WO2020200020A1 - Hexaarylbiimidazole photoinitiator and application thereof - Google Patents

Hexaarylbiimidazole photoinitiator and application thereof Download PDF

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Publication number
WO2020200020A1
WO2020200020A1 PCT/CN2020/081293 CN2020081293W WO2020200020A1 WO 2020200020 A1 WO2020200020 A1 WO 2020200020A1 CN 2020081293 W CN2020081293 W CN 2020081293W WO 2020200020 A1 WO2020200020 A1 WO 2020200020A1
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meth
photosensitive resin
acrylate
compounds
resin composition
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PCT/CN2020/081293
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French (fr)
Chinese (zh)
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钱彬
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常州格林感光新材料有限公司
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Priority to JP2021558511A priority Critical patent/JP7212971B2/en
Priority to KR1020217035296A priority patent/KR102700610B1/en
Publication of WO2020200020A1 publication Critical patent/WO2020200020A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the invention belongs to the field of organic chemistry, and specifically relates to a hexaarylbisimidazole photoinitiator, a photosensitive resin composition containing the photoinitiator, and applications thereof.
  • photosensitive resin compositions With the miniaturization of precision electronic equipment, photosensitive resin compositions have become a research hotspot. Among them, the influence of photoinitiators on the sensitivity, solubility, hydrophilicity, resolution and developability of photosensitive resin compositions is the focus of research. The most important. As an indispensable component of the photosensitive resin composition, photoinitiators are generally required to have high initiation efficiency, excellent solubility, and excellent hydrophilicity. However, the application found that not all physical and chemical indicators are as high as possible. For example, as the application becomes more and more refined, too high sensitivity of the photoinitiator will easily lead to insufficient manufacturing accuracy and high defective rate.
  • Hexaarylbisimidazole compounds are a kind of known photoinitiators.
  • relevant research mainly focuses on: changing the substituent groups on the aryl group to increase the hydrophilicity, thereby reducing the development waste; changing the substituent groups on the aryl group Group to increase sensitivity; increase color-changing group to improve development recognition and so on.
  • the applicant further studied the substituents introduced on the aryl groups in the hexaarylbisimidazole photoinitiators, the proportion and composition of the redshift groups in the substituents , And then comprehensively control the properties of sensitivity, solubility, hydrophilicity, resolution and developability, so that the photosensitive resin composition using the photoinitiator has an appropriate curing rate in the application without affecting Development to obtain the required photolithography pattern, but also has the advantages of low development waste, thereby broadening the practical application of hexaarylbisimidazole photoinitiators.
  • the purpose of the present invention is first to provide a hexaarylbisimidazole photoinitiator to solve the problem of inverted trapezoids that do not meet the application requirements and the development waste cannot be effectively reduced when the existing photoinitiators are used in high-precision circuits. problem.
  • the photoinitiator of the present invention When the photoinitiator of the present invention is applied to a photosensitive resin composition, it has moderate sensitivity, good solubility, excellent resolution and developability, does not appear inverted trapezoid shape during development, and has good hydrophilicity, which can significantly reduce The amount of sludge in the developer during recycling enables the developer to be used repeatedly and effectively.
  • hexaarylbisimidazole photoinitiator of the present invention is prepared by the following steps:
  • R 1 -R 30 each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, or C 2 -C
  • the alkenyl group of 10 , and the methylene group in each group may be optionally substituted by oxygen, sulfur, and imino groups;
  • the premise is that the molar ratio of the red-shifted substituents at all substitutable positions of the hexaarylbisimidazole photoinitiator, namely R 1 -R 30 , is 6-16%.
  • the object of the present invention is also to provide a photosensitive resin composition containing the above-mentioned photoinitiator, and the application of the composition in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
  • Another object of the present invention is to provide an application of the above-mentioned photosensitive resin composition in the manufacture of a color filter, a color filter, and a liquid crystal display module containing the color filter.
  • sludge and "developing garbage” in this application refer to substances accumulated in the developer solution, which are insoluble in the developer solution and will re-deposit on the developed substrate, thereby reducing the efficiency of the developer solution.
  • the hexaarylbisimidazole photoinitiator of the present invention is prepared by the following steps:
  • R 1 -R 30 each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, or C 2 -C
  • the alkenyl group of 10 , and the methylene group in each group may be optionally substituted by oxygen, sulfur, and imino groups;
  • the premise is that the molar ratio of the red-shifted substituents at all substitutable positions of the hexaarylbisimidazole photoinitiator, namely R 1 -R 30 , is 6-16%.
  • the red-shifted substituent mentioned in the present invention refers to the substituted group introduced on the aromatic ring to increase the conjugation degree of the hexaarylbisimidazole structure, which in turn causes the ultraviolet absorption wavelength to shift toward the long wavelength (that is, redshift Phenomenon) group.
  • the red-shifted substituents include chlorine, bromine, nitro, cyano, amine, hydroxyl, C 2 -C 10 alkenyl, C 1 -C 10 alkoxy, wherein the sub-group in each group
  • the methyl group may be optionally substituted with oxygen, sulfur, or imino groups.
  • the red-shifted substituent is selected from chlorine, bromine, hydroxyl, amine, and C 1 -C 5 alkoxy.
  • the molar ratio of the red-shifted substituents in all substitutable sites (ie, R 1 -R 30 ) of the hexaarylbisimidazole photoinitiator is 6-16%. If the molar ratio of the red-shifted substituents is greater than 16%, the surface is easily cured but the inside is not completely cured due to the high sensitivity, which makes the narrow lines of photolithography appear inverted trapezoid after development Therefore, the prepared product does not meet the application requirements; if the molar ratio of the red-shifted substituent is less than 6%, the sensitivity is low, the curing speed is slow, and the preparation efficiency is reduced.
  • the application shows that when the hexaarylbisimidazole photoinitiator of the present invention is applied to a photosensitive resin composition, the composition has moderate sensitivity, good solubility, excellent resolution and developability, and does not appear inverted trapezoid during development. . In addition, it also has good hydrophilicity, which can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be used repeatedly and effectively.
  • 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, which is characterized by comprising the following components:
  • the hexaarylbisimidazole photoinitiator of the present invention does not limit the attachment position of the bisimidazole.
  • the hexaarylbisimidazole-based photoinitiator may be selected from or include at least one of the following compounds:
  • the content of the hexaarylbisimidazole-based photoinitiator (A) is 1-20 parts by mass, preferably 1-10 parts by mass. If the content is too small, there is a defect that the photosensitivity is reduced; if the content is too large, there is a defect that the photoresist pattern tends to become wider than the line width of the photomask.
  • the alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition.
  • any polymer having such characteristics can be used without particular limitation.
  • suitable alkali-soluble polymers can be (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethanes (meth) Base) Acrylate polymer, amide resin, amide epoxy resin, alkyd resin, phenolic resin, etc.
  • the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer.
  • polymerizable monomers include: styrene, vinyl toluene, ⁇ -methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene, etc.
  • styrene derivatives in the ⁇ -position or aromatic Ring-substituted polymerizable styrene derivatives; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid , ⁇ -bromo(meth)acrylic acid, ⁇ -chloro(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, ⁇ -styryl(meth)acrylic acid and other (meth)acrylic acid derivatives; Alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ( (Meth) diethylaminoethyl acrylate, glycidyl (meth)acrylate,
  • 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; and may further include (meth)acrylic acid in addition to (meth)acrylic acid.
  • Meth) acrylic acid alkyl ester as a copolymer of monomer units; in addition to (meth) acrylic acid, it can also contain polymerizable monomers other than (meth) acrylic acid and (meth) acrylic acid alkyl esters (such as A monomer having an ethylenically unsaturated group) is a copolymer as a monomer component.
  • alkali-soluble polymers containing carboxyl groups can be obtained by radical polymerization of polymerizable monomers having carboxyl groups with other polymerizable monomers, especially those made from (meth)acrylates, ethylenically unsaturated carboxylic acids and other A (meth)acrylate-based polymer formed by copolymerization of copolymerizable monomers.
  • the (meth)acrylate can be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate , Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylic acid Decyl ester, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethyl (meth)acrylate Amino ethyl, dimethylamino ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)
  • the ethylenically unsaturated carboxylic acid can be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, particularly preferably acrylic acid and methacrylic acid. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more kinds.
  • the other copolymerizable monomers can be (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinyl naphthalene, (meth)acrylonitrile, vinyl acetate, vinyl cyclohexane Wait. These other copolymerizable monomers may be used alone or in combination of two or more.
  • the alkali-soluble polymer may be used alone or in combination of two or more.
  • the alkali-soluble polymer used in combination of two or more kinds two or more kinds of alkali-soluble polymers composed of different copolymerization components, two or more kinds of alkali-soluble polymers with different weight average molecular weights, and two kinds of different dispersion degrees can be cited.
  • the weight average molecular weight of the alkali-soluble polymer is not particularly limited, and it should be adapted to the specific application environment. Considering the mechanical strength and alkali developability comprehensively, the weight average molecular weight is preferably 15,000 to 200,000, more preferably 30,000 to 150,000, and particularly preferably 30,000 to 120,000. When the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved. When the weight average molecular weight is less than 200,000, the development time tends to become shorter, and it can maintain the compatibility with other components such as photoinitiators. Compatibility.
  • the weight average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC), and is obtained by conversion using a standard curve of standard polystyrene.
  • the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, still more preferably 70-250 mgKOH/g, and particularly preferably 100- 250mgKOH/g.
  • the acid value of the alkali-soluble resin is less than 50mgKOH/g, it is difficult to ensure a sufficient development speed.
  • it exceeds 300mgKOH/g the adhesion is reduced, pattern short-circuiting is likely to occur, and the composition is likely to decrease storage stability and viscosity The problem of rising.
  • the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5-6.0, particularly preferably 1.8-3.7. When the molecular weight distribution is in the range, the developability is excellent.
  • the content of the alkali-soluble polymer in the composition is preferably 20-70 parts by mass, more preferably 30-60 parts by mass.
  • the content of the alkali-soluble polymer is 20 parts by mass or more, it can ensure that the photosensitive resin composition has improved durability for plating treatment, etching treatment, etc., and when the content is less than 70 parts by mass, it is beneficial to improve the photosensitive resin composition The sensitivity.
  • 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, as long as a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used.
  • examples include: compounds obtained by reacting ⁇ , ⁇ -unsaturated carboxylic acids with polyhydric alcohols, bisphenol A (meth)acrylate compounds, ⁇ , ⁇ -unsaturated carboxylic acids, and glycidyl-containing compounds
  • urethane monomers such as (meth)acrylate compounds with urethane bonds in the molecule, nonylphenoxy polyvinyloxy acrylate, ⁇ -chloro- ⁇ -hydroxypropyl - ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxypropyl- ⁇ '-(meth)
  • Examples of the compound obtained by reacting the above-mentioned ⁇ , ⁇ -unsaturated carboxylic acid with a polyhydric alcohol include polyethylene glycol di(meth)acrylate having an ethylene number of 2-14, and a propylene number of 2 Polypropylene glycol di(meth)acrylate of 14, ethylene number of 2-14 and propylene number of 2-14 polyethylene ⁇ polypropylene glycol di(meth)acrylate, trimethylol Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate Base) acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, two Pentaerythritol penta
  • EO means ethylene oxide
  • PO stands for propylene oxide
  • a PO-modified compound refers to a compound having a block structure of an oxypropylene group.
  • Examples of the bisphenol A-based (meth)acrylate compound include: 2,2-bis ⁇ 4-[(meth)acryloxypolyethoxy]phenyl ⁇ propane, 2,2- Bis ⁇ 4-[(meth)acryloxypolypropoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxypolybutoxy]phenyl ⁇ propane, 2,2-Bis ⁇ 4-[(meth)acryloyloxypolyethoxypolypropoxy]phenyl ⁇ propane and the like.
  • 2,2-bis ⁇ 4-[(meth)acryloyloxypolyethoxy]phenyl ⁇ propane there may be mentioned: 2,2-bis ⁇ 4-[(meth)acryloyloxy Diethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxytriethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(methyl )Acryloyloxytetraethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxypentaethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4- [(Meth)acryloyloxyhexaethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloyloxyheptethoxy]phenyl ⁇ propane, 2,2- Bis ⁇ 4-[(meth)acryloyloxyoctaethoxy]phenyl ⁇ propane, 2,2-bis ⁇
  • the number of oxyethylene groups in one molecule of the 2,2-bis ⁇ 4-[(meth)acryloyloxypolyethoxy]phenyl ⁇ propane is preferably 4-20, and more preferably 8-15. These compounds may be used alone or in combination of two or more kinds.
  • the (meth)acrylate compound having a urethane bond in the molecule a (meth)acrylic monomer having an OH group at the ⁇ -position and a diisocyanate compound (isophorone diisocyanate, 2 ,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tris((meth)acryloyloxytetraethylene glycol isocyanate) ] Hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO, PO modified urethane di(meth)acrylic acid Ester etc. These compounds may be used alone or in combination of two or more kinds.
  • nonylphenoxy polyvinyloxy acrylate nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy hexaethylene Oxyacrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxydecaethyleneoxy Acrylate, nonylphenoxyundecenyloxy acrylate, etc. These compounds may be used alone or in combination of two or more kinds.
  • phthalic acid compound examples include: ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl phthalate, ⁇ -hydroxyalkyl- ⁇ '-(Meth)acryloyloxyalkyl phthalate, etc. These compounds may be used alone or in combination of two or more kinds.
  • the alkyl (meth)acrylate may, for example, be 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, (methyl) ) Isobornyl acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-hydroxypropyl ester, benzyl (meth)acrylate, amyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)
  • These compounds may be used alone or in combination of two or more kinds.
  • the compound having an ethylenically unsaturated double bond is preferably a bisphenol A (meth)acrylate compound and a compound having a urethane bond in the molecule ( Meth)acrylate compound. From the viewpoint of improving sensitivity and resolution, bisphenol A-based (meth)acrylate compounds are preferred.
  • the content of the compound having an ethylenically unsaturated double bond is preferably 20-50 parts by mass, more preferably 25-45 parts by mass.
  • the sensitivity and resolution of the photosensitive resin composition will be further improved; when the content is less than 50 parts by mass, the photosensitive resin composition is more easily The film becomes thinner, and the durability against etching treatment is further improved.
  • the photosensitive resin composition of the present invention further includes a hydrogen donor in order to improve sensitivity.
  • the bisimidazole compounds are cleaved after exposure to light, and the monoimidazole radicals produced are larger in volume. The steric hindrance makes the activity less, and it is difficult to initiate monomer polymerization alone. If used in conjunction with hydrogen donors, the monoimidazole radicals are easy The active hydrogen on the hydrogen donor is taken away to generate new active free radicals, which in turn initiates monomer polymerization.
  • Amine compounds are not particularly limited, and may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as 4-dimethylaminobenzoic acid methyl Ester, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N , N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.
  • aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.
  • aromatic amine compounds such as 4-dimethylaminobenzoic acid methyl Ester,
  • the carboxylic acid compounds are not particularly limited, and may include (but are not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylsulfide Acetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenyl Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.
  • the organosulfur compounds containing mercapto groups are not particularly limited, and may include (but are not limited to): 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis( 3-mercaptobutyrate), 1,2-propanediol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), Octanediol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptobutyrate) , Ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol
  • 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 0.01-20 parts by weight, preferably 0.01-10 parts by weight.
  • the content of the hydrogen donor is within the above range, it is advantageous to control the sensitivity of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention may further contain an appropriate amount of other auxiliary agents as needed.
  • the auxiliary agent may include other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, light developers, fillers, plasticizers, stabilizers, coating aids, peeling promoters, etc. At least one of them.
  • the other photoinitiators and/or sensitizers may include (but are not limited to): bisimidazoles, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, three Azazines, coumarins, thioxanthones, acridines and other photoinitiators known to those skilled in the art.
  • bisimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tris(ortho Chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tris(2-fluoro Phenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4 ,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxy Phenyl)-4',5'-diphenyl-diimidazole, 2,2'
  • the aromatic ketone compounds include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 ,1-Dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyl Diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino)benzophenone, 4-p-toluene mercaptobenzophenone, 2 ,4,6-Trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethyl Amino) benzophenone, acetophenone dimethyl ketal, benzil dimethyl ket
  • anthraquinone compounds include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl, 1,2,3-trimethylanthracene-9,10-dioctyl, 2-ethylanthracene-9,10-bis(4-chlorobutyric acid Methyl ester), 2- ⁇ 3-[(3-ethyloxetan-3-yl)methoxy]-3-oxopropyl ⁇ anthracene-9,10-diethyl ester, 9,10 -Dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethy
  • 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 can be used alone or in combination of two or more.
  • the oxime ester compound may include: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-[6-(2-methyl Benzoyl)-9-ethylcarbazol-3-yl]-ethane-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole -3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-propan-1-one- Oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-cyclohexyl-methane-1-one-oxime acetate, 1-[6 -(2-Methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-
  • triazine compounds include: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-ethylene Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazine -6-yl]phenylthio)propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3- ⁇ 4-[2,4-bis(trichloromethyl)-s- Triazine-6-yl]phenylthio ⁇ propionate, ethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio ⁇ ethyl Ester, 2-ethoxyethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-y
  • the coumarin compound includes: 3,3'-carbonyl bis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin, 3,3'-carbonyl Bis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7 -(Diethylamino)-4-methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3-benzoyl-7- Methoxycoumarin and its analogues.
  • These coumarin compounds can be used alone or in combination of two or more.
  • 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 can be used alone or in combination of two or more.
  • acridine compounds include: 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methylphenyl acridine, 9-o-chlorophenyl acridine, 9-o-fluoro Phenylacridine, 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine , 1,7-bis(9-acridine) heptane, 1,5-bis(9-acridine pentane), 1,3-bis(9-acridine) propane and the like. These acridine compounds can be used alone or in combination of two or more.
  • the organic solvent only needs to be able to dissolve the aforementioned components.
  • it may be glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, chlorine-containing solvents, etc., and colorants are particularly preferred.
  • 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 two Alcohol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol) ), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether), but
  • dyes, pigments and light developers include: tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, fluoran dye, toluene sulfonate Acid monohydrate, basic fuchsin, phthalocyanine green and phthalocyanine blue and other phthalocyanines, auramine base, para-fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green , Basic Blue 20, Brilliant Green, Eosin, Ethyl Violet, Erythrosine Sodium B, Methyl Green, Phenolphthalein, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinadine Red, Rose Red Sodium agar, mitanil yellow, thymol sulfophthalein, xylenol blue, methyl orange, tangerine IV, diphenyl flow carbachol,
  • the filler includes fillers such as silica, alumina, talc, calcium carbonate, and barium sulfate (not including the above-mentioned inorganic pigments).
  • the filler may be used alone or in combination of two or more.
  • the plasticizer includes: phthalate esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, three Glycol esters such as glycol diacetate, tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide, triphenyl phosphate, trimethyl phosphoric acid Esters, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, tricresyl phosphate, 2-naphthyl diphenyl phosphate Ester, cresyl bis 2,6-xylyl phosphate, aromatic condensed phosphate, tris(chloropropyl) phosphate, tris(ch
  • the stabilizer includes: 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 hydroquinone and quinone, tert-butylcatechol, 1,2,3-benzenetriol, copper resinate, naphthylamine, ⁇ - Naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloranil, etc.
  • the stabilizer can be used singly or in combination of two or more.
  • the coating aids include: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, ⁇ -butyrolactone, dichloromethane, etc.
  • the coating aids can be used alone or in combination of two or more.
  • the peeling accelerator includes: benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl and other alkyl benzene sulfonic acids Acid etc.
  • the peeling accelerator may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention can be prepared into a dry film, that is, a photosensitive resin laminate, and applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages. Form the required pattern on the substrate.
  • the photosensitive resin composition of the present invention can also be applied to the corresponding substrate in each corresponding manufacturing step by a wet film coater, that is, applied as a wet film to printed circuit boards, protective patterns, conductor patterns, lead wires, In the manufacture of semiconductor packages, the required patterns are formed on different substrates through different processes.
  • the dry film of the present invention which is a photosensitive resin laminate, includes a photosensitive resin layer formed of a photosensitive resin composition and a support that supports the photosensitive resin layer.
  • the preparation of the dry film includes: coating the photosensitive resin composition on the support and drying to form a photosensitive resin layer; optionally, bonding a cover film (protective layer) as needed.
  • the drying conditions are drying at 60-100°C for 0.5-15 minutes.
  • the thickness of the photosensitive resin layer is preferably 5-95 ⁇ m, more preferably 10-50 ⁇ m, and more preferably 15-30 ⁇ m. If the thickness of the photosensitive resin layer is less than 5 ⁇ m, the insulation is poor, and if the thickness of the photosensitive resin layer exceeds 95 ⁇ m, the resolution may be poor.
  • plastic films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polymethacrylate Ester, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene Vinyl fluoride, polytrifluoroethylene and the like.
  • composite materials composed of two or more materials can also be used.
  • polyethylene terephthalate having excellent light penetration is used.
  • the thickness of the support is preferably 5-150 ⁇ m, more preferably 10-50 ⁇ m.
  • the coating of the photosensitive resin composition There are no particular restrictions on the coating of the photosensitive resin composition.
  • spray coating, roller coating, spin coating, slit coating, compression coating, curtain coating, and dye coating can be used.
  • Conventional methods such as cloth method, line coating method, knife coating method, roll coating method, knife coating method, spraying method, dip coating method, etc.
  • the present invention provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:
  • Exposure step exposing the photosensitive resin layer in the photosensitive resin laminate, irradiating active light in an image form to photocuring the exposed part;
  • Conductor pattern formation process etching or plating the part of the surface of the copper clad laminate or flexible substrate that is not covered by the protective pattern;
  • Peeling step peeling the protective pattern from the copper clad laminate or flexible substrate.
  • the present invention provides the application of the above-mentioned dry film in the manufacture of protective patterns, including the lamination process, exposure process, and development process as described above.
  • the difference is that the photosensitive resin laminate can be laminated on various materials in the lamination process. On the substrate.
  • the present invention provides the application of the above-mentioned dry film in the manufacture of conductor patterns, including the lamination process, exposure process, development process, and conductor pattern formation process as described above.
  • the difference is that the photosensitive resin laminate is laminated on the metal in the lamination process. Board or metal coated insulating board.
