12 ◎ ○ □ □ Level 0
Comparative example 1 ○ ◎ △ △ Level 1
Comparative example 2 ◎ ◎ △ △ Grade 5
Comparative example 3 ◎ ◎ △ △ Grade 5
Comparative example 4 ○ ◎ □ △ Level 1
Comparative example 5 ○ ◎ △ △ Level 1
Comparative example 6 ◎ ◎ △ △ Grade 5
Comparative example 7 ◎ ◎ △ △ Grade 5
Comparative example 8 ○ ◎ □ △ Level 1
The photosensitive resin composition has moderate sensitivity, good solubility, excellent resolution and developability, and does not generate an inverted trapezoid during development. In addition, the hydrophilic developing solution has better hydrophilicity, and can obviously reduce the amount of sludge in the developing solution during recycling, so that the developing solution can be repeatedly and effectively used.
The photosensitive resin composition can be widely applied to the aspects of manufacturing printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages and the like in a dry film and wet film mode, and can also be applied to the manufacturing of color filters and liquid crystal display components.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (15)

1. A hexaarylbisimidazole photoinitiator is prepared by the following steps:
(1) aromatic aldehyde shown in a general formula (I) and aromatic aldehyde shown in a general formula (II) are subjected to condensation and oxidation reaction to obtain a benzil compound; the benzil compound and aromatic aldehyde shown in a general formula (III) generate a mono-imidazole compound M through cyclization reaction;
(2) the aromatic aldehyde shown in the general formula (IV) and the aromatic aldehyde shown in the general formula (V) are subjected to condensation and oxidation reaction to obtain a benzil compound; the benzil compound and aromatic aldehyde shown in a general formula (VI) generate a mono-imidazole compound N through a cyclization reaction;
(3) the single imidazole compound M and the single imidazole compound N generate a hexaaryl bisimidazole photoinitiator through oxidation reaction;
Figure FDA0002011767640000011
wherein R is1-R30Each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxy, C1-C10Alkyl of (C)1-C10Alkoxy of, or C2-C10And the methylene groups in each group may be optionally substituted by oxygen, sulfur, imino groups;
provided that the red-shifted substituent is at all substitutable sites of the hexaarylbisimidazole photoinitiator, namely R1-R30The molar ratio of (A) is 6-16%.
2. The hexaarylbisimidazole photoinitiator according to claim 1, characterized in that: the red-shifted substituent comprises chlorine, bromine, nitro, cyano, amino, hydroxyl and C2-C10Alkenyl of (C)1-C10Wherein the methylene group in each group may be optionally substituted by oxygen, sulfur, an imino group; preferably, the bathochromic substituent is selected from the group consisting of chlorine, bromine, hydroxyl, amine, and C1-C5Alkoxy group of (2).
3. A photosensitive resin composition comprising the following components:
(A) a hexaarylbisimidazole-based photoinitiator according to claim 1 or 2;
(B) an alkali soluble polymer;
(C) a compound having an ethylenically unsaturated double bond;
(D) a hydrogen donor;
(E) other optional adjuvants.
4. The photosensitive resin composition according to claim 3, wherein: the alkali-soluble polymer is a (meth) acrylic polymer, a styrene polymer, an epoxy polymer, an aliphatic urethane (meth) acrylate polymer, an aromatic urethane (meth) acrylate polymer, an amide resin, an amide epoxy resin, an alkyd resin, or a phenolic resin.
5. The photosensitive resin composition according to claim 4, wherein: the alkali-soluble polymer is an alkali-soluble polymer containing a carboxyl group; preferably, the carboxyl group-containing alkali-soluble polymer is a (meth) acrylate-based polymer obtained by copolymerizing a (meth) acrylate, an ethylenically unsaturated carboxylic acid, and other copolymerizable monomers.
6. The photosensitive resin composition according to claim 3, wherein: the weight average molecular weight of the alkali-soluble polymer is 15000-200000, preferably 30000-150000, particularly preferably 30000-120000; the acid value is 50 to 300mgKOH/g, preferably 50 to 250mgKOH/g, more preferably 70 to 250mgKOH/g, and particularly preferably 100 to 250 mgKOH/g.
7. The photosensitive resin composition according to claim 3, wherein: the compound having an ethylenically unsaturated double bond is selected from at least one of the following compounds:
a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol a-based (meth) acrylate compound, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a (meth) acrylate compound having a urethane bond in the molecule, nonylphenoxy polyethyleneoxy acrylate, γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, a phthalic compound, and an alkyl (meth) acrylate.
8. The photosensitive resin composition according to claim 7, wherein: the compound having an ethylenically unsaturated double bond is selected from bisphenol A (meth) acrylate compounds and (meth) acrylate compounds having an urethane bond in the molecule.
9. The photosensitive resin composition according to claim 3, wherein: the hydrogen donor is at least one selected from amine compounds, carboxylic acid compounds, organic sulfur compounds containing sulfydryl and alcohol compounds.
10. The photosensitive resin composition according to claim 3, wherein: and at least one of other photoinitiator and/or sensitizer, organic solvent, dye, pigment, optical developer, filler, plasticizer, stabilizer, coating auxiliary agent and stripping accelerator.
11. A photosensitive resin laminate comprising: a photosensitive resin layer formed of the photosensitive resin composition according to any one of claims 3 to 10, and a support for supporting the photosensitive resin layer.
12. Use of the photosensitive resin composition according to any one of claims 3 to 10 or the photosensitive resin laminate according to claim 11 for the production of printed wiring boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.
13. Use of the photosensitive resin composition according to any one of claims 3 to 10 or the photosensitive resin laminate according to claim 11 for producing a color filter.
14. A color filter comprising: a support, and a colored pattern formed on the support by using the photosensitive resin composition according to any one of claims 3 to 10 or the photosensitive resin laminate according to claim 11.
15. A liquid crystal display device comprising the color filter according to claim 14.
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