  • the present invention provides the application of the above-mentioned dry film in the manufacture of lead wire, including the lamination process, exposure process, development process, and conductor pattern forming process as described above, the difference lies in: the photosensitive resin laminate is laminated in the lamination process On the metal plate, the portion not covered by the protective pattern is etched during the conductor pattern forming process.
  • the present invention provides the application of the above-mentioned dry film in the manufacture of semiconductor packages, including the lamination process, exposure process, development process, and conductor pattern forming process as described above.
  • the difference is that the photosensitive resin laminate is laminated in the lamination process.
  • the portion not covered by the protective pattern is plated in the conductor pattern formation process.
  • the photosensitive resin composition of the present invention can be directly coated on a substrate by a wet film method, and used for the production of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
  • the photosensitive resin composition can be coated on the substrate by conventional methods such as roll coating, knife coating, spray coating, and dip coating, and dried to form a photosensitive resin layer.
  • the exposure can include the mask exposure method (a method in which the negative or positive mask pattern of the wiring pattern irradiates the active light in an image), the projection exposure method, the direct imaging exposure method by laser, and the digital optics
  • the direct drawing exposure method such as the processing exposure method, irradiates active light in an image.
  • the light source of active light well-known light sources can be used, such as carbon arc lamp, mercury vapor arc lamp, ultra-high pressure indicator lamp, high pressure indicator lamp, xenon lamp, gas laser such as argon laser, solid laser such as YAG laser, semiconductor laser, and gallium nitride It is a light source that effectively emits ultraviolet rays such as a blue-violet laser.
  • the photosensitive resin composition of the present invention has no particular limitation on the type of light source of active light, and the exposure amount is preferably 10-1000 mJ/cm 2 .
  • the unexposed portion of the photosensitive resin layer is removed with a developer.
  • the support can be removed using an automatic peeler or the like, and then the unexposed part can be removed using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • the alkaline aqueous solution may be 0.1-5% by mass sodium carbonate solution, 0.1-5% by mass potassium carbonate solution, 0.1-5% by mass sodium hydroxide solution, etc.
  • the pH value is preferably 9-11.
  • Surfactants, defoamers, organic solvents, etc. can also be added to the alkaline aqueous solution.
  • the development method can be conventional methods such as dipping, spraying, and brushing.
  • the resist pattern (ie, protective pattern) formed on the substrate is used as a mask to etch away the uncovered conductor layer of the circuit forming substrate, thereby forming a conductor pattern.
  • the etching method can 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 alkali etching solution, and a hydrogen peroxide-based etching solution.
  • the resist pattern formed on the substrate is used as a mask, and copper, solder, etc. are plated on the insulating plate of the circuit formation substrate that is not covered. After the plating process, the resist pattern is removed to form a conductor pattern.
  • the plating treatment method may be electroplating treatment or electroless plating treatment, but electroless plating treatment is preferred. Examples of electroless plating include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, and Watt bath (nickel sulfate-chlorinated Nickel) plating and nickel plating such as sulfamate nickel plating, and gold plating such as hard gold plating and soft gold plating.
  • the removal of the resist pattern can be performed by an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step.
  • an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step.
  • a strong alkaline aqueous solution for example, 1-10% by mass aqueous sodium hydroxide solution can be used.
  • the present invention also relates to the use of the above-mentioned photosensitive resin composition in the manufacture of color filters, color filters, and liquid crystal display modules containing the color filters.
  • the color filter made from the above-mentioned photosensitive resin composition includes a support and a colored pattern formed on the support using the photosensitive resin composition.
  • the technology of preparing RGB, BM, photo-spacers, etc. by photocuring and photolithography using the photosensitive resin composition is well known to those skilled in the art. It usually includes the following steps: a process of applying a photosensitive resin composition on a support to form a photosensitive resin layer (abbreviated as “forming process”); a process of exposing the photosensitive resin layer through a mask (abbreviated as “exposing process”) "); and the step of developing the exposed photosensitive resin layer to form a colored pattern (referred to simply as "development step”).
  • the photosensitive resin composition of the present invention is coated on a support (substrate) directly or with other layers interposed therebetween to form a photosensitive resin layer; exposure is performed through a predetermined mask pattern, and only the light irradiated
  • the coating film is partially cured; it is developed with a developer to form a patterned film composed of pixels of each color (three colors or four colors), thereby manufacturing the color filter of the present invention.
  • 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.
  • Suitable supports include, for example, soda lime glass, alkali-free glass, pyrex glass, quartz glass, plastic substrates used in liquid crystal display elements, etc., and transparent conductive materials attached to the support
  • the photoelectric conversion element substrate used in the support body obtained by the film, the imaging element, etc., for example, a silicon substrate, etc., a complementary metal oxide film semiconductor (CMOS), and the like.
  • CMOS complementary metal oxide film semiconductor
  • the above-mentioned substrate is sometimes formed with a black matrix to isolate each pixel.
  • an undercoat layer may be provided on the support as required to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.
  • various coating methods such as slit coating, inkjet method, spin coating, roll coating, and screen printing method can be applied.
  • the coating film thickness of the photosensitive resin composition is preferably 0.1-10 ⁇ m, more preferably 0.5-3 ⁇ m.
  • the drying temperature of the photosensitive resin composition coated on the support is 70-110°C, and the drying time is 2-4 minutes.
  • the exposure step is to expose the photosensitive resin layer formed in the aforementioned photosensitive resin layer forming step through a mask to cure only the portion of the coating film irradiated with light.
  • Exposure is preferably performed by irradiating radiation.
  • the radiation that can be used for exposure ultraviolet rays such as g-line and i-line are particularly preferably used, and a high-pressure mercury lamp is more preferred.
  • the irradiation intensity is preferably 5-1500 mJ/cm 2 , and more preferably 10-500 mJ/cm 2 .
  • An alkaline development process (development process) is performed after the exposure process, and the unexposed part in the exposure process is melt
  • the developing temperature is usually 20-30°C, and the developing time is 20-90 seconds.
  • a post-curing step of further curing the formed colored pattern by heating and/or exposure may be added.
  • the above-mentioned photosensitive resin layer formation process, exposure process, and development process (and post-curing process added as necessary) are repeated to produce a color filter composed of the desired color tone.
  • Figure 1 is a high performance liquid phase spectrum of compound a1.
  • LCMS was used to confirm the structure of a1-2, and mass spectrometry was used to obtain 211 and 212 molecular fragment peaks with the aid of the software attached to the instrument.
  • the molecular weight of product a1-2a was 210, which was consistent with T+1 and T+2; and 245 and 246 molecular fragment peaks were obtained.
  • the molecular weight of a1-2b is 244, which is consistent with T+1 and T+2; the 279 and 280 molecular fragment peaks are obtained, and the molecular weight of product a1-2c is 278, which is consistent with T+1 and T+2.
  • LCMS proved that the brown liquid a1-2 is composed of a1-2a, a1-2b and a1-2c.
  • LCMS was used to confirm the structure of a1-3, and mass spectrometry analysis used the software attached to the instrument to obtain molecular fragmentation peaks of 311 and 312.
  • the molecular weight of product a1-3a was 330, which was consistent with T+1 and T+2; and molecular fragmentation peaks of 365 and 366 were obtained.
  • the molecular weight of a1-3b is 364, which is consistent with T+1 and T+2; the 399 and 400 molecular fragment peaks are obtained, and the molecular weight of product a1-3c is 398, which is consistent with T+1 and T+2.
  • LCMS proved that the brown liquid a1-3 is composed of a1-3a, a1-3b and a1-3c.
  • the product a1 was analyzed by high performance liquid chromatography, and the result was shown in Figure 1.
  • the total content of bisimidazole in the product a1 was 94.5%.
  • a8 is a BCIM (single-structure HABI) produced by Changzhou Qiangli Electronic New Materials Co., Ltd., in which the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 6.7%.
  • TR-HABI-104 single structure HABI
  • the molar ratio of the red-shifted substituents in all substitutable sites of the hexaarylbisimidazole photoinitiator is 13.3%.
  • a10 is a TCDM (hybrid HABI) produced by Changzhou Qiangli Electronic New Materials Co., Ltd., in which the mole ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 16.7%.
  • Preparation of alkali-soluble polymer B In a nitrogen atmosphere, add a mixed solvent of methyl cellosolve and toluene (mass ratio 3:2) into a flask equipped with a stirrer, a reflux cooler, a thermometer and a dropping funnel 500g, after stirring and heating to 80°C, the 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 added dropwise to the flask The dropping time was 4 hours, and the reaction was continued for 2 hours after the dropping.
  • a mixed solvent of methyl cellosolve and toluene mass ratio 3:2
  • the liquid composition is coated on a glass substrate using a spin coater, and then dried at 100°C for 5 minutes to remove the solvent to form a coating film with a thickness of 10 ⁇ m; in order to obtain a coating film with the above thickness,
  • the coating process can be completed at one time or in multiple steps; the substrate with the coating film is cooled to room temperature.
  • the coated film was irradiated at a wavelength of 365 nm through a mask of 20 ⁇ m in length ⁇ 20 ⁇ m in width and with an exposure amount of 50 mJ/cm 2 . After the irradiation, the coating film was developed at 23° C.
  • the width of the pixel pattern obtained is determined based on the following criteria, and the criteria are as follows:
  • ⁇ 20 ⁇ m or more and less than 35 ⁇ m
  • the resolution is the minimum value of the pattern after the unexposed part is removed from the resist pattern formed by development after exposure, and is classified as follows:
  • ⁇ The resolution value is below 30 ⁇ m
  • the resolution value is 30 ⁇ m-50 ⁇ m, excluding the end value
  • ⁇ The resolution value is above 50 ⁇ m.
  • the developability is evaluated according to the following criteria:
  • ⁇ The shape of the resist pattern confirmed the undercut and the lack of the upper part of the resist pattern, and the linearity of the pattern outline was poor.
  • the hydrophilicity is evaluated by the amount of precipitation after the photosensitive resin layer is dissolved.
  • the photosensitive resin composition was sufficiently stirred, and it was uniformly coated on the surface of a 25 ⁇ m thick polyethylene terephthalate film as a support using a bar coater. Dry in a dryer at 95°C for 4 minutes to form a photosensitive resin layer with a thickness of about 30.5 ⁇ m and a weight of about 3.2 g.
  • Dissolve 20g of sodium carbonate in 2L of water add 1.5ml of Pluronic RPG3110 (BASF, Mt. Olive, NJ, this reagent is a polyoxyethylene and polyoxypropylene copolymer plasticizer) to prepare a developer. Put the above-mentioned film with photosensitive resin layer into 100g developer, and let the sample stand until the resin layer is dissolved.
  • the amount of precipitation is determined according to the following grades:
  • Example 1 Sensitivity Resolution Developability Resist pattern shape Hydrophilic
  • 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 ⁇ ⁇ ⁇ Level 5 Comparative example 3 ⁇ ⁇ ⁇ ⁇ Level 5 Comparative example 4 ⁇ ⁇ ⁇ ⁇ Level 1 Comparative example 5 ⁇ ⁇ ⁇ ⁇ Level 1 Comparative example 6 ⁇ ⁇ ⁇ ⁇ Level
  • the photosensitive resin composition of the present invention has moderate sensitivity, good solubility, excellent resolution and developability, and does not appear inverted trapezoid during development. In addition, it also has good hydrophilicity, which can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be used repeatedly and effectively.
  • the photosensitive resin composition can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc. in the form of dry film and wet film, and can also be applied to color filters and liquid crystal displays Component manufacturing.

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Abstract

The present invention discloses a hexaarylbiimidazole photoinitiator and an application thereof; the mole ratio of red-shift substituents at all substitutable sites is 6-16%. The photoinitiator, when applied to photosensitive resin compositions, has moderate photosensitivity, good solubility, high resolution and excellent developing properties so as not to show an inverted trapezoid when developed; besides, it has good hydrophilicity, thereby greatly reducing the sludge quantity in the developing liquid when reused, enabling repeatable and effective use of the developing liquid. The present invention further provides a photosensitive resin composition containing the described photoinitiator, and an application of the composition.

Description

一种六芳基双咪唑类光引发剂及其应用A kind of hexaaryl bisimidazole photoinitiator and its application 技术领域Technical field
本发明属于有机化学领域，具体涉及一种六芳基双咪唑类光引发剂，含有该光引发剂的感光性树脂组合物及其应用。The invention belongs to the field of organic chemistry, and specifically relates to a hexaarylbisimidazole photoinitiator, a photosensitive resin composition containing the photoinitiator, and applications thereof.
背景技术Background technique
随着精密电子设备的微小化，感光性树脂组合物成为研究热点，其中光引发剂对感光性树脂组合物的感光度、溶解性、亲水性、分辨率和显影性的影响是研究的重中之重。光引发剂作为感光性树脂组合物中必不可少的组分，通常要求具有高的引发效率、优良的溶解性、优良的亲水性等。但是应用发现，并非所有理化指标都是越高越好，例如随着应用越来越精细化，光引发剂感光度过高就容易带来制造精度不够、次品率高的问题。With the miniaturization of precision electronic equipment, photosensitive resin compositions have become a research hotspot. Among them, the influence of photoinitiators on the sensitivity, solubility, hydrophilicity, resolution and developability of photosensitive resin compositions is the focus of research. The most important. As an indispensable component of the photosensitive resin composition, photoinitiators are generally required to have high initiation efficiency, excellent solubility, and excellent hydrophilicity. However, the application found that not all physical and chemical indicators are as high as possible. For example, as the application becomes more and more refined, too high sensitivity of the photoinitiator will easily lead to insufficient manufacturing accuracy and high defective rate.
六芳基双咪唑类化合物是一类已知的光引发剂，目前相关研究主要集中在：改变芳基上的取代基团以增加亲水性，进而降低显影垃圾；改变芳基上的取代基团以增加感光度；增加变色基团以改善显影识别等等。研究发现，低感光度的六芳基双咪唑类光引发剂(如BCIM)会使得感光性树脂组合物用于具有较窄线宽的光刻时，虽然具有优异的分辨率和解析度，但是显影液中的淤渣量较多，影响显影液的重复使用；而高感光度的六芳基双咪唑类光引发剂(如TCDM-HABI)会使得感光性树脂组合物用于具有较窄线宽的光刻时，底部固化不完全，进而在显影时出现倒梯形，使得产品不符合应用要求。市场中现有的六芳基双咪唑光引发剂，由于组分不稳定、差异性大且显影垃圾量大，在精细线路中应用时成品率低，严重影响 产品质量和客户使用感受。Hexaarylbisimidazole compounds are a kind of known photoinitiators. At present, relevant research mainly focuses on: changing the substituent groups on the aryl group to increase the hydrophilicity, thereby reducing the development waste; changing the substituent groups on the aryl group Group to increase sensitivity; increase color-changing group to improve development recognition and so on. Studies have found that low-sensitivity hexaarylbisimidazole-based photoinitiators (such as BCIM) will enable the photosensitive resin composition to be used in lithography with a narrow line width, although it has excellent resolution and resolution, but The amount of sludge in the developer is large, which affects the repeated use of the developer; and the high-sensitivity hexaarylbisimidazole photoinitiator (such as TCDM-HABI) will make the photosensitive resin composition used with a narrow line In wide lithography, the bottom is not fully cured, and then an inverted trapezoid appears during development, making the product not meet the application requirements. The existing hexaarylbisimidazole photoinitiators in the market have low yield when applied in fine circuits due to unstable components, large differences and large amounts of developing garbage, which seriously affects product quality and customer experience.
申请人在现有六芳基双咪唑类化合物的基础上，进一步研究六芳基双咪唑类光引发剂中芳基上引入的取代基、取代基中红移基团的占比量和组成情况，进而对感光度、溶解性、亲水性、分辨率和显影性等性能做出综合调控，以使得应用该光引发剂的感光性树脂组合物在应用中既具有合适的固化速率而不影响显影制得所需的光刻图形，还能兼具低显影垃圾的优点，从而拓宽六芳基双咪唑类光引发剂的实际应用。On the basis of the existing hexaarylbisimidazole compounds, the applicant further studied the substituents introduced on the aryl groups in the hexaarylbisimidazole photoinitiators, the proportion and composition of the redshift groups in the substituents , And then comprehensively control the properties of sensitivity, solubility, hydrophilicity, resolution and developability, so that the photosensitive resin composition using the photoinitiator has an appropriate curing rate in the application without affecting Development to obtain the required photolithography pattern, but also has the advantages of low development waste, thereby broadening the practical application of hexaarylbisimidazole photoinitiators.
发明内容Summary of the invention
本发明的目的首先在于提供一种六芳基双咪唑类光引发剂，以解决现有该类光引发剂在高精密线路中使用时出现倒梯形等不符合应用要求、显影垃圾不能有效降低等问题。本发明的光引发剂应用于感光性树脂组合物时感光度适中、溶解性好、分辨率和显影性优异，不会在显影时出现倒梯形，并且具有较好的亲水性，能显著减少循环使用时显影液中的淤渣量，使得显影液可重复多次、有效使用。The purpose of the present invention is first to provide a hexaarylbisimidazole photoinitiator to solve the problem of inverted trapezoids that do not meet the application requirements and the development waste cannot be effectively reduced when the existing photoinitiators are used in high-precision circuits. problem. When the photoinitiator of the present invention is applied to a photosensitive resin composition, it has moderate sensitivity, good solubility, excellent resolution and developability, does not appear inverted trapezoid shape during development, and has good hydrophilicity, which can significantly reduce The amount of sludge in the developer during recycling enables the developer to be used repeatedly and effectively.
具体来说，本发明的六芳基双咪唑类光引发剂，通过以下步骤制备而成：Specifically, the hexaarylbisimidazole photoinitiator of the present invention is prepared by the following steps:
(1)通式(Ⅰ)所示的芳香醛和通式(Ⅱ)所示的芳香醛通过缩合、氧化反应，得到苯偶酰类化合物；该苯偶酰类化合物与通式(Ⅲ)所示的芳香醛通过成环反应生成单咪唑化合物M；(1) The aromatic aldehyde represented by the general formula (I) and the aromatic aldehyde represented by the general formula (II) are condensed and oxidized to obtain a benzyl compound; the benzyl compound is combined with the general formula (III) The aromatic aldehyde shown in the ring-forming reaction generates monoimidazole compound M;
(2)通式(Ⅳ)所示的芳香醛和通式(Ⅴ)所示的芳香醛通过缩合、氧化反应，得到苯偶酰类化合物；该苯偶酰类化合物与通式(Ⅵ)所示的芳香醛通过成环反应生成单咪唑化合物N；(2) The aromatic aldehyde represented by the general formula (IV) and the aromatic aldehyde represented by the general formula (V) are condensed and oxidized to obtain a benzil compound; the benzyl compound is with the general formula (VI) The aromatic aldehyde shown in the ring-forming reaction generates monoimidazole compound N;
(3)单咪唑化合物M和N通过氧化反应，生成六芳基双咪唑类光引发剂；(3) Monoimidazole compounds M and N undergo oxidation reactions to generate hexaarylbisimidazole photoinitiators;
Figure PCTCN2020081293-appb-000001
Figure PCTCN2020081293-appb-000001
其中，R 1-R 30各自独立地表示氢、卤素、硝基、氰基、胺基、羟基、C 1-C 10的烷基、C 1-C 10的烷氧基、或C 2-C 10的链烯基，且各基团中的亚甲基可以任选地被氧、硫、亚胺基所取代； Wherein, R 1 -R 30 each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, or C 2 -C The alkenyl group of 10 , and the methylene group in each group may be optionally substituted by oxygen, sulfur, and imino groups;
前提是，红移取代基在六芳基双咪唑类光引发剂的所有可取代位点即R 1-R 30中的摩尔占比为6-16％。 The premise is that the molar ratio of the red-shifted substituents at all substitutable positions of the hexaarylbisimidazole photoinitiator, namely R 1 -R 30 , is 6-16%.
本发明的目的还在于提供包含上述光引发剂的感光性树脂组合物，以及该组合物在制造印刷电路板、保护图案、导体图案、引框线、半导体封装等方面的应用。The object of the present invention is also to provide a photosensitive resin composition containing the above-mentioned photoinitiator, and the application of the composition in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
本发明的另一个目的在于提供上述感光性树脂组成物在制造彩色滤光片中的应用、彩色滤光片及含有彩色滤光片的液晶显示组件。Another object of the present invention is to provide an application of the above-mentioned photosensitive resin composition in the manufacture of a color filter, a color filter, and a liquid crystal display module containing the color filter.
发明详述Detailed description of the invention
基于本发明的目的，以下对各方面进行更详细的说明。Based on the purpose of the present invention, each aspect will be described in more detail below.
本申请中的术语“淤渣”和“显影垃圾”是指在显影液中积累起来的物质， 它不溶于显影液并会再沉积于已显影的基底上，从而降低显影液的效率。The terms "sludge" and "developing garbage" in this application refer to substances accumulated in the developer solution, which are insoluble in the developer solution and will re-deposit on the developed substrate, thereby reducing the efficiency of the developer solution.
<六芳基双咪唑类光引发剂><Six aryl bisimidazole photoinitiator>
如上所述，本发明的六芳基双咪唑类光引发剂，通过以下步骤制备而成：As mentioned above, the hexaarylbisimidazole photoinitiator of the present invention is prepared by the following steps:
(1)通式(Ⅰ)所示的芳香醛和通式(Ⅱ)所示的芳香醛通过缩合、氧化反应，得到苯偶酰类化合物；该苯偶酰类化合物与通式(Ⅲ)所示的芳香醛通过成环反应生成单咪唑化合物M；(1) The aromatic aldehyde represented by the general formula (I) and the aromatic aldehyde represented by the general formula (II) are condensed and oxidized to obtain a benzyl compound; the benzyl compound is combined with the general formula (III) The aromatic aldehyde shown in the ring-forming reaction generates monoimidazole compound M;
(2)通式(Ⅳ)所示的芳香醛和通式(Ⅴ)所示的芳香醛通过缩合、氧化反应，得到苯偶酰类化合物；该苯偶酰类化合物与通式(Ⅵ)所示的芳香醛通过成环反应生成单咪唑化合物N；(2) The aromatic aldehyde represented by the general formula (IV) and the aromatic aldehyde represented by the general formula (V) are condensed and oxidized to obtain a benzil compound; the benzyl compound is with the general formula (VI) The aromatic aldehyde shown in the ring-forming reaction generates monoimidazole compound N;
(3)单咪唑化合物M和N通过氧化反应，生成六芳基双咪唑类光引发剂；(3) Monoimidazole compounds M and N undergo oxidation reactions to generate hexaarylbisimidazole photoinitiators;
Figure PCTCN2020081293-appb-000002
Figure PCTCN2020081293-appb-000002
其中，R 1-R 30各自独立地表示氢、卤素、硝基、氰基、胺基、羟基、C 1-C 10的烷基、C 1-C 10的烷氧基、或C 2-C 10的链烯基，且各基团中的亚甲基可以任选地被氧、硫、亚胺基所取代； Wherein, R 1 -R 30 each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, or C 2 -C The alkenyl group of 10 , and the methylene group in each group may be optionally substituted by oxygen, sulfur, and imino groups;
前提是，红移取代基在六芳基双咪唑类光引发剂的所有可取代位点即R 1-R 30中的摩尔占比为6-16％。 The premise is that the molar ratio of the red-shifted substituents at all substitutable positions of the hexaarylbisimidazole photoinitiator, namely R 1 -R 30 , is 6-16%.
本发明所述的红移取代基，是指芳香环上引入的取代基团使得六芳基双咪唑结构的共轭度变大，进而导致紫外吸收波长向着长波长的方向移动(即产生红移现象)的基团。优选地，红移取代基包括氯、溴、硝基、氰基、胺基、羟基、C 2-C 10的链烯基、C 1-C 10的烷氧基，其中各基团中的亚甲基可以任选地被氧、硫、亚胺基所取代。进一步优选地，红移取代基选自氯、溴、羟基、胺基、和C 1-C 5的烷氧基。 The red-shifted substituent mentioned in the present invention refers to the substituted group introduced on the aromatic ring to increase the conjugation degree of the hexaarylbisimidazole structure, which in turn causes the ultraviolet absorption wavelength to shift toward the long wavelength (that is, redshift Phenomenon) group. Preferably, the red-shifted substituents include chlorine, bromine, nitro, cyano, amine, hydroxyl, C 2 -C 10 alkenyl, C 1 -C 10 alkoxy, wherein the sub-group in each group The methyl group may be optionally substituted with oxygen, sulfur, or imino groups. Further preferably, the red-shifted substituent is selected from chlorine, bromine, hydroxyl, amine, and C 1 -C 5 alkoxy.
红移取代基在六芳基双咪唑类光引发剂的所有可取代位点(即R 1-R 30)中的摩尔占比为6-16％。如果红移取代基的摩尔占比大于16％，存在由于感光度过高使得容易出现表面固化完全但内部还未完全固化的情况，这就使得进行光刻的窄线条在显影后会呈现倒梯形，从而使制得的产品不符合应用要求；如果红移取代基的摩尔占比小于6％，则感光度偏低，固化速度慢，降低了制备效率。 The molar ratio of the red-shifted substituents in all substitutable sites (ie, R 1 -R 30 ) of the hexaarylbisimidazole photoinitiator is 6-16%. If the molar ratio of the red-shifted substituents is greater than 16%, the surface is easily cured but the inside is not completely cured due to the high sensitivity, which makes the narrow lines of photolithography appear inverted trapezoid after development Therefore, the prepared product does not meet the application requirements; if the molar ratio of the red-shifted substituent is less than 6%, the sensitivity is low, the curing speed is slow, and the preparation efficiency is reduced.
应用表明，本发明的六芳基双咪唑类光引发剂应用于感光性树脂组合物时，组合物的感光度适中、溶解性好、分辨率和显影性优异，不会在显影时出现倒梯形。此外，还具有较好的亲水性，能显著减少循环使用时显影液中的淤渣量，使得显影液可重复多次、有效使用。The application shows that when the hexaarylbisimidazole photoinitiator of the present invention is applied to a photosensitive resin composition, the composition has moderate sensitivity, good solubility, excellent resolution and developability, and does not appear inverted trapezoid during development. . In addition, it also has good hydrophilicity, which can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be used repeatedly and effectively.
本申请中，红移取代基的摩尔占比计算方法如下：In this application, the calculation method for the molar ratio of the red-shifted substituents is as follows:
(1)a mol通式(Ⅰ)所示的芳香醛(R 1-R 5中红移取代基的个数为A)和b mol通式(Ⅱ)所示的芳香醛(R 6-R 10中红移取代基的个数为B)通过缩合、氧化反应，得到(a+b)/2mol的苯偶酰类化合物；该苯偶酰类化合物与(a+b)/2mol通式(Ⅲ)所示的芳香醛(R 11-R 15中红移取代基的个数为C) 通过成环反应生成单咪唑化合物M，M中红移取代基的个数为m； (1) The aromatic aldehyde represented by a mol general formula (I) (the number of red-shifted substituents in R 1 -R 5 is A) and the aromatic aldehyde represented by b mol general formula (II) (R 6 -R The number of red-shifted substituents in 10 is B) Through condensation and oxidation reaction, (a+b)/2mol benzil compounds are obtained; the benzil compounds and (a+b)/2mol general formula ( Ⅲ) The aromatic aldehyde shown (the number of red-shifted substituents in R 11 -R 15 is C) is formed into a monoimidazole compound M through a ring-forming reaction, and the number of red-shifted substituents in M is m;
Figure PCTCN2020081293-appb-000003
Figure PCTCN2020081293-appb-000003
(2)a’mol通式(Ⅳ)所示的芳香醛(R 16-R 20中红移取代基的个数为A’)和b’mol通式(Ⅴ)所示的芳香醛(R 21-R 25中红移取代基的个数为B’)通过缩合、氧化反应，得到(a’+b’)/2mol的苯偶酰类化合物；该苯偶酰类化合物与(a’+b’)/2mol通式(Ⅵ)所示的芳香醛(R 26-R 30中红移取代基的个数为C’)通过成环反应生成单咪唑化合物N，N中红移取代基的个数为n； (2) The aromatic aldehyde represented by a'mol general formula (IV) (the number of red-shifted substituents in R 16 -R 20 is A') and the aromatic aldehyde represented by b'mol general formula (V) (R The number of red-shifting substituents in 21 -R 25 is B') through condensation and oxidation reactions, (a'+b')/2mol benzyl compounds are obtained; the benzyl compounds and (a'+ b')/2mol of the aromatic aldehyde represented by the general formula (VI) (the number of red-shifted substituents in R 26 -R 30 is C') through the ring-forming reaction to generate monoimidazole compound N, the red-shifted substituent of N The number is n;
Figure PCTCN2020081293-appb-000004
Figure PCTCN2020081293-appb-000004
(3)e mol单咪唑化合物M和f mol单咪唑化合物N通过氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂的所有可取代位点(即R 1-R 30)中的摩尔占比为p。 (3) e mol monoimidazole compound M and f mol monoimidazole compound N are oxidized to generate hexaarylbisimidazole photoinitiator, and the red-shifted substituents are at all substitutable positions of the hexaarylbisimidazole photoinitiator The mole ratio in the point (ie, R 1 -R 30 ) is p.
Figure PCTCN2020081293-appb-000005
Figure PCTCN2020081293-appb-000005
<感光性树脂组合物><Photosensitive resin composition>
如上文所述，本发明的六芳基双咪唑类光引发剂应用于感光性树脂组合物时具有优异的性能表现。因此相应地，本发明还提供一种感光性树脂组合物，其特征在于，包含下列组分：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, which is characterized by comprising the following components:
(A)如上所述的六芳基双咪唑类光引发剂；(A) The hexaarylbisimidazole photoinitiator as described above;
(B)碱可溶性聚合物；(B) Alkali-soluble polymer;
(C)具有烯属不饱和双键的化合物；(C) Compounds with ethylenically unsaturated double bonds;
(D)供氢体；(D) Hydrogen donor;
(E)其它任选的助剂。(E) Other optional auxiliary agents.
以下将对各组分进行更加详细的说明。Each component will be described in more detail below.
六芳基双咪唑类光引发剂(A)Hexaaryl bisimidazole photoinitiator (A)
在如上文所述的特征限定范围内，本发明的六芳基双咪唑类光引发剂对双咪唑的连接位不做限定。示例性地，所述六芳基双咪唑类光引发剂可选自或包括下列化合物中的至少一种：Within the limited range of characteristics as described above, the hexaarylbisimidazole photoinitiator of the present invention does not limit the attachment position of the bisimidazole. Exemplarily, the hexaarylbisimidazole-based photoinitiator may be selected from or include at least one of the following compounds:
化合物1(红移取代基的摩尔占比为10％)：Compound 1 (the molar ratio of the red-shifted substituent is 10%):
(1)1mol苯甲醛与1mol邻氯苯甲醛通过自身缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol邻氯苯甲醛通过成环反应生成单咪唑化合物M1，M1中红移取代基的个数为2。(1) 1 mol of benzaldehyde and 1 mol of o-chlorobenzaldehyde undergo self-condensation and oxidation reaction to obtain 1 mol of benzil compounds; this benzaldehyde compound and 1 mol of o-chlorobenzaldehyde form a monoimidazole compound M1 through a ring-forming reaction, The number of redshift substituents in M1 is 2.
(2)2mol苯甲醛通过自身缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol邻氯苯甲醛通过成环反应生成单咪唑化合物N1，N1中红移取代基的个数为1。(2) 2 mol of benzaldehyde undergoes self-condensation and oxidation to obtain 1 mol of benzil compounds; this benzyl compound and 1 mol of o-chlorobenzaldehyde form a ring-forming reaction to form a monoimidazole compound N1, and the red shift substituent in N1 The number of is 1.
(3)1mol单咪唑化合物M1和1mol单咪唑化合物N1通过氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为10％。(3) 1 mol of monoimidazole compound M1 and 1 mol of monoimidazole compound N1 are oxidized to generate hexaarylbisimidazole photoinitiator, and the red-shifted substituents are in all substitutable positions of the hexaarylbisimidazole photoinitiator The mole ratio is 10%.
化合物2(红移取代基的摩尔占比为7.3％)：Compound 2 (the molar ratio of the red-shifted substituent is 7.3%):
1mol单咪唑化合物M1和9mol单咪唑化合物N1通过氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为7.3％。1mol of monoimidazole compound M1 and 9mol of monoimidazole compound N1 are oxidized to generate hexaarylbisimidazole photoinitiator, and the mole ratio of the red-shifted substituents in all substitutable sites of the hexaarylbisimidazole photoinitiator Is 7.3%.
化合物3(红移取代基的摩尔占比为12.7％)：Compound 3 (the molar ratio of the red-shifted substituent is 12.7%):
9mol单咪唑化合物M1和1mol单咪唑化合物N1通过氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂所有可取代 位点中的摩尔占比为12.7％。9mol of monoimidazole compound M1 and 1mol of monoimidazole compound N1 are oxidized to generate hexaarylbisimidazole photoinitiator, and the mole ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator It is 12.7%.
化合物4(红移取代基的摩尔占比为13.3％)：Compound 4 (the molar ratio of the red-shifted substituent is 13.3%):
(1)1mol对甲基苯甲醛和1mol邻氯苯甲醛通过缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol 2,4-二氯苯甲醛通过成环反应生成单咪唑化合物M2，M2中红移取代基的个数为3。(1) 1 mol of p-methylbenzaldehyde and 1 mol of o-chlorobenzaldehyde are condensed and oxidized to obtain 1 mol of benzaldehyde compounds; this benzaldehyde compound and 1 mol of 2,4-dichlorobenzaldehyde undergo a ring-forming reaction The monoimidazole compound M2 is produced, and the number of red-shifted substituents in M2 is 3.
(2)1mol单咪唑化合物M2和1mol单咪唑化合物N1通过氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为13.3％。(2) 1mol of monoimidazole compound M2 and 1mol of monoimidazole compound N1 are oxidized to generate hexaarylbisimidazole photoinitiator, and the red-shifted substituents are in all substitutable positions of the hexaarylbisimidazole photoinitiator The mole ratio is 13.3%.
化合物5(红移取代基的摩尔占比为15.6％)：Compound 5 (the molar ratio of the red-shifted substituent is 15.6%):
2mol单咪唑化合物M2和1mol单咪唑化合物N1通过氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为15.6％。2mol of monoimidazole compound M2 and 1mol of monoimidazole compound N1 are oxidized to generate hexaarylbisimidazole photoinitiator, and the mole ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator It is 15.6%.
化合物6(红移取代基的摩尔占比为6.7％)：Compound 6 (the molar ratio of the red-shifted substituent is 6.7%):
(1)1mol对甲基苯甲醛和1mol苯甲醛通过缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol邻氯苯甲醛通过成环反应生成单咪唑化合物M3，M3中红移取代基的个数为1。(1) 1 mol of p-methylbenzaldehyde and 1 mol of benzaldehyde undergo condensation and oxidation reactions to obtain 1 mol of benzyl compounds; this benzyl compound and 1 mol of o-chlorobenzaldehyde react to form monoimidazole compound M3, The number of red-shifted substituents in M3 is 1.
(2)2mol单咪唑化合物M3通过自身氧化反应，生成六芳基双咪唑类光引发剂，红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为6.7％。(2) 2mol of monoimidazole compound M3 generates hexaarylbisimidazole photoinitiator through self-oxidation reaction, and the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 6.7 %.
在100质量份感光性树脂组合物中，六芳基双咪唑类光引发剂(A)的含量为1-20质量份，优选1-10质量份。若含量过小，存在光致灵敏度下降的缺陷；如果含量过大，则存在光阻图案趋于变宽超过光掩模线宽的缺陷。In 100 parts by mass of the photosensitive resin composition, the content of the hexaarylbisimidazole-based photoinitiator (A) is 1-20 parts by mass, preferably 1-10 parts by mass. If the content is too small, there is a defect that the photosensitivity is reduced; if the content is too large, there is a defect that the photoresist pattern tends to become wider than the line width of the photomask.
碱可溶性聚合物(B)Alkali-soluble polymer (B)
碱可溶性聚合物可赋予感光性树脂组合物成膜功能。作为碱可溶性聚合物，只要是具有这样特性的聚合物就可以没有特别限制地适用。The alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition. As the alkali-soluble polymer, any polymer having such characteristics can be used without particular limitation.
示例性地，适用的碱可溶性聚合物可以是(甲基)丙烯酸系聚合物、苯乙烯系聚合物、环氧系聚合物、脂肪族聚氨酯(甲基)丙烯酸酯聚合物、芳香族聚氨酯(甲基)丙烯酸酯聚合物、酰胺系树脂、酰胺环氧系树脂、醇酸系树脂以及酚醛系树脂等。Exemplarily, suitable alkali-soluble polymers can be (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethanes (meth) Base) Acrylate polymer, amide resin, amide epoxy resin, alkyd resin, phenolic resin, etc.
进一步地，碱可溶性聚合物可经由聚合性单体进行自由基聚合而得到。作为聚合性单体，可例举出：苯乙烯、乙烯基甲苯、α-甲基苯乙烯、对甲基苯乙烯、对乙基苯乙烯、对氯苯乙烯等在α-位或在芳香族环上被取代的可聚合的苯乙烯衍生物；丙烯酰胺、双丙酮丙烯酰胺等丙烯酰胺衍生物；丙烯腈、乙烯基正丁基醚等乙烯基醇的醚类衍生物；(甲基)丙烯酸、α-溴代(甲基)丙烯酸、α-氯代(甲基)丙烯酸、β-呋喃基(甲基)丙烯酸、β-苯乙烯基(甲基)丙烯酸等(甲基)丙烯酸衍生物；(甲基)丙烯酸烷基酯、(甲基)丙烯酸苄酯、甲基丙烯酸苯氧基乙酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸缩水甘油酯、2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸缩水甘油酯等(甲基)丙烯酸酯类化合物；马来酸、马来酸酐、马来酸单甲酯、马来酸单乙酯、马来酸单异丙酯等马来酸单酯；富马酸、肉桂酸、α-氰基肉桂酸、衣康酸、巴豆酸、丙醇酸、N-乙烯基己内酰胺；N-乙烯基吡咯烷酮等。这些聚合性单体可以单独使用，也可以两种以上组合使用。Further, the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer. Examples of polymerizable monomers include: styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene, etc. in the α-position or aromatic Ring-substituted polymerizable styrene derivatives; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid , Α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, β-styryl(meth)acrylic acid and other (meth)acrylic acid derivatives; Alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ( (Meth) diethylaminoethyl 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, diethylamino (meth)acrylate (Meth)acrylate compounds such as ethyl ester and glycidyl (meth)acrylate; maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate And other maleic acid monoesters; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propanolic acid, N-vinylcaprolactam; N-vinylpyrrolidone, etc. These polymerizable monomers may be used alone or in combination of two or more kinds.
进一步地，从碱显影性和密合性的角度考虑，优选使用含羧基的碱可 溶性聚合物。具有羧基的碱可溶性聚合物可以为包含(甲基)丙烯酸作为单体单元的丙烯酸树脂，其通过使用(甲基)丙烯酸作为单体单元导入羧基；可以为除(甲基)丙烯酸以外进一步包含(甲基)丙烯酸烷基酯作为单体单元的共聚物；也可以为除(甲基)丙烯酸以外进一步含有除(甲基)丙烯酸和(甲基)丙烯酸烷基酯以外的聚合性单体(如具有乙烯性不饱和基团的单体)作为单体成分的共聚物。Further, from the viewpoint of alkali developability and adhesion, it is preferable to use a carboxyl group-containing alkali-soluble polymer. The alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth)acrylic acid as a monomer unit, which introduces a carboxyl group by using (meth)acrylic acid as a monomer unit; and may further include (meth)acrylic acid in addition to (meth)acrylic acid. Meth) acrylic acid alkyl ester as a copolymer of monomer units; in addition to (meth) acrylic acid, it can also contain polymerizable monomers other than (meth) acrylic acid and (meth) acrylic acid alkyl esters (such as A monomer having an ethylenically unsaturated group) is a copolymer as a monomer component.
进一步地，含羧基的碱可溶性聚合物可通过具有羧基的聚合性单体与其它聚合性单体进行自由基聚合而得到，特别是由(甲基)丙烯酸酯、乙烯性不饱和羧酸和其它可共聚单体共聚而成的(甲基)丙烯酸酯系聚合物。Further, alkali-soluble polymers containing carboxyl groups can be obtained by radical polymerization of polymerizable monomers having carboxyl groups with other polymerizable monomers, especially those made from (meth)acrylates, ethylenically unsaturated carboxylic acids and other A (meth)acrylate-based polymer formed by copolymerization of copolymerizable monomers.
所述的(甲基)丙烯酸酯可以是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸缩水甘油酯等。这些(甲基)丙烯酸酯可以单独使用，也可以两种以上组合使用。The (meth)acrylate can be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate , Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylic acid Decyl ester, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethyl (meth)acrylate Amino ethyl, dimethylamino ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)acrylate, (meth)acrylic acid Glycidyl esters and so on. These (meth)acrylates may be used alone or in combination of two or more kinds.
所述的乙烯性不饱和羧酸可以是丙烯酸、甲基丙烯酸、丁烯酸、马来酸、富马酸、衣康酸，特别优选丙烯酸、甲基丙烯酸。这些乙烯性不饱和羧酸可以单独使用，也可以两种以上组合使用。The ethylenically unsaturated carboxylic acid can be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, particularly preferably acrylic acid and methacrylic acid. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more kinds.
所述的其它可共聚单体可以是(甲基)丙烯酰胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基环己烷等。这些其它可共聚单体可以单独使用，也可以两种以上组合使用。The other copolymerizable monomers can be (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinyl naphthalene, (meth)acrylonitrile, vinyl acetate, vinyl cyclohexane Wait. These other copolymerizable monomers may be used alone or in combination of two or more.
碱可溶性聚合物可以单独一种使用，也可以两种以上组合使用。作为组合两种以上使用的碱可溶性聚合物，可列举出由不同共聚成分构成的两种以上的碱可溶性聚合物、不同重均分子量的两种以上的碱可溶性聚合物、不同分散度的两种以上的碱可溶性聚合物等。The alkali-soluble polymer may be used alone or in combination of two or more. As the alkali-soluble polymer used in combination of two or more kinds, two or more kinds of alkali-soluble polymers composed of different copolymerization components, two or more kinds of alkali-soluble polymers with different weight average molecular weights, and two kinds of different dispersion degrees can be cited. The above alkali-soluble polymer, etc.
在本发明的感光性树脂组合物中，对碱可溶性聚合物的重均分子量没有特别限制，其应与具体应用环境相适应。从机械强度与碱显影性方面综合考虑，重均分子量优选为15000-200000，更优选为30000-150000，特别优选为30000-120000。当重均分子量大于15000时，曝光后耐显影液性有进一步提高的倾向，当该重均分子量小于200000时，显影时间有变得更短的倾向，且可以保持与光引发剂等其它组分的相容性。碱可溶性聚合物的重均分子量通过凝胶渗透色谱法(GPC)进行测定，通过使用标准聚苯乙烯的标准曲线进行换算而得到。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 the specific application environment. Considering the mechanical strength and alkali developability comprehensively, the weight average molecular weight is preferably 15,000 to 200,000, more preferably 30,000 to 150,000, and particularly preferably 30,000 to 120,000. When the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved. When the weight average molecular weight is less than 200,000, the development time tends to become shorter, and it can maintain the compatibility with other components such as photoinitiators. Compatibility. The weight average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC), and is obtained by conversion using a standard curve of standard polystyrene.
进一步地，从碱显影性良好的角度考虑，碱可溶性聚合物的酸值优选为50-300mgKOH/g，更优选为50-250mgKOH/g，进一步优选为70-250mgKOH/g，特别优选为100-250mgKOH/g。当碱可溶性树脂的酸值低于50mgKOH/g时，难以确保充分的显影速度，当超过300mgKOH/g时，密合性减小，容易发生图案短路，且易出现组合物贮存稳定性降低、粘度上升的问题。Further, from the viewpoint of good alkali developability, the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, still more preferably 70-250 mgKOH/g, and particularly preferably 100- 250mgKOH/g. When the acid value of the alkali-soluble resin is less than 50mgKOH/g, it is difficult to ensure a sufficient development speed. When it exceeds 300mgKOH/g, the adhesion is reduced, pattern short-circuiting is likely to occur, and the composition is likely to decrease storage stability and viscosity The problem of rising.
碱可溶性树脂的分子量分布[重均分子量(Mw)/数均分子量(Mn)]优选为1.5-6.0，特别优选为1.8-3.7。当分子量分布处于所述范围时，显影性优异。The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5-6.0, particularly preferably 1.8-3.7. When the molecular weight distribution is in the range, the developability is excellent.
在100质量份感光性树脂组合物中，碱可溶性聚合物在组合物中的含量优选20-70质量份，更优选30-60质量份。当碱可溶性聚合物的含量在20质量份以上，可确保感光性树脂组合物对于镀敷处理、蚀刻处理等的耐久性得 到提高，当含量在70质量份以下，有利于提高感光性树脂组合物的灵敏度。In 100 parts by mass of the photosensitive resin composition, the content of the alkali-soluble polymer in the composition is preferably 20-70 parts by mass, more preferably 30-60 parts by mass. When the content of the alkali-soluble polymer is 20 parts by mass or more, it can ensure that the photosensitive resin composition has improved durability for plating treatment, etching treatment, etc., and when the content is less than 70 parts by mass, it is beneficial to improve the photosensitive resin composition The sensitivity.
具有烯属不饱和双键的化合物(C)Compounds with ethylenically unsaturated double bonds (C)
具有烯属不饱和双键的化合物可促进感光性树脂组合物成膜。The compound having an ethylenically unsaturated double bond can promote film formation of the photosensitive resin composition.
对具有烯属不饱和双键的化合物没有特别限定，只要在分子内具有至少一个乙烯性不饱和键的光聚合性化合物就可以使用。示例性地，可列举出：α,β-不饱和羧酸与多元醇反应而得的化合物、双酚A类(甲基)丙烯酸酯化合物、α,β-不饱和羧酸与含缩水甘油基的化合物反应而得的化合物、分子内具有氨酯键的(甲基)丙烯酸酯化合物等氨基甲酸酯单体、壬基苯氧基多乙烯氧基丙烯酸酯、γ-氯-β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基乙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、苯二甲酸类化合物、(甲基)丙烯酸烷基酯等。这些化合物可以单独使用，也可两种以上组合使用。The compound having an ethylenically unsaturated double bond is not particularly limited, as long as a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used. Illustratively, examples include: compounds obtained by reacting α, β-unsaturated carboxylic acids with polyhydric alcohols, bisphenol A (meth)acrylate compounds, α, β-unsaturated carboxylic acids, and glycidyl-containing compounds Compounds obtained by the reaction of compounds, urethane monomers such as (meth)acrylate compounds with urethane bonds in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl -Β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, alkyl (meth)acrylate, etc. These compounds may be used alone or in combination of two or more kinds.
作为上述α,β-不饱和羧酸与多元醇反应而得的化合物，可例举出：亚乙基数为2-14的聚乙二醇二(甲基)丙烯酸酯、亚丙基数为2-14的聚丙二醇二(甲基)丙烯酸酯、亚乙基数为2-14且亚丙基数为2-14的聚亚乙基·聚亚丙基二醇二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、EO改性三羟甲基丙烷三(甲基)丙烯酸酯、PO改性三羟甲基丙烷三(甲基)丙烯酸酯、EO,PO改性三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯、聚乙二醇单(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。在这里，“EO”表示环氧乙烷，经EO改性的化合物是指具有氧化乙烯基的嵌段结构的化合物。“PO” 表示环氧丙烷，经PO改性的化合物是指具有氧化丙烯基的嵌段结构的化合物。Examples of the compound obtained by reacting the above-mentioned α,β-unsaturated carboxylic acid with a polyhydric alcohol include polyethylene glycol di(meth)acrylate having an ethylene number of 2-14, and a propylene number of 2 Polypropylene glycol di(meth)acrylate of 14, ethylene number of 2-14 and propylene number of 2-14 polyethylene·polypropylene glycol di(meth)acrylate, trimethylol Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate Base) acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, two Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, tripropylene glycol di(meth)acrylate Wait. These compounds may be used alone or in combination of two or more kinds. Here, "EO" means ethylene oxide, and the EO-modified compound means a compound having a block structure of an oxyethylene group. "PO" stands for propylene oxide, and a PO-modified compound refers to a compound having a block structure of an oxypropylene group.
作为上述双酚A类(甲基)丙烯酸酯化合物，可例举出：2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基多丙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基多丁氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基多乙氧基多丙氧基]苯基}丙烷等。作为上述2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷，可例举出：2,2-双{4-[(甲基)丙烯酰氧基二乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基三乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基四乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基五乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基六乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基七乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基八乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基九乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十一乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十二乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十三乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十四乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十五乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十六乙氧基]苯基}丙烷等。上述2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷的1分子内的氧化乙烯基数优选为4-20，更优选为8-15。这些化合物可以单独使用，也可两种以上组合使用。Examples of the bisphenol A-based (meth)acrylate compound include: 2,2-bis{4-[(meth)acryloxypolyethoxy]phenyl}propane, 2,2- Bis{4-[(meth)acryloxypolypropoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxypolybutoxy]phenyl}propane, 2,2-Bis{4-[(meth)acryloyloxypolyethoxypolypropoxy]phenyl}propane and the like. As the above-mentioned 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane, there may be mentioned: 2,2-bis{4-[(meth)acryloyloxy Diethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxytriethoxy]phenyl}propane, 2,2-bis{4-[(methyl )Acryloyloxytetraethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxypentaethoxy]phenyl}propane, 2,2-bis{4- [(Meth)acryloyloxyhexaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyheptethoxy]phenyl}propane, 2,2- Bis{4-[(meth)acryloyloxyoctaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxynonaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyundecethoxy] Phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydodecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxy Thirteen ethoxy] phenyl} propane, 2,2-bis{4-[(meth)acryloyloxytetradecethoxy] phenyl}propane, 2,2-bis{4-[(甲Yl)acryloyloxypentadecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexadecethoxy]phenyl}propane, etc. The number of oxyethylene groups in one molecule of the 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane is preferably 4-20, and more preferably 8-15. These compounds may be used alone or in combination of two or more kinds.
作为上述分子内具有氨酯键的(甲基)丙烯酸酯化合物，可例举出：在β位具有OH基的(甲基)丙烯酸类单体和二异氰酸酯化合物(异佛尔酮二异氰酸酯、2,6-甲苯二异氰酸酯、2,4-甲苯二异氰酸酯、1,6-六亚甲基二异氰酸 酯等)的加成反应产物、三[(甲基)丙烯酰氧基四亚乙基二醇异氰酸酯]六亚甲基异氰脲酸酯、EO改性氨酯二(甲基)丙烯酸酯、PO改性氨酯二(甲基)丙烯酸酯、EO,PO改性氨酯二(甲基)丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。As the (meth)acrylate compound having a urethane bond in the molecule, a (meth)acrylic monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2 ,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tris((meth)acryloyloxytetraethylene glycol isocyanate) ] Hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO, PO modified urethane di(meth)acrylic acid Ester etc. These compounds may be used alone or in combination of two or more kinds.
作为上述壬基苯氧基多乙烯氧基丙烯酸酯，可例举出：壬基苯氧基四乙烯氧基丙烯酸酯、壬基苯氧基五乙烯氧基丙烯酸酯、壬基苯氧基六乙烯氧基丙烯酸酯、壬基苯氧基七乙烯氧基丙烯酸酯、壬基苯氧基八乙烯氧基丙烯酸酯、壬基苯氧基九乙烯氧基丙烯酸酯、壬基苯氧基十乙烯氧基丙烯酸酯、壬基苯氧基十一乙烯氧基丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。As the nonylphenoxy polyvinyloxy acrylate, nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy hexaethylene Oxyacrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxydecaethyleneoxy Acrylate, nonylphenoxyundecenyloxy acrylate, etc. These compounds may be used alone or in combination of two or more kinds.
作为上述苯二甲酸类化合物，可例举出：γ-氯-β-羟基丙基-β’-(甲基)丙烯酰氧基乙基邻苯二甲酸酯、β-羟基烷基-β’-(甲基)丙烯酰氧基烷基邻苯二甲酸酯等。这些化合物可以单独使用，也可两种以上组合使用。Examples of the phthalic acid compound include: γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyalkyl-β '-(Meth)acryloyloxyalkyl phthalate, etc. These compounds may be used alone or in combination of two or more kinds.
作为上述(甲基)丙烯酸烷基酯，可例举出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸羟甲酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸异辛酯、乙氧基化壬基酚(甲基)丙烯酸酯、丙二醇聚丙烯醚二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙氧基化聚四氢呋喃二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯等。其中，优选为(甲基)丙烯酸甲酯、(甲基)丙烯 酸乙酯、三羟甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯。这些化合物可以单独使用，也可两种以上组合使用。The alkyl (meth)acrylate may, for example, be 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, (methyl) ) Isobornyl acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-hydroxypropyl ester, benzyl (meth)acrylate, amyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)acrylate, ethoxylated nonyl Phenol (meth)acrylate, propylene glycol polypropylene ether di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, Ethoxylated polytetrahydrofuran glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, etc. 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, dipentaerythritol hexaacrylate. These compounds may be used alone or in combination of two or more kinds.
从提高分辨率、耐镀覆性、密合性的角度来看，所述具有烯属不饱和双键的化合物优选双酚A类(甲基)丙烯酸酯化合物和分子内具有氨酯键的(甲基)丙烯酸酯化合物。从可以提高灵敏度和解析度的角度来看，优选双酚A类(甲基)丙烯酸酯化合物。作为双酚A类(甲基)丙烯酸酯化合物的市售品，示例性地，有2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷(新中村化学工业株式会社制，BPE-200)、2,2-双{4-[(甲基)丙烯酰氧基多丙氧基]苯基)丙烷(新中村化学工业株式会社制，BPE-5000；日立化成株式会社制，FA-321M)、2,2-双{4-[(甲基)丙烯酰氧基多丁氧基]苯基}丙烷(新中村化学工业株式会社，BPE-1300)等。From the standpoint of improving resolution, plating resistance, and adhesion, the compound having an ethylenically unsaturated double bond is preferably a bisphenol A (meth)acrylate compound and a compound having a urethane bond in the molecule ( Meth)acrylate compound. From the viewpoint of improving sensitivity and resolution, bisphenol A-based (meth)acrylate compounds are preferred. As a commercially available product of bisphenol A-based (meth)acrylate compounds, exemplarily, there is 2,2-bis{4-[(meth)acryloxypolyethoxy]phenyl}propane (new Nakamura Chemical Industry Co., Ltd., BPE-200), 2,2-bis{4-[(meth)acryloyloxypolypropoxy]phenyl)propane (Shin Nakamura Chemical Industry Co., Ltd., BPE-5000 ; Hitachi Chemical Co., Ltd., FA-321M), 2,2-bis{4-[(meth)acryloxypolybutoxy]phenyl}propane (Shin Nakamura Chemical Industry Co., Ltd., BPE-1300) Wait.
在100质量份感光性树脂组合物中，具有烯属不饱和双键的化合物的含量优选20-50质量份，更优选25-45质量份。当所述具有烯属不饱和双键的化合物的含量在20质量份以上时，感光性树脂组合物的灵敏度和解析度会进一步提高；当其含量在50质量份以下，感光性树脂组合物更易薄膜化，且对于蚀刻处理的耐久性进一步提高。In 100 parts by mass of the photosensitive resin composition, the content of the compound having an ethylenically unsaturated double bond is preferably 20-50 parts by mass, more preferably 25-45 parts by mass. When the content of the compound having ethylenically unsaturated double bonds is more than 20 parts by mass, the sensitivity and resolution of the photosensitive resin composition will be further improved; when the content is less than 50 parts by mass, the photosensitive resin composition is more easily The film becomes thinner, and the durability against etching treatment is further improved.
供氢体(D)Hydrogen donor (D)
本发明的感光性树脂组合物还包括供氢体，以便改善感光度。双咪唑类化合物经光照后裂解，产生的单咪唑自由基体积较大，位阻效应使得活性较小，很难单独引发单体聚合，而如果和供氢体配合使用，则单咪唑自由基容易夺取供氢体上的活泼氢，产生新的活性自由基，进而引发单体聚 合。The photosensitive resin composition of the present invention further includes a hydrogen donor in order to improve sensitivity. The bisimidazole compounds are cleaved after exposure to light, and the monoimidazole radicals produced are larger in volume. The steric hindrance makes the activity less, and it is difficult to initiate monomer polymerization alone. If used in conjunction with hydrogen donors, the monoimidazole radicals are easy The active hydrogen on the hydrogen donor is taken away to generate new active free radicals, which in turn initiates monomer polymerization.
只要是具有上述特性的供氢体，在具体种类方面就没有特别限制，可以包括(但不限于)：胺类化合物、羧酸类化合物、含有巯基的有机硫化合物或醇类化合物等。这些化合物可单独使用，或以其中的两种以上组合使用。As long as it is a hydrogen donor with the above characteristics, there is no particular limitation in terms of specific types, and it may include (but not limited to): amine compounds, carboxylic acid compounds, mercapto-containing organic sulfur compounds or alcohol compounds, etc. These compounds can be used alone or in combination of two or more of them.
胺类化合物没有特别限制，可以包括(但不限于)：脂肪族胺化合物，如三乙醇胺、甲基二乙醇胺、三异丙醇胺等；芳香族胺化合物，如4-二甲氨基苯甲酸甲酯、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸异戊酯、4-二甲氨基苯甲酸2-乙基己酯、2-二甲氨基乙基苯甲酸酯、N,N-二甲基对甲苯胺、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(二乙氨基)二苯甲酮等。Amine compounds are not particularly limited, and may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as 4-dimethylaminobenzoic acid methyl Ester, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N , N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.
羧酸类化合物没有特别限制，可以包括(但不限于)：芳香族杂乙酸、苯基硫代乙酸、甲基苯基硫代乙酸、乙基苯基硫代乙酸、甲基乙基苯基硫代乙酸、二甲基苯基硫代乙酸、甲氧基苯基硫代乙酸、二甲氧基苯基硫代乙酸、氯苯基硫代乙酸、二氯苯基硫代乙酸、N-苯基甘氨酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘氨酸、萘氧基乙酸等。The carboxylic acid compounds are not particularly limited, and may include (but are not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylsulfide Acetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenyl Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.
含有巯基的有机硫化合物没有特别限制，可以包括(但不限于)：2-巯基苯并噻唑(MBO)、2-巯基苯并咪唑(MBI)、十二烷基硫醇、乙二醇双(3-巯基丁酸酯)、1,2-丙二醇双(3-巯基丁酸酯)、二乙二醇双(3-巯基丁酸酯)、丁二醇双(3-巯基丁酸酯)、辛二醇双(3-巯基丁酸酯)、三羟甲基丙烷三(3-巯基丁酸酯)、季戊四醇四(3-巯基丁酸酯)、二季戊四醇六(3-巯基丁酸酯)、乙二醇双(2-巯基丙酸酯)、丙二醇双(2-巯基丙酸酯)、二乙二醇双(2-巯基丙酸酯)、丁二醇双(2-巯基丙酸酯)、辛二醇双(2-巯基丙酸酯)、三羟甲基丙烷三(2-巯基丙酸酯)、季戊四醇四(3-巯基丙酸酯)、二季戊四醇六(2-巯基丙酸酯)、 乙二醇双(3-巯基异丁酸酯)、1,2-丙二醇双(3-巯基异丁酸酯)、二乙二醇双(3-巯基异丁酸酯)、丁二醇双(3-巯基异丁酸酯)、辛二醇双(3-巯基异丁酸酯)、三羟甲基丙烷三(3-巯基异丁酸酯)、季戊四醇四(3-巯基异丁酸酯)、二季戊四醇六(3-巯基异丁酸酯)、乙二醇双(2-巯基异丁酸酯)、1,2-丙二醇双(2-巯基异丁酸酯)、二乙二醇双(2-巯基异丁酸酯)、丁二醇双(2-巯基异丁酸酯)、辛二醇双(2-巯基异丁酸酯)、三羟甲基丙烷三(2-巯基异丁酸酯)、季戊四醇四(2-巯基异丁酸酯)、二季戊四醇六(2-巯基异丁酸酯)、乙二醇双(4-巯基戊酸酯)、1,2-丙二醇双(4-巯基异戊酸酯)、二乙二醇双(4-巯基戊酸酯)、丁二醇双(4-巯基戊酸酯)、辛二醇双(4-巯基戊酸酯)、三羟甲基丙烷三(4-巯基戊酸酯)、季戊四醇四(4-巯基戊酸酯)、二季戊四醇六(4-巯基戊酸酯)、乙二醇双(3-巯基戊酸酯)、1,2-丙二醇双(3-巯基戊酸酯)、二乙二醇双(3-巯基戊酸酯)、丁二醇双(3-巯基戊酸酯)、辛二醇双(3-巯基戊酸酯)、三羟甲基丙烷三(3-巯基戊酸酯)、季戊四醇四(3-巯基戊酸酯)、二季戊四醇六(3-巯基戊酸酯)等脂肪族二级多官能硫醇化合物；芳香族二级多官能硫醇化合物，如邻苯二甲酸二(1-巯基乙酯)、邻苯二甲酸二(2-巯基丙酯)、邻苯二甲酸二(3-巯基丁酯)、邻苯二甲酸二(3-巯基异丁酯)等。The organosulfur compounds containing mercapto groups are not particularly limited, and may include (but are not limited to): 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis( 3-mercaptobutyrate), 1,2-propanediol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), Octanediol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptobutyrate) , Ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate) ), octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(2-mercaptopropionate) Ester), ethylene glycol bis(3-mercaptoisobutyrate), 1,2-propanediol bis(3-mercaptoisobutyrate), diethylene glycol bis(3-mercaptoisobutyrate), butane Alcohol bis(3-mercaptoisobutyrate), octanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), pentaerythritol tetra(3-mercaptoisobutyrate) Acid ester), dipentaerythritol hexa(3-mercaptoisobutyrate), ethylene glycol bis(2-mercaptoisobutyrate), 1,2-propanediol bis(2-mercaptoisobutyrate), diethylene two Alcohol bis(2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane tris(2-mercapto Isobutyrate), pentaerythritol tetra (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1,2-propanediol bis (4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), Trimethylolpropane tris(4-mercaptovalerate), pentaerythritol tetra(4-mercaptovalerate), dipentaerythritol hexa(4-mercaptovalerate), ethylene glycol bis(3-mercaptovalerate) , 1,2-propanediol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3- Mercaptovalerate), trimethylolpropane tris(3-mercaptovalerate), pentaerythritol tetra(3-mercaptovalerate), dipentaerythritol hexa(3-mercaptovalerate) and other aliphatic secondary polyfunctional Thiol compounds; aromatic secondary polyfunctional thiol compounds, such as bis(1-mercaptoethyl) phthalate, bis(2-mercaptopropyl) phthalate, bis(3-mercaptophthalate) Butyl ester), phthalic acid bis(3-mercaptoisobutyl ester), etc.
醇类化合物没有特别限制，可以包括(但不限于)：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、新戊醇、正己醇、环已醇、乙二醇、1,2-丙二醇、1,2,3-丙三醇、苯甲醇、苯乙醇等。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.
在100质量份感光性树脂组合物中，供氢体(D)的含量可以为0.01-20重量份，优选0.01-10重量份。当供氢体的含量在上述范围内，对调控感光性树脂组合物的感光度是有利的。In 100 parts by mass of the photosensitive resin composition, the content of the hydrogen donor (D) may be 0.01-20 parts by weight, preferably 0.01-10 parts by weight. When the content of the hydrogen donor is within the above range, it is advantageous to control the sensitivity of the photosensitive resin composition.
其它任选的助剂(E)Other optional additives (E)
除了上述各组分，任选地，本发明的感光性树脂组合物中还可以根据需要包含适量的其它助剂。示例性地，助剂可以包括其它光引发剂和/或增感剂、有机溶剂、染料、颜料、光显色剂、填充剂、增塑剂、稳定剂、涂布助剂、剥离促进剂等中的至少一种。In addition to the above-mentioned components, optionally, the photosensitive resin composition of the present invention may further contain an appropriate amount of other auxiliary agents as needed. Exemplarily, the auxiliary agent may include other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, light developers, fillers, plasticizers, stabilizers, coating aids, peeling promoters, etc. At least one of them.
所述其它光引发剂和/或增感剂可包括(但不限于)：双咪唑类、芳香族酮类、蒽醌类、苯偶姻和苯偶姻烷基醚类、肟酯类、三嗪类、香豆素类、噻吨酮类、吖啶类及其它本领域技术人员已知的光引发剂。The other photoinitiators and/or sensitizers may include (but are not limited to): bisimidazoles, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, three Azazines, coumarins, thioxanthones, acridines and other photoinitiators known to those skilled in the art.
示例性地，双咪唑类化合物包括：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,1’-二咪唑、2,2’,5-三(2-氟苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-二咪唑、2,2’-二(2,4-二氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-氟苯基)-4-(邻氯苯基)-5-(3,4-二甲氧基苯基)-4’,5’-二苯基-二咪唑、2,2’-二(2-氟苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-甲氧基苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-氯-5-硝基苯基)-4,4’-二(3,4-二甲氧基苯基)-5,5’-二(邻氯苯基)-二咪唑、2,2’-二(2-氯-5-硝基苯基)-4-(3,4-二甲氧基苯基)-5-(邻氯苯基)-4’,5’-二苯基-二咪唑、2,2’-二(2,4-二氯苯基)-4,4’-二(3,4-二甲氧基苯基)-5,5’-二(邻氯苯基)-二咪唑、2-(2,4-二氯苯基)-4-(3,4-二甲氧基苯基)-2’,5-二(邻氯苯基)-4’,5’-二苯基-二咪唑、2-(2,4-二氯苯基)-2’-(邻氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2,4-二氯苯基)-4,4’,5,5’-四苯基-二咪唑及其相似物。这些双咪唑类化合物可以单独使用或两种以上组合使用。Exemplarily, bisimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tris(ortho Chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tris(2-fluoro Phenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4 ,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxy Phenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2, 2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)- 4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitro Phenyl)-4-(3,4-dimethoxyphenyl)-5-(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2, 4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2-(2,4- Dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-bis(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2-( 2,4-Dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2,4-dichloro (Phenyl)-4,4',5,5'-tetraphenyl-diimidazole and its analogues. These bisimidazole compounds can be used alone or in combination of two or more.
示例性地，芳香族酮类化合物包括：苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、二苯甲酮、4-苯甲酰基二苯硫醚、4-苯甲酰基-4’-甲基二苯硫醚、4-苯甲酰基-4’-乙基二苯硫醚、 4-苯甲酰基-4’-丙基二苯硫醚、4,4’-双(二乙基氨基)二苯甲酮、4-对甲苯巯基二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(甲基、乙基氨基)二苯甲酮、苯乙酮二甲基缩酮、苯偶酰二甲基缩酮、α,α’-二甲基苯偶酰缩酮、α,α’-二乙氧基苯乙酮、2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯甲酮、2-羟基-2-甲基-1-对羟乙基醚基苯基丙酮、2-甲基1-(4-甲巯基苯基)-2-吗啉1-丙酮、2-苄基-2-二甲氨基-1-(4-吗啉苯基)1-丁酮、苯基双(2,4,6-三甲基苯甲酰基)氧膦、2,4,6(三甲基苯甲酰基)二苯基氧化膦、2-羟基-1-{3-[4-(2-羟基-2-甲基-丙酰基)-苯基]-1,1,3-三甲基-茚-5-基}-2-甲基丙酮、2-羟基-1-{1-[4-(2-羟基-2-甲基-丙酰基)-苯基]-1,3,3-三甲基-茚-5-基}-2-甲基丙酮、1-(4-异丙基苯基)-2-羟基-2-甲基丙-1-酮、4-(2-羟基乙氧基)-苯基-(2-羟基-2-丙基)酮及其相似物。这些芳香族酮类化合物可以单独使用或两种以上组合使用。Exemplarily, the aromatic ketone compounds include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 ,1-Dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyl Diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino)benzophenone, 4-p-toluene mercaptobenzophenone, 2 ,4,6-Trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethyl Amino) benzophenone, acetophenone dimethyl ketal, benzil dimethyl ketal, α,α'-dimethyl benzil ketal, α,α'-diethoxy styrene Ketone, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, 2-methyl 1-(4-Methylmercaptophenyl)-2-morpholine 1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)-1-butanone, phenylbis( 2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6(trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-1-{3-[4-(2- Hydroxy-2-methyl-propionyl)-phenyl]-1,1,3-trimethyl-inden-5-yl}-2-methylacetone, 2-hydroxy-1-{1-[4- (2-Hydroxy-2-methyl-propionyl)-phenyl)-1,3,3-trimethyl-inden-5-yl)-2-methylacetone, 1-(4-isopropylbenzene Yl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone and the like. These aromatic ketone compounds can be used alone or in combination of two or more.
示例性地，蒽醌类化合物包括：2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、2,3-二甲基蒽醌、2-乙基蒽-9,10-二乙酯、1,2,3-三甲基蒽-9,10-二辛脂、2-乙基蒽-9,10-二(4-氯丁酸甲酯)、2-{3-[(3-乙基氧杂环丁烷-3-基)甲氧基]-3-氧代丙基}蒽-9,10-二乙酯、9,10-二丁氧基蒽、9,10-二乙氧基-2-乙基蒽、9,10-二(3-氯丙氧基)蒽、9,10-二(2-羟基乙巯基)蒽、9,10-二(3-羟基-1-丙巯基)蒽及其相似物。这些蒽醌类化合物可以单独使用或两种以上组合使用。Exemplarily, anthraquinone compounds include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl, 1,2,3-trimethylanthracene-9,10-dioctyl, 2-ethylanthracene-9,10-bis(4-chlorobutyric acid Methyl ester), 2-{3-[(3-ethyloxetan-3-yl)methoxy]-3-oxopropyl}anthracene-9,10-diethyl ester, 9,10 -Dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethylmercapto)anthracene , 9,10-Bis(3-hydroxy-1-propanethiol)anthracene and its analogues. These anthraquinone compounds can be used alone or in combination of two or more.
示例性地，苯偶姻和苯偶姻烷基醚类化合物包括：苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻苯基醚及其相似物。这些苯偶姻和苯偶姻烷基醚类化合物可以单独使用或两种以上组合使用。Illustratively, 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 can be used alone or in combination of two or more.
示例性地，肟酯类化合物可以包括：1-(4-苯硫基苯基)-正辛烷-1,2-二酮 -2-苯甲酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-乙烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-丁烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-丙烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-1-环己基-甲烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-(3-环戊基)-丙烷-1-酮-乙酸肟酯、1-(4-苯硫基苯基)-(3-环戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯硫基苯基)-(3-环己基)-丙烷-1,2-二酮-2-环己基甲酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-(3-环戊基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基丙酮)-1-肟乙酸酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基丙酮)-1-肟环己基甲酸酯、1-(4-苯甲酰基二苯硫醚)-3-环戊基丙酮)-1-肟环己基甲酸酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-邻甲基苯甲酸肟酯、1-(4-苯硫基苯基)-(3-环戊基)-丙烷-1,2-二酮-2-环己基甲酸肟酯、1-(4-噻吩甲酰基-二苯硫醚-4’-基)-3-环戊基-丙烷-1-酮-乙酸肟酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基)-丙烷-1,2-二酮-2-肟乙酸酯、1-(6-硝基-9-乙基咔唑-3-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(6-噻吩甲酰基-9-乙基咔唑-3-基)-(3-环己基丙酮)-1-肟乙酸酯、1-(6-呋喃糠甲酰基-9-乙基咔唑-3-基)-(3-环戊基丙酮)-1-肟乙酸酯、1,4-二苯基丙烷-1,3-二酮-2-乙酸肟酯、1-(6-糠酰基-9-乙基咔唑-3-基)-(3-环己基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(4-苯硫基苯基)-(3-环已基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(6-呋喃糠甲酰基-9-乙基咔唑-3-基)-(3-环己基丙酮)-1-肟乙酸酯、1-(4-苯硫基苯基)-(3-环已基)-丙烷-1,2-二酮-3-苯甲酸肟酯、1-(6-噻吩甲酰基-9-乙基咔唑-3-基)-(3-环己基)-丙烷-1, 2-二酮-2-乙酸肟酯、2-[(苯甲酰氧基)亚氨基]-1-苯基丙烷-1-酮、1-苯基-1,2-丙二酮-2-(氧代乙酰基)肟、1-(4-苯硫基苯基)-2-(2-甲基苯基)-乙烷-1,2-二酮-2-乙酸肟酯、1-(9,9-二丁基-7-硝基芴-2-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-{4-[4-(噻吩-2-甲酰基)苯硫基]苯基}-3-环戊基丙烷-1,2-二酮-2-乙酸肟酯、1-[9,9-二丁基-2-基]-3-环己基丙基丙烷-1,2-二酮-2-乙酸肟酯、1-[6-(2-苯甲酰氧基亚氨基)-3-环己基丙基-9-乙基咔唑-3-基]辛烷-1,2-二酮-2-苯甲酸肟酯、1-(7-硝基-9,9-二烯丙基芴-2-基)-1-(2-甲基苯基)甲酮-乙酸肟酯、1-[6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基]-3-环戊基-丙烷-1-酮-苯甲酸肟酯、1-[7-(2-甲基苯甲酰基)-9,9-二丁基芴-2-基]-3-环己基丙烷-1,2-二酮-2-乙酸肟酯、1-[6-(呋喃-2-甲酰基)-9-乙基咔唑-3-基]-3-环己基丙烷-1,2-二酮-2-乙氧甲酰肟酯及其相似物。这些肟酯类化合物可以单独使用或两种以上组合使用。Exemplarily, the oxime ester compound may include: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-[6-(2-methyl Benzoyl)-9-ethylcarbazol-3-yl]-ethane-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole -3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-propan-1-one- Oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-cyclohexyl-methane-1-one-oxime acetate, 1-[6 -(2-Methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propan-1-one-oxime acetate, 1-(4-phenylthiobenzene Yl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1, 2-Diketone-2-cyclohexyl oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-(3-cyclopentyl)-propane- 1,2-Dione-2-oxime acetate, 1-(6-O-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2 -Dione-2-oxime benzoate, 1-(4-benzoyl diphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-o-methylbenzene Formyl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(4-benzoyldiphenyl sulfide)-3-ring Pentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1, 2-diketone-2-o-methylbenzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime Esters, 1-(4-thenoyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-oxime acetate, 1-(4-benzoyl diphenyl sulfide )-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazol-3-yl)-3-cyclohexyl -Propan-1-one-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propane-1-one-oxime acetate, 1-(6-thenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanfuroyl-9-ethyl Carbazol-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-Furfurfuryl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3- Cyclohexyl)-propane-1,2-dione-3-benzoic acid oxime ester, 1-(6-thenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane -1, 2-Dione-2-oxime acetate, 2-[(benzoyloxy)imino]-1-phenylpropane-1-one, 1-phenyl-1,2-propanedione -2-(oxoacetyl)oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane-1,2-dione-2-acetoxime ester, 1-(9,9-Dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane-1-one-oxime acetate, 1-{4-[4-(thiophen-2- Formyl)phenylthio)phenyl)-3-cyclopentylpropane-1,2-dione-2-oxime acetate, 1-[9,9-dibutyl-2-yl]-3-ring Hexylpropylpropane-1,2-dione-2-oxime acetate, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazole-3 -Yl]octane-1,2-dione-2-oxime benzoate, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methyl Phenyl) ketone-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-3-cyclopentyl-propane-1-one-benzene Oxime formate, 1-[7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-acetic oxime Esters, 1-[6-(furan-2-formyl)-9-ethylcarbazol-3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxycarbonyl oxime ester and Its analogues. These oxime ester compounds can be used alone or in combination of two or more.
示例性地，三嗪类化合物包括：2-(4-乙基联苯)-4,6-双(三氯甲基)-1,3,5-三嗪、2-(3,4-亚甲氧基苯基)-4,6-双(三氯甲基)-1,3,5-三嗪、3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、1,1,1,3,3,3-六氟异丙基-3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸酯、乙基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、2-乙氧基乙基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、环己基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、芐基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、3-{氯-4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙醯胺、2,4-双(三氯甲基)-6-p-甲氧基苯乙烯基-s-三嗪、2,4-双(三氯甲基)-6-(1-p-二甲基胺基苯基)-1,3-丁二烯基-s-三嗪、2-三氯甲基-4-胺基-6-p-甲氧基苯乙烯基-s-三嗪及其相似物。这些三嗪类化合物可以单独使用或两种以上组合使用。Exemplarily, triazine compounds include: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-ethylene Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazine -6-yl]phenylthio)propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s- Triazine-6-yl]phenylthio}propionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}ethyl Ester, 2-ethoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, cyclohexyl-2 -{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(tri Chloromethyl)-s-triazin-6-yl]phenylthio) acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl ]Phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propanamide, 2,4-bis(trichloromethyl) Chloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1 ,3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like. These triazine compounds can be used alone or in combination of two or more.
示例性地，香豆素类化合物包括：3,3’-羰基双(7-二乙胺香豆素)、3-苯甲酰基-7-二乙胺香豆素、3,3’-羰基双(7-甲氧基香豆素)、7-二乙氨基-4-甲基香豆素、3-(2-苯并噻唑)-7-(二乙基胺基)香豆素、7-(二乙氨基)-4-甲基-2H-1-苯并吡喃-2-酮[7-(二乙氨基)-4-甲基香豆素]、3-苯甲酰基-7-甲氧基香豆素及其相似物。这些香豆素类化合物可以单独使用或两种以上组合使用。Exemplarily, the coumarin compound includes: 3,3'-carbonyl bis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin, 3,3'-carbonyl Bis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7 -(Diethylamino)-4-methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3-benzoyl-7- Methoxycoumarin and its analogues. These coumarin compounds can be used alone or in combination of two or more.
示例性地，噻吨酮类化合物包括：噻吨酮、2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮、2-氯噻吨酮、1-氯-4-丙氧基噻吨酮、异丙基噻吨酮、二异丙基噻吨酮及相似物。这些噻吨酮类化合物可以单独使用或两种以上组合使用。Illustratively, 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 can be used alone or in combination of two or more.
示例性地，吖啶类化合物包括：9-苯基吖啶、9-对甲基苯基吖啶、9-间甲基苯基吖啶、9-邻氯苯基吖啶、9-邻氟苯基吖啶、1,7-二(9-吖啶基)庚烷、9-乙基吖啶、9-(4-溴苯基)吖啶、9-(3-氯苯基)吖啶、1,7-双(9-吖啶)庚烷、1,5-双(9-吖啶戊烷)、1,3-双(9-吖啶)丙烷及其相似物。这些吖啶类化合物可以单独使用或两种以上组合使用。Exemplarily, acridine compounds include: 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methylphenyl acridine, 9-o-chlorophenyl acridine, 9-o-fluoro Phenylacridine, 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine , 1,7-bis(9-acridine) heptane, 1,5-bis(9-acridine pentane), 1,3-bis(9-acridine) propane and the like. These acridine compounds can be used alone or in combination of two or more.
有机溶剂只要能够溶解前述各组分即可，示例性地，可以是二醇醚系溶剂、醇系溶剂、酯系溶剂、酮系溶剂、酰胺系溶剂、含氯溶剂等，优选特别考虑着色剂、碱可溶性聚合物的溶解性、涂布性、安全性等因素来进行选择。优选地，有机溶剂可以是乙基溶纤剂(乙二醇单乙基醚)、甲基溶纤剂(乙二醇单甲基醚)、丁基溶纤剂(乙二醇单丁基醚)、甲基甲氧基丁醇(3-甲基-3-甲氧基丁醇)、丁基卡必醇(二甘醇单丁基醚)、乙二醇单乙基醚乙酸酯、乙二醇单叔丁基醚、丙二醇单甲基醚乙酸酯、丙二醇单甲基醚(1-甲氧基-2-丙醇)、丙二醇单乙基醚(1-乙氧基-2-丙醇)、丙二醇单乙基醚乙酸酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸溶纤剂(乙二醇单甲基醚乙酸酯)、 乙酸甲氧基丁酯(乙酸3-甲氧基丁酯)、乙酸3-甲基-3-甲氧基丁酯、3-乙氧基丙酸乙酯(EEP)、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、2-丁酮(MEK)、甲基异丁基酮(MIBK)、环己酮、环戊酮、二丙酮醇(4-羟基-4-甲基-2-戊酮)、异佛尔酮(3,5,5-三甲基-2-环己烯-1-酮)、二异丁基酮(2,6-二甲基-4-庚酮)、N-甲基吡咯烷酮(4-甲基氨基内酰胺或NMP)、甲醇、乙醇、异丙醇、正丙醇、异丁醇、正丁醇等。这些溶剂可单独使用，或以其中两种以上组合使用。The organic solvent only needs to be able to dissolve the aforementioned components. Illustratively, it may be glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, chlorine-containing solvents, etc., and colorants are particularly preferred. , Alkali-soluble polymer solubility, coatability, safety and other factors to choose. 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 two Alcohol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol) ), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (acetic acid 3-methoxybutyl ester), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate Esters, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophor Ketone (3,5,5-trimethyl-2-cyclohexene-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4 -Methylaminolactam or NMP), methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, etc. These solvents can be used alone or in combination of two or more of them.
示例性地，染料、颜料及光显色剂包括：三(4-二甲基氨基苯基)甲烷、三(4-二甲基氨基-2甲基苯基)甲烷、荧烷染料、甲苯磺酸一水合物、碱性品红、酞菁绿及酞菁蓝等酞菁系、金胺碱、副品红、结晶紫、甲基橙、尼罗蓝2B、维多利亚蓝、孔雀绿、金刚绿、碱性蓝20、艳绿、伊红、乙基紫、赤藓红钠盐B、甲基绿、苯酚酞、茜素红S、百里香酚酞、甲基紫2B、喹那定红、玫瑰红钠琼脂、米塔尼尔黄、百里香酚磺酞、二甲苯酚蓝、甲基橘、橘IV、二苯基流卡巴腙、2,7-二氯荧光素、泛甲基红、刚果红、本佐红紫4B、α-萘基红、非那西汀、甲基紫、维多利亚纯蓝BOH、罗丹明6G、二苯基胺、二苄基苯胺、三苯基胺、二乙基苯胺、二-对伸二胺、对甲苯胺、苯并三氮唑、甲基苯丙三唑、4,4’-联二胺、邻氯苯胺、白色结晶紫、白色孔雀绿、白色苯胺、白色甲基紫、偶氮系等有机颜料，二氧化钛等无机颜料。在具有良好对比度的考量下，优选使用三(4-二甲基氨基苯基)甲烷(即隐色结晶紫，LCV)。这些染料、颜料及光显色剂可以单独一种使用，也可两种以上混合使用。Exemplarily, dyes, pigments and light developers include: tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, fluoran dye, toluene sulfonate Acid monohydrate, basic fuchsin, phthalocyanine green and phthalocyanine blue and other phthalocyanines, auramine base, para-fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, diamond green , Basic Blue 20, Brilliant Green, Eosin, Ethyl Violet, Erythrosine Sodium B, Methyl Green, Phenolphthalein, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinadine Red, Rose Red Sodium agar, mitanil yellow, thymol sulfophthalein, xylenol blue, methyl orange, tangerine IV, diphenyl flow carbachol, 2,7-dichlorofluorescein, pan-methyl red, Congo red, Benzo Red Violet 4B, α-Naphthyl Red, Phenacetin, Methyl Violet, Victoria Pure Blue BOH, Rhodamine 6G, Diphenylamine, Dibenzylaniline, Triphenylamine, Diethylaniline, Di-p-diamine, p-toluidine, benzotriazole, methamphetamine, 4,4'-diamine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl Organic pigments such as violet and azo, inorganic pigments such as titanium dioxide. In consideration of good contrast, tris(4-dimethylaminophenyl)methane (ie leuco crystal violet, LCV) is preferably used. These dyes, pigments and light developers may be used alone or in combination of two or more.
示例性地，填充剂包括：二氧化硅、氧化铝、滑石、碳酸钙、硫酸钡等填充剂(不包含上述无机颜料)。填充剂可以单独一种使用，也可两种 以上混合使用。Exemplarily, the filler includes fillers such as silica, alumina, talc, calcium carbonate, and barium sulfate (not including the above-mentioned inorganic pigments). The filler may be used alone or in combination of two or more.
示例性地，增塑剂包括：邻苯二甲酸二丁酯、邻苯二甲酸二庚酯、邻苯二甲酸二辛酯、邻苯二甲酸二烯丙酯等邻苯二甲酸酯，三甘醇二乙酸酯、四乙二醇二乙酸酯等乙二醇酯，对甲苯磺酰胺、苯磺酰胺、正丁基苯磺酰胺等磺酰胺类，磷酸三苯酯、三甲基磷酸酯、三乙基磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、三二甲苯基磷酸酯、甲苯基二苯基磷酸酯、三二甲苯基磷酸酯、2-萘基二苯基磷酸酯、甲苯基二2,6-二甲苯基磷酸酯、芳香族缩合磷酸酯、三(氯丙基)磷酸酯、三(三溴新戊基)磷酸酯、含卤缩合磷酸酯，二辛酸三甘醇酯，二(2-乙基己酸)三甘醇酯、二庚酸四甘醇酯、癸二酸二乙酯、辛二酸二丁酯、磷酸三(2-乙基乙酯)、Brij30[C 12H 25(OCH 2CH 2) 4OH]、和Brij35[C 12H 25(OCH 2CH 2) 20OH]等。增塑剂可以单独一种使用，也可两种以上混合使用。 Exemplarily, the plasticizer includes: phthalate esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, three Glycol esters such as glycol diacetate, tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide, triphenyl phosphate, trimethyl phosphoric acid Esters, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, tricresyl phosphate, 2-naphthyl diphenyl phosphate Ester, cresyl bis 2,6-xylyl phosphate, aromatic condensed phosphate, tris(chloropropyl) phosphate, tris(tribromoneopentyl) phosphate, halogen-containing condensed phosphate, dicaprylic acid three Glycol ester, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris(2-ethylethyl) phosphate , Brij30[C 12 H 25 (OCH 2 CH 2 ) 4 OH], and Brij35[C 12 H 25 (OCH 2 CH 2 ) 20 OH] and so on. The plasticizer can be used alone or in a mixture of two or more.
示例性地，稳定剂包括：氢醌、1,4,4-三甲基-重氮二环(3.2.2)-壬-2-烯-2,3-二氧化物、1-苯基-3-吡唑烷酮、对甲氧基苯酚、烷基和芳基取代的氢醌和醌、叔丁基邻苯二酚、1,2,3-苯三酚、树脂酸铜、萘胺、β-萘酚、氯化亚铜、2,6-二叔丁基对甲酚、吩噻嗪、吡啶、硝基苯、二硝基苯、对甲苯醌和氯醌等。稳定剂可以单独一种使用，也可两种以上混合使用。Exemplarily, the stabilizer includes: 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 hydroquinone and quinone, tert-butylcatechol, 1,2,3-benzenetriol, copper resinate, naphthylamine, β- Naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloranil, etc. The stabilizer can be used singly or in combination of two or more.
示例性地，涂布助剂包括：丙酮、甲醇、甲基醇、乙基醇、异丙基醇、甲基乙基酮、丙二醇单甲基醚乙酸酯、乳酸乙酯、环己酮、γ-丁内酯、二氯甲烷等。涂布助剂可以单独一种使用，也可两种以上混合使用。Exemplarily, the coating aids include: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, γ-butyrolactone, dichloromethane, etc. The coating aids can be used alone or in combination of two or more.
示例性地，剥离促进剂包括：苯磺酸、甲苯磺酸、二甲苯磺酸、苯酚磺酸，甲基、丙基、庚基、辛基、癸基、十二烷基等烷基苯磺酸等。剥离促进剂可以单独一种使用，也可两种以上混合使用。Exemplarily, the peeling accelerator includes: benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl and other alkyl benzene sulfonic acids Acid etc. The peeling accelerator may be used alone or in combination of two or more.
<干膜和湿膜应用><Dry film and wet film application>
本发明的感光性树脂组合物可以制备成干膜，即感光性树脂层叠体，并应用于印刷电路板、保护图案、导体图案、引框线、半导体封装的制造中，经过不同的工序在不同的基材上形成所需要的图案。The photosensitive resin composition of the present invention can be prepared into a dry film, that is, a photosensitive resin laminate, and applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages. Form the required pattern on the substrate.
本发明的感光性树脂组合物也可以通过湿膜涂布机涂布至各对应制造步骤中对应的基材上，即作为湿膜应用于印刷电路板、保护图案、导体图案、引框线、半导体封装的制造中，经过不同的工序在不同的基材上形成所需要的图案。The photosensitive resin composition of the present invention can also be applied to the corresponding substrate in each corresponding manufacturing step by a wet film coater, that is, applied as a wet film to printed circuit boards, protective patterns, conductor patterns, lead wires, In the manufacture of semiconductor packages, the required patterns are formed on different substrates through different processes.
干膜应用Dry film application
本发明的干膜即感光性树脂层叠体，其包含：感光性树脂组合物形成的感光性树脂层以及支撑该感光性树脂层的支撑体。The dry film of the present invention, which is a photosensitive resin laminate, includes a photosensitive resin layer formed of a photosensitive resin composition and a support that supports the photosensitive resin layer.
通常，干膜的制作包括：将感光性树脂组合物涂布在支撑体上，干燥以形成感光性树脂层；任选地，根据需要贴合覆盖膜(保护层)。较佳地，干燥条件是60-100℃下干燥0.5-15min。感光性树脂层的厚度优选为5-95μm，再优选为10-50μm，更优选为15-30μm。若感光性树脂层的厚度小于5μm，则绝缘性不佳，而若感光性树脂层的厚度超过95μm，则解析度可能会较差。Generally, the preparation of the dry film includes: coating the photosensitive resin composition on the support and drying to form a photosensitive resin layer; optionally, bonding a cover film (protective layer) as needed. Preferably, the drying conditions are drying at 60-100°C for 0.5-15 minutes. The thickness of the photosensitive resin layer is preferably 5-95 μm, more preferably 10-50 μm, and more preferably 15-30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation is poor, and if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be poor.
作为支撑体，具体实例可以是各种类型的塑胶膜，如聚对苯二甲酸乙二醇酯、聚乙烯萘二酸酯、聚丙烯、聚乙烯、纤维素乙酸酯、聚甲基丙烯酸烷酯、甲基丙烯酸酯共聚物、聚氯乙烯、聚乙烯醇、聚碳酸酯、聚苯乙烯、玻璃纸、氯乙烯共聚物、聚酰胺、聚亚酰胺、乙烯氯-乙酸乙烯酯共聚物、聚四氟乙烯、聚三氟乙烯及其相似物。此外，亦可使用由两种或以上 材料所组成的复合材料。优选地，使用的是具有极佳光穿透性的聚对苯二甲酸乙二醇酯。支撑体的厚度优选为5-150μm，更优选为10-50μm。As the support, specific examples may be various types of plastic films, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polymethacrylate Ester, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene Vinyl fluoride, polytrifluoroethylene and the like. In addition, composite materials composed of two or more materials can also be used. Preferably, polyethylene terephthalate having excellent light penetration is used. The thickness of the support is preferably 5-150 μm, more preferably 10-50 μm.
对感光性树脂组合物的涂布并无特殊限制，例如可使用喷涂法、滚筒式涂布法、旋转式涂布法、狭缝式涂布法、压缩涂布法、帘涂法、染料涂布法、线条涂布法、刮刀涂布法、辊涂法、刮涂法、喷涂法、浸涂法等常规方法。There are no particular restrictions on the coating of the photosensitive resin composition. For example, spray coating, roller coating, spin coating, slit coating, compression coating, curtain coating, and dye coating can be used. Conventional methods such as cloth method, line coating method, knife coating method, roll coating method, knife coating method, spraying method, dip coating method, etc.
进一步地，本发明提供上述干膜在制造印刷电路板中的应用，包括：Further, the present invention provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:
(1)层叠工序：将感光性树脂层叠体层叠于覆铜层叠板或柔性基板上；(1) Laminating process: Laminating the photosensitive resin laminate on the copper clad laminate or flexible substrate;
(2)曝光工序：对感光性树脂层叠体中的感光性树脂层进行曝光，以图像状照射活性光线使曝光部分进行光固化；(2) Exposure step: exposing the photosensitive resin layer in the photosensitive resin laminate, irradiating active light in an image form to photocuring the exposed part;
(3)显影工序：将感光性树脂层的未曝光部分用显影液去除，以形成保护图案；(3) Developing process: removing the unexposed part of the photosensitive resin layer with a developing solution to form a protective pattern;
(4)导体图案形成工序：对覆铜层叠板或柔性基板表面的未被保护图案覆盖的部分进行刻蚀或镀覆；(4) Conductor pattern formation process: etching or plating the part of the surface of the copper clad laminate or flexible substrate that is not covered by the protective pattern;
(5)剥离工序：将保护图案从该覆铜层叠板或柔性基板剥离。(5) Peeling step: peeling the protective pattern from the copper clad laminate or flexible substrate.
进一步地，本发明提供上述干膜在制造保护图案中的应用，包括如上所述的层叠工序、曝光工序和显影工序，不同在于：层叠工序中感光性树脂层叠体可层叠于各种不同材质的基板上。Further, the present invention provides the application of the above-mentioned dry film in the manufacture of protective patterns, including the lamination process, exposure process, and development process as described above. The difference is that the photosensitive resin laminate can be laminated on various materials in the lamination process. On the substrate.
进一步地，本发明提供上述干膜在制造导体图案中的应用，包括如上所述的层叠工序、曝光工序、显影工序和导体图案形成工序，不同在于：层叠工序中感光性树脂层叠体层叠于金属板或金属覆膜绝缘板上。Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of conductor patterns, including the lamination process, exposure process, development process, and conductor pattern formation process as described above. The difference is that the photosensitive resin laminate is laminated on the metal in the lamination process. Board or metal coated insulating board.
进一步地，本发明提供上述干膜在制造引框线中的应用，包括如上所述的层叠工序、曝光工序、显影工序、和导体图案形成工序，不同在于： 层叠工序中感光性树脂层叠体层叠于金属板上，导体图案形成工序中对未被保护图案覆盖的部分进行刻蚀。Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of lead wire, including the lamination process, exposure process, development process, and conductor pattern forming process as described above, the difference lies in: the photosensitive resin laminate is laminated in the lamination process On the metal plate, the portion not covered by the protective pattern is etched during the conductor pattern forming process.
进一步地，本发明提供上述干膜在制造半导体封装中的应用，包括如上所述的层叠工序、曝光工序、显影工序、和导体图案形成工序，不同在于：层叠工序中感光性树脂层叠体层叠于具有大规模集成电路的晶片上，导体图案形成工序中对未被保护图案覆盖的部分进行镀覆。Further, the present invention provides the application of the above-mentioned dry film in the manufacture of semiconductor packages, including the lamination process, exposure process, development process, and conductor pattern forming process as described above. The difference is that the photosensitive resin laminate is laminated in the lamination process. On a wafer with a large-scale integrated circuit, the portion not covered by the protective pattern is plated in the conductor pattern formation process.
湿膜应用Wet film application
本发明的感光性树脂组合物可以湿膜方式直接涂布在基板上使用，以用于印刷电路板、保护图案、导体图案、引框线、半导体封装等的制造。The photosensitive resin composition of the present invention can be directly coated on a substrate by a wet film method, and used for the production of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
非限制性地，可利用辊涂、刮涂、喷涂、浸涂等常规方法将感光性树脂组合物涂布于基板上，干燥后形成感光性树脂层。Without limitation, the photosensitive resin composition can be coated on the substrate by conventional methods such as roll coating, knife coating, spray coating, and dip coating, and dried to form a photosensitive resin layer.
在基板上形成感光性树脂层后，后续工序如曝光工序、显影工序、导体图案形成工序和剥离工序，均可参照干膜应用的方式进行。After the photosensitive resin layer is formed on the substrate, subsequent processes such as exposure process, development process, conductor pattern formation process, and peeling process can all be performed with reference to the way of dry film application.
曝光工序中，曝光可以列举出掩模曝光法(布线图的负或正掩模图形将活性光线呈图像状地照射的方法)、投影曝光法，也可以采用通过激光直接成像曝光法、数字光学处理曝光法等直接描画曝光法将活性光线呈图像状地照射的方法。作为活性光线的光源，可使用公知的光源，如碳弧灯、汞蒸气弧灯、超高压示灯、高压示灯、氙灯、氩气激光等气体激光、YAG激光等固体激光、半导体激光和氮化镓系蓝紫色激光等有效放射出紫外线的光源。此外，还可以使用照相用泛光灯、日光灯等有效放射出可见光的光源。本发明的感光性树脂组合物对活性光线的光源种类没有特别限制，曝光量优选为10-1000mJ/cm 2。 In the exposure process, the exposure can include the mask exposure method (a method in which the negative or positive mask pattern of the wiring pattern irradiates the active light in an image), the projection exposure method, the direct imaging exposure method by laser, and the digital optics The direct drawing exposure method, such as the processing exposure method, irradiates active light in an image. As the light source of active light, well-known light sources can be used, such as carbon arc lamp, mercury vapor arc lamp, ultra-high pressure indicator lamp, high pressure indicator lamp, xenon lamp, gas laser such as argon laser, solid laser such as YAG laser, semiconductor laser, and gallium nitride It is a light source that effectively emits ultraviolet rays such as a blue-violet laser. In addition, you can also use a light source that effectively emits visible light, such as a floodlight for photography and a fluorescent lamp. The photosensitive resin composition of the present invention has no particular limitation on the type of light source of active light, and the exposure amount is preferably 10-1000 mJ/cm 2 .
显影工序中，将感光性树脂层的未曝光部分用显影液去除。在感光性 树脂层上存在支撑体的情况下，可利用自动剥离器等先除去支撑体，然后再使用碱性水溶液、水系显影液、有机溶剂等显影液除去未曝光部分。碱性水溶液的例子可以是0.1-5质量％的碳酸钠溶液、0.1-5质量％的碳酸钾溶液、0.1-5质量％的氢氧化钠溶液等，pH值优选为9-11。碱性水溶液中还可以加入表面活性剂、消泡剂、有机溶剂等。显影的方式可以是浸渍、喷雾、刷洗等常规方式。In the development step, the unexposed portion of the photosensitive resin layer is removed with a developer. When there is a support on the photosensitive resin layer, the support can be removed using an automatic peeler or the like, and then the unexposed part can be removed using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Examples of the alkaline aqueous solution may be 0.1-5% by mass sodium carbonate solution, 0.1-5% by mass potassium carbonate solution, 0.1-5% by mass sodium hydroxide solution, etc. The pH value is preferably 9-11. Surfactants, defoamers, organic solvents, etc. can also be added to the alkaline aqueous solution. The development method can be conventional methods such as dipping, spraying, and brushing.
刻蚀处理中，以形成于基板上的抗蚀图案(即保护图案)作为掩模，将未被覆盖的电路形成用基板的导体层刻蚀除去，从而形成导体图案。刻蚀处理的方法可以根据待去除的导体层而选择。例如，作为蚀刻液可以列举出氧化铜溶液、氧化铁溶液、碱蚀刻溶液、过氧化氢系蚀刻液等。In the etching process, the resist pattern (ie, protective pattern) formed on the substrate is used as a mask to etch away the uncovered conductor layer of the circuit forming substrate, thereby forming a conductor pattern. The etching method can be selected according to the conductor layer to be removed. For example, examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkali etching solution, and a hydrogen peroxide-based etching solution.
镀敷处理中，以形成于基板上的抗蚀图案为掩模，在未被覆盖的电路形成用基板的绝缘板上镀覆铜和焊锡等。镀敷处理后，除去抗蚀图案从而形成导体图案。作为镀敷处理的方法，既可以是电镀处理，也可以是无电解镀覆处理，优选无电解镀覆处理。作为无电解镀覆处理，可以列举出：硫酸铜镀敷和焦磷酸铜镀敷等铜镀敷、高均匀焊锡(high-throw solder)镀敷等焊锡镀敷、瓦特浴(硫酸镍-氯化镍)镀敷和氨基磺酸镍镀敷等镍镀敷、硬质金镀敷和软质金镀敷等金镀敷。In the plating process, the resist pattern formed on the substrate is used as a mask, and copper, solder, etc. are plated on the insulating plate of the circuit formation substrate that is not covered. After the plating process, the resist pattern is removed to form a conductor pattern. The plating treatment method may be electroplating treatment or electroless plating treatment, but electroless plating treatment is preferred. Examples of electroless plating include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, and Watt bath (nickel sulfate-chlorinated Nickel) plating and nickel plating such as sulfamate nickel plating, and gold plating such as hard gold plating and soft gold plating.
抗蚀图案的除去可以通过比显影工序中使用的碱性水溶液碱性更强的水溶液来进行剥离。作为强碱性水溶液的实例，可使用例如1-10质量％的氢氧化钠水溶液。The removal of the resist pattern can be performed by an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step. As an example of a strong alkaline aqueous solution, for example, 1-10% by mass aqueous sodium hydroxide solution can be used.
<彩色滤光片及其制造方法><Color filter and its manufacturing method>
本发明还涉及上述感光性树脂组合物在制造彩色滤光片的应用、彩色 滤光片以及含有彩色滤光片的液晶显示组件。The present invention also relates to the use of the above-mentioned photosensitive resin composition in the manufacture of color filters, color filters, and liquid crystal display modules containing the color filters.
利用上述感光性树脂组合物制成的彩色滤光片，包括：支撑体，以及在支撑体上使用感光性树脂组合物形成的着色图案。The color filter made from the above-mentioned photosensitive resin composition includes a support and a colored pattern formed on the support using the photosensitive resin composition.
利用感光性树脂组合物通过光固化和光刻工艺制备RGB、BM、光间隔物等的技术已经为本领域的技术人员所熟知。通常包括以下步骤：在支撑体上涂布感光性树脂组合物来形成感光性树脂层的工序(简称为“形成工序”)；将感光性树脂层通过掩模曝光的工序(简称为“曝光工序”)；和将曝光后的感光性树脂层显影来形成着色图案的工序(简称为“显影工序”)。The technology of preparing RGB, BM, photo-spacers, etc. by photocuring and photolithography using the photosensitive resin composition is well known to those skilled in the art. It usually includes the following steps: a process of applying a photosensitive resin composition on a support to form a photosensitive resin layer (abbreviated as "forming process"); a process of exposing the photosensitive resin layer through a mask (abbreviated as "exposing process") "); and the step of developing the exposed photosensitive resin layer to form a colored pattern (referred to simply as "development step").
具体而言，将本发明的感光性树脂组合物直接或间隔其它层而涂布在支撑体(基板)上，形成感光性树脂层；通过规定的掩模图案进行曝光，仅使被光照射的涂布膜部分固化；用显影液显影，由此形成由各色(3色或4色)的像素构成的图案状被膜，从而制造本发明的彩色滤光片。Specifically, the photosensitive resin composition of the present invention is coated on a support (substrate) directly or with other layers interposed therebetween to form a photosensitive resin layer; exposure is performed through a predetermined mask pattern, and only the light irradiated The coating film is partially cured; it is developed with a developer to form a patterned film composed of pixels of each color (three colors or four colors), thereby manufacturing the color filter of the present invention.
下面，对本发明的制造方法中的各工序进行说明。Hereinafter, each step in the manufacturing method of the present invention will be described.
形成工序Formation process
感光性树脂层形成工序是在支撑体上涂布本发明的感光性树脂组合物，形成感光性树脂层。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.
作为适用的支撑体，例如可以举出液晶显示元件等中所用的钠钙玻璃、无碱玻璃、派瑞克斯(pyrex)玻璃、石英玻璃、塑料基板、以及在上述支撑体上附着有透明导电膜而得到的支撑体、摄像元件等中所用的光电转换元件基板例如硅基板等、互补性金属氧化膜半导体(CMOS)等。上述基板有时形成有隔离各像素的黑色矩阵(black matrix)。Suitable supports include, for example, soda lime glass, alkali-free glass, pyrex glass, quartz glass, plastic substrates used in liquid crystal display elements, etc., and transparent conductive materials attached to the support The photoelectric conversion element substrate used in the support body obtained by the film, the imaging element, etc., for example, a silicon substrate, etc., a complementary metal oxide film semiconductor (CMOS), and the like. The above-mentioned substrate is sometimes formed with a black matrix to isolate each pixel.
另外，支撑体上可以根据需要设置下涂层，以改良与上部的层的粘附性、防止物质扩散或将基板表面平坦化。In addition, an undercoat layer may be provided on the support as required to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate.
作为在支撑体上涂布本发明的感光性树脂组合物的方法，可以适用狭缝涂布、喷墨法、旋涂、辊涂、丝网印刷法等各种涂布方法。As a method of coating the photosensitive resin composition of the present invention on the support, various coating methods such as slit coating, inkjet method, spin coating, roll coating, and screen printing method can be applied.
作为感光性树脂组合物的涂布膜厚，优选为0.1-10μm，进一步优选为0.5-3μm。The coating film thickness of the photosensitive resin composition is preferably 0.1-10 μm, more preferably 0.5-3 μm.
涂布在支撑体上的感光性树脂组合物的烘干温度为70-110℃，烘干时间为2-4分钟。The drying temperature of the photosensitive resin composition coated on the support is 70-110°C, and the drying time is 2-4 minutes.
曝光工序Exposure process
曝光工序是将在上述感光性树脂层形成工序中形成的感光性树脂层通过掩模曝光，仅固化被光照射的涂布膜部分。The exposure step is to expose the photosensitive resin layer formed in the aforementioned photosensitive resin layer forming step through a mask to cure only the portion of the coating film irradiated with light.
曝光优选通过照射放射线来进行，作为曝光时能用的放射线，特别优选使用g线、i线等紫外线，较优选高压汞灯。照射强度优选为5-1500mJ/cm 2，进一步优选为10-500mJ/cm 2。 Exposure is preferably performed by irradiating radiation. As the radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used, and a high-pressure mercury lamp is more preferred. The irradiation intensity is preferably 5-1500 mJ/cm 2 , and more preferably 10-500 mJ/cm 2 .
显影工序Development process
曝光工序之后进行碱性显影处理(显影工序)，使曝光工序中的未曝光部分溶出于碱性水溶液。由此，仅残留光固化的部分。An alkaline development process (development process) is performed after the exposure process, and the unexposed part in the exposure process is melt|dissolved in an alkaline aqueous solution. Thus, only the photocured part remains.
显影温度，通常为20-30℃，显影时间为20-90秒。The developing temperature is usually 20-30°C, and the developing time is 20-90 seconds.
本发明的制造方法中，进行了上述感光性树脂层形成工序、曝光工序、及显影工序后，根据需要也可以增加通过加热及/或曝光使形成的着色图案进一步固化的后固化工序。In the production method of the present invention, after the photosensitive resin layer forming step, the exposure step, and the development step are performed, if necessary, a post-curing step of further curing the formed colored pattern by heating and/or exposure may be added.
根据所希望的色调数，重复上述感光性树脂层形成工序、曝光工序、及显影工序(以及根据需要增加的后固化工序)，即可制作由所希望的色调组成的彩色滤光片。According to the desired number of tones, the above-mentioned photosensitive resin layer formation process, exposure process, and development process (and post-curing process added as necessary) are repeated to produce a color filter composed of the desired color tone.
附图说明Description of the drawings
附图1是化合物a1的高效液相谱图。Figure 1 is a high performance liquid phase spectrum of compound a1.
具体实施方式detailed description
以下通过实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。The following examples illustrate the present invention in further detail, but they should not be understood as limiting the protection scope of the present invention.
1.六芳基双咪唑类光引发剂的制备1. Preparation of hexaarylbisimidazole photoinitiator
1.1六芳基双咪唑类光引发剂a11.1 Hexaryl bisimidazole photoinitiator a1
1.1.1单咪唑化合物a1-3的制备1.1.1 Preparation of monoimidazole compound a1-3
在1L四口烧瓶中加入66g维生素B1、195g纯水和195g乙醇，开启搅拌，冰浴冷却至内温0-10℃时，滴加99g 10％NaOH水溶液，约20分钟滴加完毕，此时pH为8-9。然后滴加75g苯甲醛(0.7mol)和99g邻氯苯甲醛(0.7mol)的混合溶液，约40分钟滴加完毕，升温至内温65℃保温反应(期间通过补加10％NaOH水溶液以控制pH为8-9)。取样HPLC中控至苯甲醛和邻氯苯甲醛均小于1％，结束保温，分去水层。先用200g纯水洗涤一次，再用100mL 10％NaHSO 3水溶液洗涤一次，最后用200g纯水洗涤两次，得到156g褐色液体a1-1。 Add 66g of vitamin B1, 195g of pure water and 195g of ethanol into a 1L four-necked flask, start stirring, and when the ice bath is cooled to an internal temperature of 0-10℃, add 99g of 10% NaOH aqueous solution dropwise, and the addition is complete in about 20 minutes. The pH is 8-9. Then a mixed solution of 75g benzaldehyde (0.7mol) and 99g o-chlorobenzaldehyde (0.7mol) was added dropwise, and the addition was completed in about 40 minutes, and the temperature was raised to an internal temperature of 65°C to keep the reaction (during the period by adding 10% NaOH aqueous solution to control The pH is 8-9). Sampling HPLC control until benzaldehyde and o-chlorobenzaldehyde are both less than 1%, end the heat preservation, and separate the water layer. Firstly, it was washed once with 200 g of pure water, then with 100 mL of 10% NaHSO 3 aqueous solution, and finally with 200 g of pure water twice, to obtain 156 g of brown liquid a1-1.
在1L四口烧瓶中加入300g冰醋酸、0.8g醋酸铜和157g硝酸铵，开启搅拌，升温至内温100℃后，将上述反应得到的156g褐色液体a1-1用150g冰醋酸溶清后，约30分钟滴加入反应体系中。取样HPLC中控至a1-1小于1％，结束保温。常压蒸馏除去冰醋酸后，先用200mL 10％NaOH水溶液洗涤一次，再用200g纯水洗涤两次，得到134g褐色液体a1-2。Add 300g of glacial acetic acid, 0.8g of copper acetate and 157g of ammonium nitrate into a 1L four-necked flask, turn on the stirring, raise the temperature to 100°C, and then dissolve 156g of brown liquid a1-1 from the above reaction with 150g of glacial acetic acid. Add dropwise to the reaction system for about 30 minutes. Sampling HPLC controlled to a1-1 less than 1%, and the heat preservation was ended. After the glacial acetic acid is removed by atmospheric distillation, it is washed once with 200 mL 10% NaOH aqueous solution, and then washed twice with 200 g of pure water to obtain 134 g of brown liquid a1-2.
Figure PCTCN2020081293-appb-000006
Figure PCTCN2020081293-appb-000006
使用LCMS确认a1-2结构，质谱分析借助仪器附带软件得到211与212分子碎片峰，产品a1-2a的分子量为210，与T+1和T+2吻合；得到245与246分子碎片峰，产品a1-2b的分子量为244，与T+1和T+2吻合；得到279与280分子碎片峰，产品a1-2c的分子量为278，与T+1和T+2吻合。LCMS证明褐色液体a1-2是由a1-2a、a1-2b和a1-2c三个组分组成。LCMS was used to confirm the structure of a1-2, and mass spectrometry was used to obtain 211 and 212 molecular fragment peaks with the aid of the software attached to the instrument. The molecular weight of product a1-2a was 210, which was consistent with T+1 and T+2; and 245 and 246 molecular fragment peaks were obtained. The molecular weight of a1-2b is 244, which is consistent with T+1 and T+2; the 279 and 280 molecular fragment peaks are obtained, and the molecular weight of product a1-2c is 278, which is consistent with T+1 and T+2. LCMS proved that the brown liquid a1-2 is composed of a1-2a, a1-2b and a1-2c.
在1L四口烧瓶中加入134g褐色液体a1-2、75g邻氯苯甲醛(0.7mol)、118g醋酸铵和500g冰醋酸，开启搅拌，升温至内温115℃后，保温反应3小时。取样HPLC中控至a1-2和邻氯苯甲醛均小于1％后，常压蒸馏冰醋酸，剩余50g左右冰醋酸后降温至内温100℃，缓慢滴加200g纯水，约40分钟完成，趁热分去水层，用10％NaOH水溶液将pH调至7-8。用100mL 10％NaHSO 3水溶液洗涤一次，最后用200g纯水洗涤两次，得到褐色油状液体。用50mL甲醇将褐色油状液体溶清，随后滴加到500mL纯水中，滴加完成后继续搅拌30分钟，抽滤得到350g黄色固体a1-3。 Add 134g of brown liquid a1-2, 75g of o-chlorobenzaldehyde (0.7mol), 118g of ammonium acetate and 500g of glacial acetic acid into a 1L four-necked flask, turn on the stirring, raise the temperature to 115°C, and then heat and react for 3 hours. After sampling HPLC to control that both a1-2 and o-chlorobenzaldehyde are less than 1%, glacial acetic acid is distilled at atmospheric pressure, and the remaining 50g glacial acetic acid is cooled to an internal temperature of 100°C, and 200g of pure water is slowly added dropwise, about 40 minutes to complete. Separate the water layer while it is hot, and adjust the pH to 7-8 with 10% NaOH aqueous solution. It was washed once with 100 mL of 10% NaHSO 3 aqueous solution, and finally washed twice with 200 g of pure water to obtain a brown oily liquid. The brown oily liquid was dissolved in 50 mL methanol, and then added dropwise to 500 mL pure water. After the addition was completed, stirring was continued for 30 minutes, and 350 g of yellow solid a1-3 was obtained by suction filtration.
Figure PCTCN2020081293-appb-000007
Figure PCTCN2020081293-appb-000007
使用LCMS确认a1-3结构，质谱分析借助仪器附带软件得到311与312分子碎片峰，产品a1-3a的分子量为330，与T+1和T+2吻合；得到365与366分 子碎片峰，产品a1-3b的分子量为364，与T+1和T+2吻合；得到399与400分子碎片峰，产品a1-3c的分子量为398，与T+1和T+2吻合。LCMS证明褐色液体a1-3是由a1-3a、a1-3b和a1-3c三个组分组成。LCMS was used to confirm the structure of a1-3, and mass spectrometry analysis used the software attached to the instrument to obtain molecular fragmentation peaks of 311 and 312. The molecular weight of product a1-3a was 330, which was consistent with T+1 and T+2; and molecular fragmentation peaks of 365 and 366 were obtained. The molecular weight of a1-3b is 364, which is consistent with T+1 and T+2; the 399 and 400 molecular fragment peaks are obtained, and the molecular weight of product a1-3c is 398, which is consistent with T+1 and T+2. LCMS proved that the brown liquid a1-3 is composed of a1-3a, a1-3b and a1-3c.
根据上文中公式计算，a1-3中红移取代基的个数为2(其中a＝0.7，b＝0.7，A＝0，B＝1，C＝1)。According to the above formula, the number of red-shifted substituents in a1-3 is 2 (where a=0.7, b=0.7, A=0, B=1, C=1).
Figure PCTCN2020081293-appb-000008
Figure PCTCN2020081293-appb-000008
1.1.2单咪唑化合物INC的制备1.1.2 Preparation of monoimidazole compound INC
参照a1-3的制备工艺制备INC，不同在于：2mol苯甲醛通过自身缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol邻氯苯甲醛通过成环反应生成单咪唑化合物INC。使用LCMS确认INC结构，质谱分析借助仪器附带软件得到311与312分子碎片峰，产品INC的分子量为330，与T+1和T+2吻合。Refer to the preparation process of a1-3 to prepare INC. The difference is that: 2mol of benzaldehyde undergoes self-condensation and oxidation reaction to obtain 1mol of benzil compounds; this benzaldehyde compound and 1mol of o-chlorobenzaldehyde are formed by ring-forming reaction. Imidazole compound INC. LCMS was used to confirm the INC structure, and mass spectrometry analysis used the software attached to the instrument to obtain 311 and 312 molecular fragment peaks. The molecular weight of the product INC was 330, which was consistent with T+1 and T+2.
Figure PCTCN2020081293-appb-000009
Figure PCTCN2020081293-appb-000009
根据上文中公式计算，INC中红移取代基的个数为1(其中a’＝1，b’＝1，A’＝0，B’＝0，C’＝1)。According to the above formula, the number of redshift substituents in INC is 1 (where a'=1, b'=1, A'=0, B'=0, C'=1).
Figure PCTCN2020081293-appb-000010
Figure PCTCN2020081293-appb-000010
1.1.3六芳基双咪唑类光引发剂a1的制备1.1.3 Preparation of hexaarylbisimidazole photoinitiator a1
氮气保护下，向500mL的四口烧瓶中投入13.0g黄色固体a1-3 (0.036mol)、11.9g 2-(邻氯苯基)-4,5-二苯基-咪唑(INC)(0.036mol)、0.5g 30％液碱、0.5g四丁基溴化铵和100g甲苯，加热搅拌，并在内温60-65℃时滴加40g次氯酸钠(11％的水溶液)，滴加结束后保温反应，取样通过HPLC中控，至a1-3和INC均小于1％，反应完全，结束保温。保温反应结束后，用50g纯水洗涤四次，然后用20g甲苯萃取一次水层，将有机层进行减压蒸馏。向蒸馏得到的物料中加入20g甲醇，加热搅拌至溶清，再将溶清液滴加至由20g甲醇和200g纯水配置而成的溶液中，滴加结束后进行过滤、淋洗、烘干，得到23.4g产物a1。Under nitrogen protection, put 13.0g yellow solid a1-3 (0.036mol), 11.9g 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (INC) (0.036mol) into a 500mL four-necked flask ), 0.5g 30% liquid caustic soda, 0.5g tetrabutylammonium bromide and 100g toluene, heated and stirred, and 40g sodium hypochlorite (11% aqueous solution) was added dropwise at an internal temperature of 60-65℃, and the reaction was kept warm after the addition was completed , Sampling was controlled by HPLC until both a1-3 and INC were less than 1%, the reaction was complete, and the insulation was finished. After the completion of the heat preservation reaction, it was washed four times with 50 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was subjected to vacuum distillation. Add 20g methanol to the material obtained by distillation, heat and stir until it is clear, and then add the dissolved clear liquid dropwise to a solution of 20g methanol and 200g pure water. After the addition is complete, filter, rinse and dry , 23.4 g of product a1 was obtained.
使用高效液相色谱对产物a1进行分析，结果如附图1所示，产物a1中双咪唑的总含量为94.5％。The product a1 was analyzed by high performance liquid chromatography, and the result was shown in Figure 1. The total content of bisimidazole in the product a1 was 94.5%.
产物a1在丁酮中的溶解度为23.1％。The solubility of product a1 in butanone was 23.1%.
根据上文中公式计算，产物a1的红移取代基在六芳基双咪唑类光引发剂的所有可取代位点中的摩尔占比为10.0％(其中e＝0.036，f＝0.036，m＝2，n＝1)。Calculated according to the above formula, the molar ratio of the red-shifted substituent of product a1 in all substitutable sites of the hexaarylbisimidazole photoinitiator is 10.0% (where e=0.036, f=0.036, m=2 , N=1).
Figure PCTCN2020081293-appb-000011
Figure PCTCN2020081293-appb-000011
1.2六芳基双咪唑类光引发剂a21.2 Hexaryl bisimidazole photoinitiator a2
参照a1的制备工艺，使用0.0072mol的a1-3与0.0648mol的INC反应，其它参数条件不变，得到产物a2。使用高效液相色谱对产物a2进行分析，产物a2中双咪唑的总含量为93.6％。Refer to the preparation process of a1, use 0.0072mol of a1-3 to react with 0.0648mol of INC, and other parameters and conditions remain unchanged, to obtain the product a2. The product a2 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a2 was 93.6%.
产物a2在丁酮中的溶解度为19.8％。The solubility of product a2 in butanone was 19.8%.
根据上文中公式计算，产物a2的红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为7.3％(其中e＝0.0072，f＝0.0648，m＝2， n＝1)。Calculated according to the above formula, the molar ratio of the red-shifted substituents of product a2 in all substitutable sites of the hexaarylbisimidazole photoinitiator is 7.3% (where e = 0.0072, f = 0.0648, m = 2, n=1).
1.3六芳基双咪唑类光引发剂a31.3 Six aryl bisimidazole photoinitiator a3
参照a1的制备工艺，使用0.0648mol的a1-3与0.0072mol的INC反应，其它参数条件不变，得到产物a3。使用高效液相色谱对产物a3进行分析，产物a3中双咪唑的总含量为94.9％。Refer to the preparation process of a1, use 0.0648mol of a1-3 to react with 0.0072mol of INC, and other parameters and conditions remain unchanged to obtain product a3. The product a3 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a3 was 94.9%.
产物a3在丁酮中的溶解度为25.2％。The solubility of product a3 in butanone was 25.2%.
根据上文中公式计算，产物a3的红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为12.7％(其中e＝0.0648，f＝0.0072，m＝2，n＝1)。According to the above formula, the red-shifted substituent of product a3 accounts for 12.7% of all substitutable sites in the hexaarylbisimidazole photoinitiator (e=0.648, f=0.0072, m=2, n=1).
1.4六芳基双咪唑类光引发剂a41.4 Six aryl bisimidazole photoinitiator a4
参照a1-3的制备工艺制备a4-1，不同在于：1mol对甲基苯甲醛和1mol邻氯苯甲醛通过缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol 2,4-二氯苯甲醛通过成环反应生成单咪唑化合物a4-1。Refer to the preparation process of a1-3 to prepare a4-1, the difference is that: 1mol of p-methylbenzaldehyde and 1mol of o-chlorobenzaldehyde are subjected to condensation and oxidation to obtain 1mol of benzyl compounds; the benzyl compounds and 1mol 2,4-Dichlorobenzaldehyde generates monoimidazole compound a4-1 through a ring-forming reaction.
根据上文中公式计算，a4-1中红移取代基的个数为3(其中a＝1，b＝1，A＝0，B＝1，C＝2)。According to the above formula, the number of red-shifted substituents in a4-1 is 3 (where a=1, b=1, A=0, B=1, and C=2).
Figure PCTCN2020081293-appb-000012
Figure PCTCN2020081293-appb-000012
参照a1的制备工艺，使用0.036mol的a4-1与0.036mol的INC反应，其它参数条件不变，得到产物a4。使用高效液相色谱对产物a4进行分析，产物a4中双咪唑的总含量为93.9％。Refer to the preparation process of a1, using 0.036mol of a4-1 to react with 0.036mol of INC, and other parameters and conditions remain unchanged, to obtain the product a4. The product a4 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a4 was 93.9%.
产物a4在丁酮中的溶解度为35.7％。The solubility of product a4 in butanone was 35.7%.
根据上文中公式计算，产物a4的红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为13.3％(其中e＝0.036，f＝0.036，m＝3，n＝1)。According to the above formula, the red-shifted substituent of product a4 accounts for 13.3% of all substitutable sites in the hexaarylbisimidazole photoinitiator (where e=0.036, f=0.036, m=3, n=1).
1.5六芳基双咪唑类光引发剂a51.5 Hexaryl bisimidazole photoinitiator a5
参照a1的制备工艺，使用0.048mol的a4-1与0.024mol的INC反应，其它参数条件不变，得到产物a5。使用高效液相色谱对产物a5进行分析，产物a5中双咪唑的总含量为95.2％。Refer to the preparation process of a1, using 0.048 mol of a4-1 to react with 0.024 mol of INC, and other parameters and conditions remain unchanged, to obtain the product a5. The product a5 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a5 was 95.2%.
产物a5在丁酮中的溶解度为43.4％。The solubility of product a5 in butanone was 43.4%.
根据上文中公式计算，产物a5的红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为15.6％(其中e＝0.048，f＝0.024，m＝3，n＝1)。Calculated according to the above formula, the molar ratio of the red-shifted substituent of product a5 in all substitutable sites of the hexaarylbisimidazole photoinitiator is 15.6% (where e=0.048, f=0.024, m=3, n=1).
1.6六芳基双咪唑类光引发剂a61.6 Six aryl bisimidazole photoinitiator a6
参照a1-3的制备工艺制备a6-1，不同在于：1mol对甲基苯甲醛和1mol苯甲醛通过缩合、氧化反应，得到1mol的苯偶酰类化合物；该苯偶酰类化合物与1mol邻氯苯甲醛通过成环反应生成单咪唑化合物a6-1。Refer to the preparation process of a1-3 to prepare a6-1. The difference is that: 1mol of p-methylbenzaldehyde and 1mol of benzaldehyde undergo condensation and oxidation reactions to obtain 1mol of benzyl compounds; the benzyl compounds and 1mol of o-chlorine Benzaldehyde generates monoimidazole compound a6-1 through a ring-forming reaction.
根据上文中公式计算，a6-1中红移取代基的个数为1(其中a＝1，b＝1，A＝0，B＝0，C＝1)。Calculated according to the above formula, the number of redshift substituents in a6-1 is 1 (where a=1, b=1, A=0, B=0, C=1).
Figure PCTCN2020081293-appb-000013
Figure PCTCN2020081293-appb-000013
参照a1的制备工艺，使用0.04mol的a6-1反应，其它参数条件不变，得到产物a6。使用高效液相色谱对产物a6进行分析，产物a6中双咪唑的总含量为93.4％。Refer to the preparation process of a1, using 0.04 mol of a6-1 reaction, and other parameters and conditions remain unchanged, to obtain the product a6. The product a6 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a6 was 93.4%.
产物a6在丁酮中的溶解度为25.1％。The solubility of product a6 in butanone was 25.1%.
根据上文中公式计算，产物a6的红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为6.7％(其中e＝0.02，f＝0.02，m＝1，n＝1)。Calculated according to the above formula, the molar ratio of the red-shifted substituent of product a6 in all substitutable sites of the hexaarylbisimidazole photoinitiator is 6.7% (where e=0.02, f=0.02, m=1, n=1).
1.7六芳基双咪唑类光引发剂a7(比较例)1.7 Hexaarylbisimidazole photoinitiator a7 (comparative example)
参照a1的制备工艺，使用0.0648mol的a4-1与0.0072mol的INC反应，其 它参数条件不变，得到产物a7。使用高效液相色谱对产物a7进行分析，产物a7中双咪唑的总含量为94.1％。Refer to the preparation process of a1, use 0.0648mol of a4-1 to react with 0.0072mol of INC, and other parameters and conditions remain unchanged to obtain product a7. The product a7 was analyzed by high performance liquid chromatography, and the total content of bisimidazole in the product a7 was 94.1%.
产物a7在丁酮中的溶解度为48.1％。The solubility of product a7 in butanone was 48.1%.
根据上文中公式计算，产物a7的红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为18.7％(其中e＝0.0648，f＝0.0072，m＝3，n＝1)。Calculated according to the above formula, the molar ratio of the red-shifted substituents of product a7 in all substitutable sites of the hexaarylbisimidazole photoinitiator is 18.7% (e=0.0648, f=0.0072, m=3, n=1).
1.7六芳基双咪唑类光引发剂a8、a9和a10(比较例)1.7 Hexaarylbisimidazole photoinitiator a8, a9 and a10 (comparative example)
a8是常州强力电子新材料股份有限公司生产的BCIM(单一结构的HABI)，其中红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为6.7％。a8 is a BCIM (single-structure HABI) produced by Changzhou Qiangli Electronic New Materials Co., Ltd., in which the molar ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 6.7%.
Figure PCTCN2020081293-appb-000014
Figure PCTCN2020081293-appb-000014
a9是常州强力电子新材料股份有限公司生产的TR-HABI-104(单一结构的HABI)，其中红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为13.3％。a9 is TR-HABI-104 (single structure HABI) produced by Changzhou Qiangli Electronic New Materials Co., Ltd., in which the molar ratio of the red-shifted substituents in all substitutable sites of the hexaarylbisimidazole photoinitiator is 13.3%.
Figure PCTCN2020081293-appb-000015
Figure PCTCN2020081293-appb-000015
a10是常州强力电子新材料股份有限公司生产的TCDM(混合HABI)，其中红移取代基在六芳基双咪唑类光引发剂所有可取代位点中的摩尔占比为16.7％。a10 is a TCDM (hybrid HABI) produced by Changzhou Qiangli Electronic New Materials Co., Ltd., in which the mole ratio of the red-shifted substituent in all substitutable sites of the hexaarylbisimidazole photoinitiator is 16.7%.
Figure PCTCN2020081293-appb-000016
Figure PCTCN2020081293-appb-000016
2.感光性树脂组合物的制备2. Preparation of photosensitive resin composition
参照表1-2-1中所示配方，将各组分混合均匀制得感光性树脂组合物。如无特别说明，表1-2-1中所示份数均为质量份。Refer to the formula shown in Table 1-2-1, and mix the components uniformly to prepare a photosensitive resin composition. Unless otherwise specified, the parts shown in Table 1-2-1 are all parts by mass.
表1-2-1Table 1-2-1
Figure PCTCN2020081293-appb-000017
Figure PCTCN2020081293-appb-000017
Figure PCTCN2020081293-appb-000018
Figure PCTCN2020081293-appb-000018
表1-2-1中各组分代号表示的含义如表1-2-2中所示。The meaning of each component code in Table 1-2-1 is shown in Table 1-2-2.
表1-2-2Table 1-2-2
Figure PCTCN2020081293-appb-000019
Figure PCTCN2020081293-appb-000019
Figure PCTCN2020081293-appb-000020
Figure PCTCN2020081293-appb-000020
碱可溶性聚合物B的制备：在氮气氛围下，向配有搅拌器、回流冷却器、温度计和滴液漏斗的烧瓶中，加入甲基溶纤剂和甲苯(质量比3:2)的混合溶剂500g，搅拌加热至80℃后，将甲基丙烯酸100g、甲基丙烯酸乙酯200g、丙烯酸乙酯100g、苯乙烯100g和偶氮双异丁腈0.8g混合制得的溶液慢慢滴加至烧瓶中，滴加时间为4小时，滴加结束后继续反应2小时。接着，向烧瓶内滴加溶解有1.2g偶氮双异丁腈的混合溶剂(组成同上)100g，滴加时间为10分钟，滴加结束后，在80℃下进一步反应3小时，再升温至90℃继续反应2小时。反应结束后，过滤得到碱可溶性聚合物B，酸值为196mgKOH/g， 重均分子量约为80000。Preparation of alkali-soluble polymer B: In a nitrogen atmosphere, add a mixed solvent of methyl cellosolve and toluene (mass ratio 3:2) into a flask equipped with a stirrer, a reflux cooler, a thermometer and a dropping funnel 500g, after stirring and heating to 80°C, the 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 added dropwise to the flask The dropping time was 4 hours, and the reaction was continued for 2 hours after the dropping. Next, 100 g of a mixed solvent (with the same composition as above) in which 1.2 g of azobisisobutyronitrile was dissolved was added dropwise to the flask. The dropping time was 10 minutes. After the dropping was completed, the reaction was further carried out at 80°C for 3 hours, and then the temperature was raised to The reaction was continued at 90°C for 2 hours. After the reaction, the alkali-soluble polymer B was obtained by filtration, with an acid value of 196 mgKOH/g and a weight average molecular weight of about 80,000.
参照表1-2-3中所示配方，将各组分混合均匀制得感光性树脂组合物。如无特别说明，表中所示份数均为质量份。Refer to the formula shown in Table 1-2-3, and mix the components uniformly to prepare a photosensitive resin composition. Unless otherwise specified, the parts shown in the table are all parts by mass.
表1-2-3Table 1-2-3
Figure PCTCN2020081293-appb-000021
Figure PCTCN2020081293-appb-000021
Figure PCTCN2020081293-appb-000022
Figure PCTCN2020081293-appb-000022
其中，表1-2-3中各组分代表的含义如表1-2-4中所示。Among them, the meaning of each component in Table 1-2-3 is shown in Table 1-2-4.
表1-2-4Table 1-2-4
Figure PCTCN2020081293-appb-000023
Figure PCTCN2020081293-appb-000023
3.性能评价3. Performance evaluation
3.1感光度3.1 Sensitivity
对于感光性树脂组合物，利用旋转涂布机将液态组合物涂覆在玻璃基板上，然后在100℃下干燥5min除去溶剂，形成膜厚为10μm的涂膜；为获得 上述厚度的涂膜，涂覆过程可以是一次完成也可以分多次进行；将带有涂膜的基板冷却至室温。使用i线缩小投影曝光装置，以365nm的波长，通过纵20μm×横20μm的遮罩且以曝光量为50mJ/cm 2的方式对涂布膜进行了照射。照射后，使用显影液(商品名：CD-2000，60％，富士软片电子材料制造)将涂布膜在23℃下进行60秒显影。继而，利用流水淋洗20秒后，进行喷射干燥而获得图案画像。画像形成是利用光学显微镜来确认。所得画素图案的宽度大者为高感光度，故而较佳。 For the photosensitive resin composition, the liquid composition is coated on a glass substrate using a spin coater, and then dried at 100°C for 5 minutes to remove the solvent to form a coating film with a thickness of 10 μm; in order to obtain a coating film with the above thickness, The coating process can be completed at one time or in multiple steps; the substrate with the coating film is cooled to room temperature. Using an i-line reduction projection exposure device, the coated film was irradiated at a wavelength of 365 nm through a mask of 20 μm in length×20 μm in width and with an exposure amount of 50 mJ/cm 2 . After the irradiation, the coating film was developed at 23° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fujifilm Electronic Materials). Then, after rinsing with running water for 20 seconds, spray drying was performed to obtain a pattern image. The image formation is confirmed by an optical microscope. The larger the width of the resulting pixel pattern is the higher the sensitivity, so it is better.
以下述判定基准来判定所得画素图案的宽度，判定基准如下：The width of the pixel pattern obtained is determined based on the following criteria, and the criteria are as follows:
○：35μm以上；○: 35μm or more;
◎：20μm以上且小于35μm；◎: 20μm or more and less than 35μm;
●：小于20μm。●: Less than 20μm.
3.2分辨率3.2 Resolution
利用具有Line/Space＝10:10-150:150(单位:μm)的布线图案的光掩模进行曝光显影后，测量分辨率。分辨率是在曝光后显影形成的抗蚀图案中，未曝光部分被清除干净后的图案的最小值，进行如下分级：After exposure and development using a photomask having a wiring pattern of Line/Space=10:10-150:150 (unit: μm), the resolution was measured. The resolution is the minimum value of the pattern after the unexposed part is removed from the resist pattern formed by development after exposure, and is classified as follows:
○：分辨率值在30μm以下；○: The resolution value is below 30μm;
◎：分辨率值在30μm-50μm，不包括端值；◎: The resolution value is 30μm-50μm, excluding the end value;
●：分辨率值在50μm以上。●: The resolution value is above 50μm.
3.3显影性3.3 developability
显影之后通过扫描电子显微镜(SEM)观察光刻胶图案，以评价显影性。显影性根据以下标准评价：After development, the photoresist pattern was observed by a scanning electron microscope (SEM) to evaluate the developability. The developability is evaluated according to the following criteria:
□：在未曝光部分未观察到残留物；□: No residue was observed in the unexposed part;
△：在未曝光部分观察到少量残留物，但残留量可以接受；△: A small amount of residue is observed in the unexposed part, but the amount of residue is acceptable;
×：在未曝光部分观察到明显残留物。×: Obvious residue is observed in the unexposed part.
3.4抗蚀图案形状3.4 Shape of resist pattern
使用扫描型电子显微镜(SEM)(株式会社日立高新技术制，产品名“SU-1500”)，以加速电压15kV、倍率3000倍、倾角60度观察抗蚀图案形状，按照以下基准进行判断：Using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Co., Ltd., product name "SU-1500"), the resist pattern shape was observed at an acceleration voltage of 15kV, a magnification of 3000 times, and an inclination angle of 60 degrees, and judged according to the following criteria:
□：抗蚀图案形状未确认到底切、抗蚀图案上部的缺失，并且图案轮廓的直线性良好；□: The shape of the resist pattern has not confirmed the undercut, the lack of the upper part of the resist pattern, and the linearity of the pattern outline is good;
△：抗蚀图案形状确认到底切、抗蚀图案上部的缺失，并且图案轮廓的直线性较差。△: The shape of the resist pattern confirmed the undercut and the lack of the upper part of the resist pattern, and the linearity of the pattern outline was poor.
3.5亲水性3.5 Hydrophilicity
通过感光性树脂层溶解后的沉淀量来评价亲水性。将感光性树脂组合物充分搅拌，使用棒涂布器均匀地涂布于作为支撑体的25μm厚的聚对苯二甲酸乙二醇酯薄膜的表面上。在干燥机中95℃干燥4min，形成感光性树脂层，层厚约为30.5μm，层重约为3.2g。将20g碳酸钠溶于2L水中，加1.5ml的P1uronic RPG3110(BASF，Mt.Olive，NJ，此试剂是聚氧乙烯和聚氧丙烯共聚物增塑剂)，制得显影液。将上述附有感光性树脂层的薄膜放入100g显影液中，试样静置直至树脂层溶解，沉淀量按下列等级确定：The hydrophilicity is evaluated by the amount of precipitation after the photosensitive resin layer is dissolved. The photosensitive resin composition was sufficiently stirred, and it was uniformly coated on the surface of a 25 μm thick polyethylene terephthalate film as a support using a bar coater. Dry in a dryer at 95°C for 4 minutes to form a photosensitive resin layer with a thickness of about 30.5 μm and a weight of about 3.2 g. Dissolve 20g of sodium carbonate in 2L of water, add 1.5ml of Pluronic RPG3110 (BASF, Mt. Olive, NJ, this reagent is a polyoxyethylene and polyoxypropylene copolymer plasticizer) to prepare a developer. Put the above-mentioned film with photosensitive resin layer into 100g developer, and let the sample stand until the resin layer is dissolved. The amount of precipitation is determined according to the following grades:
0＝沉淀量低于0.005g；0=The amount of precipitation is less than 0.005g;
1＝少量的细分散浅黄物，沉淀量在0.005-0.01g之间；1 = A small amount of finely dispersed light yellow matter, the amount of precipitation is between 0.005-0.01g;
5＝中等量浅黄物(通常较细)，沉淀量在0.05-0.08g之间；5 = Medium amount of pale yellow (usually finer), the amount of precipitation is between 0.05-0.08g;
10＝有大量固体层浅黄物(通常呈薄片状)，沉淀量在0.1g以上。10 = There is a large amount of solid layer of pale yellow material (usually in the form of flakes), and the amount of precipitation is more than 0.1g.
评价结果如表2-1中所示。The evaluation results are shown in Table 2-1.
表2-1table 2-1
评价项目Evaluation item 感光度Sensitivity 分辨率Resolution 显影性Developability 抗蚀图案形状Resist pattern shape 亲水性Hydrophilic
实施例1Example 1 ◎◎ ○○ □□ □□ 0级Level 0
实施例2Example 2 ◎◎ ○○ □□ □□ 0级Level 0
实施例3Example 3 ◎◎ ○○ □□ □□ 0级Level 0
实施例4Example 4 ◎◎ ○○ □□ □□ 0级Level 0
实施例5Example 5 ◎◎ ○○ □□ □□ 0级Level 0
实施例6Example 6 ◎◎ ○○ □□ □□ 0级Level 0
实施例7Example 7 ◎◎ ○○ □□ □□ 0级Level 0
实施例8Example 8 ◎◎ ○○ □□ □□ 0级Level 0
实施例9Example 9 ◎◎ ○○ □□ □□ 0级Level 0
实施例10Example 10 ◎◎ ○○ □□ □□ 0级Level 0
实施例11Example 11 ◎◎ ○○ □□ □□ 0级Level 0
实施例12Example 12 ◎◎ ○○ □□ □□ 0级Level 0
比较例1Comparative example 1 ○○ ◎◎ △△ △△ 1级Level 1
比较例2Comparative example 2 ◎◎ ◎◎ △△ △△ 5级Level 5
比较例3Comparative example 3 ◎◎ ◎◎ △△ △△ 5级Level 5
比较例4Comparative example 4 ○○ ◎◎ □□ △△ 1级Level 1
比较例5Comparative example 5 ○○ ◎◎ △△ △△ 1级Level 1
比较例6Comparative example 6 ◎◎ ◎◎ △△ △△ 5级Level 5
比较例7Comparative example 7 ◎◎ ◎◎ △△ △△ 5级Level 5
比较例8Comparative example 8 ○○ ◎◎ □□ △△ 1级Level 1
本发明的感光性树脂组合物的感光度适中、溶解性好、分辨率和显影 性优异，不会在显影时出现倒梯形。此外，还具有较好的亲水性，能显著减少循环使用时显影液中的淤渣量，使得显影液可重复多次、有效使用。The photosensitive resin composition of the present invention has moderate sensitivity, good solubility, excellent resolution and developability, and does not appear inverted trapezoid during development. In addition, it also has good hydrophilicity, which can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be used repeatedly and effectively.
该感光性树脂组合物能够以干膜和湿膜的方式在制造印刷电路板、保护图案、导体图案、引框线、半导体封装等方面得到广泛应用，还可应用于彩色滤光片及液晶显示组件的制造。The photosensitive resin composition can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc. in the form of dry film and wet film, and can also be applied to color filters and liquid crystal displays Component manufacturing.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, etc. made without departing from the spirit and principle of the present invention Simplified, all should be equivalent replacement methods, and they are all included in the protection scope of the present invention.

Claims (15)

  1. 一种六芳基双咪唑类光引发剂，通过以下步骤制备而成：A hexaarylbisimidazole photoinitiator, prepared by the following steps:
    (1)通式(Ⅰ)所示的芳香醛和通式(Ⅱ)所示的芳香醛通过缩合、氧化反应，得到苯偶酰类化合物；该苯偶酰类化合物与通式(Ⅲ)所示的芳香醛通过成环反应生成单咪唑化合物M；(1) The aromatic aldehyde represented by the general formula (I) and the aromatic aldehyde represented by the general formula (II) are condensed and oxidized to obtain a benzyl compound; the benzyl compound is combined with the general formula (III) The aromatic aldehyde shown in the ring-forming reaction generates monoimidazole compound M;
    (2)通式(Ⅳ)所示的芳香醛和通式(Ⅴ)所示的芳香醛通过缩合、氧化反应，得到苯偶酰类化合物；该苯偶酰类化合物与通式(Ⅵ)所示的芳香醛通过成环反应生成单咪唑化合物N；(2) The aromatic aldehyde represented by the general formula (IV) and the aromatic aldehyde represented by the general formula (V) are condensed and oxidized to obtain a benzil compound; the benzyl compound is with the general formula (VI) The aromatic aldehyde shown in the ring-forming reaction generates monoimidazole compound N;
    (3)单咪唑化合物M和N通过氧化反应，生成六芳基双咪唑类光引发剂；(3) Monoimidazole compounds M and N undergo oxidation reactions to generate hexaarylbisimidazole photoinitiators;
    Figure PCTCN2020081293-appb-100001
    Figure PCTCN2020081293-appb-100001
    其中，R 1-R 30各自独立地表示氢、卤素、硝基、氰基、胺基、羟基、C 1-C 10的烷基、C 1-C 10的烷氧基、或C 2-C 10的链烯基，且各基团中的亚甲基可以任选地被氧、硫、亚胺基所取代； Wherein, R 1 -R 30 each independently represents hydrogen, halogen, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, or C 2 -C The alkenyl group of 10 , and the methylene group in each group may be optionally substituted by oxygen, sulfur, and imino groups;
    前提是，红移取代基在六芳基双咪唑类光引发剂的所有可取代位点即R 1-R 30中的摩尔占比为6-16％。 The premise is that the molar ratio of the red-shifted substituents at all substitutable positions of the hexaarylbisimidazole photoinitiator, namely R 1 -R 30 , is 6-16%.
  2. 根据权利要求1所述的六芳基双咪唑类光引发剂，其特征在于：红移取代基包括氯、溴、硝基、氰基、胺基、羟基、C 2-C 10的链烯基、C 1-C 10 的烷氧基，其中各基团中的亚甲基可以任选地被氧、硫、亚胺基所取代；优选地，红移取代基选自氯、溴、羟基、胺基、和C 1-C 5的烷氧基。 The hexaarylbisimidazole photoinitiator according to claim 1, wherein the red-shifted substituents include chlorine, bromine, nitro, cyano, amine, hydroxyl, and C 2 -C 10 alkenyl groups. , C 1 -C 10 alkoxy, wherein the methylene group in each group can be optionally substituted by oxygen, sulfur, imino group; preferably, the red shift substituent is selected from chlorine, bromine, hydroxyl, Amine group and C 1 -C 5 alkoxy group.
  3. 感光性树脂组合物，包含下列组分：The photosensitive resin composition contains the following components:
    (A)权利要求1或2所述的六芳基双咪唑类光引发剂；(A) The hexaarylbisimidazole photoinitiator of claim 1 or 2;
    (B)碱可溶性聚合物；(B) Alkali-soluble polymer;
    (C)具有烯属不饱和双键的化合物；(C) Compounds with ethylenically unsaturated double bonds;
    (D)供氢体；(D) Hydrogen donor;
    (E)其它任选的助剂。(E) Other optional auxiliary agents.
  4. 根据权利要求3所述的感光性树脂组合物，其特征在于：所述碱可溶性聚合物是(甲基)丙烯酸系聚合物、苯乙烯系聚合物、环氧系聚合物、脂肪族聚氨酯(甲基)丙烯酸酯聚合物、芳香族聚氨酯(甲基)丙烯酸酯聚合物、酰胺系树脂、酰胺环氧系树脂、醇酸系树脂以及酚醛系树脂。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 polyurethane (A Base) acrylate polymers, aromatic urethane (meth)acrylate polymers, amide resins, amide epoxy resins, alkyd resins, and phenolic resins.
  5. 根据权利要求4所述的感光性树脂组合物，其特征在于：所述碱可溶性聚合物是含羧基的碱可溶性聚合物；优选地，含羧基的碱可溶性聚合物是由(甲基)丙烯酸酯、乙烯性不饱和羧酸和其它可共聚单体共聚而成的(甲基)丙烯酸酯系聚合物。The photosensitive resin composition according to claim 4, wherein the alkali-soluble polymer is an alkali-soluble polymer containing a carboxyl group; preferably, the alkali-soluble polymer containing a carboxyl group is made of (meth)acrylate , Ethylene unsaturated carboxylic acid and other copolymerizable monomers copolymerized (meth)acrylate polymer.
  6. 根据权利要求3所述的感光性树脂组合物，其特征在于：所述碱可溶性聚合物的重均分子量为15000-200000，优选为30000-150000，特别优选为30000-120000；酸值为50-300mgKOH/g，优选为50-250mgKOH/g，进一步优选为70-250mgKOH/g，特别优选为100-250mgKOH/g。The photosensitive resin composition according to claim 3, wherein the weight average molecular weight of the alkali-soluble polymer is 15,000 to 200,000, preferably 30,000 to 150,000, particularly preferably 30,000 to 120,000; and the acid value is 50 to 300 mgKOH/g, preferably 50-250 mgKOH/g, more preferably 70-250 mgKOH/g, particularly preferably 100-250 mgKOH/g.
  7. 根据权利要求3所述的感光性树脂组合物，其特征在于：所述具有烯属不饱和双键的化合物选自下列化合物中的至少一种：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:
    α,β-不饱和羧酸与多元醇反应而得的化合物、双酚A类(甲基)丙烯酸 酯化合物、α,β-不饱和羧酸与含缩水甘油基的化合物反应而得的化合物、分子内具有氨酯键的(甲基)丙烯酸酯化合物、壬基苯氧基多乙烯氧基丙烯酸酯、γ-氯-β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基乙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、苯二甲酸类化合物、(甲基)丙烯酸烷基酯。Compounds obtained by reacting α,β-unsaturated carboxylic acids with polyhydric alcohols, bisphenol A (meth)acrylate compounds, compounds obtained by reacting α,β-unsaturated carboxylic acids with glycidyl group-containing compounds, (Meth)acrylate compounds with urethane bonds in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloxyethyl -Phthalates, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyl Oxyethyl-phthalate, phthalic acid compounds, alkyl (meth)acrylate.
  8. 根据权利要求7所述的感光性树脂组合物，其特征在于：所述具有烯属不饱和双键的化合物选自双酚A类(甲基)丙烯酸酯化合物和分子内具有氨酯键的(甲基)丙烯酸酯化合物。7. The photosensitive resin composition according to claim 7, wherein the compound having an ethylenically unsaturated double bond is selected from the group consisting of bisphenol A (meth)acrylate compounds and those having urethane bonds in the molecule ( Meth)acrylate compound.
  9. 根据权利要求3所述的感光性树脂组合物，其特征在于：所述供氢体选自胺类化合物、羧酸类化合物、含有巯基的有机硫化合物或醇类化合物中的至少一种。The photosensitive resin composition according to claim 3, wherein the hydrogen donor is at least one selected from the group consisting of amine compounds, carboxylic acid compounds, mercapto group-containing organic sulfur compounds, and alcohol compounds.
  10. 根据权利要求3所述的感光性树脂组合物，其特征在于：还包括其它光引发剂和/或增感剂、有机溶剂、染料、颜料、光显色剂、填充剂、增塑剂、稳定剂、涂布助剂、剥离促进剂中的至少一种。The photosensitive resin composition according to claim 3, characterized in that it further comprises other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers At least one of an agent, a coating aid, and a peeling accelerator.
  11. 感光性树脂层叠体，包含：权利要求3-10中任一项所述的感光性树脂组合物形成的感光性树脂层以及支撑该感光性树脂层的支撑体。The photosensitive resin laminate includes a photosensitive resin layer formed of the photosensitive resin composition according to any one of claims 3 to 10, and a support supporting the photosensitive resin layer.
  12. 权利要求3-10中任一项所述的感光性树脂组合物或权利要求11所述的感光性树脂层叠体在制造印刷电路板、保护图案、导体图案、引框线、半导体封装中的应用。Use of the photosensitive resin composition according to any one of claims 3-10 or the photosensitive resin laminate according to claim 11 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages .
  13. 权利要求3-10中任一项所述的感光性树脂组合物或权利要求11所述的感光性树脂层叠体在制造彩色滤光片中的应用。Use of the photosensitive resin composition according to any one of claims 3 to 10 or the photosensitive resin laminate according to claim 11 in the production of a color filter.
  14. 彩色滤光片，包括：支撑体，以及在支撑体上使用权利要求3-10中任一项所述的感光性树脂组合物或权利要求11所述的感光性树脂层叠体 形成的着色图案。The color filter includes a support, and a colored pattern formed by using the photosensitive resin composition according to any one of claims 3-10 or the photosensitive resin laminate according to claim 11 on the support.
  15. 液晶显示组件，包含权利要求14所述的彩色滤光片。A liquid crystal display device comprising the color filter of claim 14.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113637027A (en) * 2021-07-22 2021-11-12 海南师范大学 Phenyl triazole dicarboxylic acid-rhodamine B derivative fluorescent probe and preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062721B (en) * 2019-05-23 2023-06-30 常州正洁智造科技有限公司 HABI photoinitiator capable of improving system stability and application thereof
CN115128899A (en) * 2021-03-26 2022-09-30 常州正洁智造科技有限公司 Photosensitive resin composition with improved system hue stability

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB997396A (en) * 1962-03-21 1965-07-07 Du Pont 2,4,5 - triphenylimidazole dimers
CN1705646A (en) * 2002-10-15 2005-12-07 昭和电工株式会社 Hexaarylbiimidazole compounds and photopolymerization initiator compositions containing the same
JP2007332045A (en) * 2006-06-12 2007-12-27 Showa Denko Kk Hexaarylbiimidazole compound and photopolymerizable composition containing the compound
CN101233435A (en) * 2005-07-29 2008-07-30 富士胶片株式会社 Photosensitive resin composition for liquid crystal display element, color filter using the same, process for manufacture of the color filter, and liquid crystal display element
CN101386599A (en) * 2008-10-31 2009-03-18 上海优佰信息科技有限公司 Hexaarylbisimidazoles compounds, preparation method and application thereof and composition containing thereof
CN101418051A (en) * 2008-12-01 2009-04-29 常州强力电子新材料有限公司 Photoinitiator contaning asymmetic hexaaryl bis imidazole and preparation method thereof
WO2009135677A1 (en) * 2008-05-08 2009-11-12 Dentsply Detrey Gmbh Radical polymerisation initiators for light-curable dental materials
CN105182686A (en) * 2014-05-28 2015-12-23 奇美实业股份有限公司 Photosensitive resin composition and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3620430A1 (en) * 1986-06-18 1987-12-23 Basf Ag METHOD FOR PRODUCING HEXAARYLBISIMIDAZOLES
JP4934353B2 (en) * 2005-06-10 2012-05-16 ドンジン セミケム カンパニー リミテッド Negative photosensitive resin composition
JP5639096B2 (en) 2012-02-02 2014-12-10 富士フイルム株式会社 Photosensitive coloring composition, color filter, method for producing color filter, liquid crystal display device, organic EL display device, and solid-state imaging device
CN111258180B (en) * 2018-11-30 2024-03-08 常州正洁智造科技有限公司 Hexaarylbisimidazoles mixed photoinitiator and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB997396A (en) * 1962-03-21 1965-07-07 Du Pont 2,4,5 - triphenylimidazole dimers
CN1705646A (en) * 2002-10-15 2005-12-07 昭和电工株式会社 Hexaarylbiimidazole compounds and photopolymerization initiator compositions containing the same
CN101233435A (en) * 2005-07-29 2008-07-30 富士胶片株式会社 Photosensitive resin composition for liquid crystal display element, color filter using the same, process for manufacture of the color filter, and liquid crystal display element
JP2007332045A (en) * 2006-06-12 2007-12-27 Showa Denko Kk Hexaarylbiimidazole compound and photopolymerizable composition containing the compound
WO2009135677A1 (en) * 2008-05-08 2009-11-12 Dentsply Detrey Gmbh Radical polymerisation initiators for light-curable dental materials
CN101386599A (en) * 2008-10-31 2009-03-18 上海优佰信息科技有限公司 Hexaarylbisimidazoles compounds, preparation method and application thereof and composition containing thereof
CN101418051A (en) * 2008-12-01 2009-04-29 常州强力电子新材料有限公司 Photoinitiator contaning asymmetic hexaaryl bis imidazole and preparation method thereof
CN105182686A (en) * 2014-05-28 2015-12-23 奇美实业股份有限公司 Photosensitive resin composition and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王宝湖 等 (WANG, BAOHU ET AL.): "新型六芳基双咪唑光引发剂的合成和应用 (Synthesis and Application of Novel Hexaarylbiimidazole Photoinitiator)", 信息记录材料 (INFORMATION RECORDING MATERIALS), vol. 11,, no. 5, 31 October 2010 (2010-10-31), XP55739034, ISSN: 1009-562, DOI: 9460301 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113637027A (en) * 2021-07-22 2021-11-12 海南师范大学 Phenyl triazole dicarboxylic acid-rhodamine B derivative fluorescent probe and preparation method and application thereof
CN113637027B (en) * 2021-07-22 2022-04-05 海南师范大学 Phenyl triazole dicarboxylic acid-rhodamine B derivative fluorescent probe and preparation method and application thereof

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