WO2020200018A1 - Photosensitive resin composition for color filter, and color filter - Google Patents

Photosensitive resin composition for color filter, and color filter Download PDF

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Publication number
WO2020200018A1
WO2020200018A1 PCT/CN2020/081284 CN2020081284W WO2020200018A1 WO 2020200018 A1 WO2020200018 A1 WO 2020200018A1 CN 2020081284 W CN2020081284 W CN 2020081284W WO 2020200018 A1 WO2020200018 A1 WO 2020200018A1
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Prior art keywords
acid
photosensitive resin
bis
composition according
compounds
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PCT/CN2020/081284
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French (fr)
Chinese (zh)
Inventor
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 JP2021557998A priority Critical patent/JP7242100B2/en
Priority to KR1020217035481A priority patent/KR102649509B1/en
Publication of WO2020200018A1 publication Critical patent/WO2020200018A1/en

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    • 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
    • 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
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the invention belongs to the technical field of organic chemistry and photocuring, and specifically relates to a photosensitive resin composition used for a color filter, a color filter using the photosensitive resin composition, and a manufacturing method thereof.
  • Color filters are usually made by forming red, green, and blue pigments on a transparent substrate by dyeing, printing, and pigment dispersion methods.
  • the pigment dispersion method is currently the mainstream method in the industry.
  • a photosensitive resin composition containing a colorant is coated on a transparent substrate, and then the image is exposed, developed, and post-cured as necessary.
  • the color filter is formed by repeating these processes .
  • This method has the advantages of high heat resistance, no need for dyeing, etc., and can form a high-precision colored layer.
  • the main purpose of the present invention is to provide a photosensitive resin composition for color filters, which has excellent sensitivity and good developability when applied, and has high brightness after curing. , And excellent adhesion to the substrate.
  • a photosensitive resin composition for color filters comprising the following components:
  • Photopolymerization initiator including photopolymerization initiator A1 and at least one oxime ester photoinitiator A2;
  • the photopolymerization initiator A1 is a hexaarylbisimidazole (ie HABI) type mixed photoinitiator, which has a structure as shown in the general formula (I), which contains 2-1', 2-3', 2'-1 And 2'-3 four bisimidazole compounds at the connection position, and the total mass percentage of the four bisimidazole compounds at the connection position in A1 is more than 92%,
  • HABI hexaarylbisimidazole
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group;
  • the molar extinction coefficient of the photopolymerization initiator (A) at the i-line (365nm) is between 5000-10000.
  • Another object of the present invention is to provide a color filter using the above-mentioned photosensitive resin composition and a manufacturing method thereof.
  • the photopolymerization initiator A1 of the present invention is a HABI-based mixed photoinitiator, having a structure as shown in the general formula (I), which contains 2-1', 2-3', 2'-1 and 2 '-3 Four kinds of bisimidazole compounds with connection positions, and the total mass percentage of the four kinds of bisimidazole compounds with connection positions in the photopolymerization initiator A1 is 92% or more,
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group;
  • the molar extinction coefficient of the photopolymerization initiator (A) at the i-line (365nm) is between 5000-10000.
  • the bisimidazole compounds satisfying the four connection positions 2-1', 2-3', 2'-1 and 2'-3 of the structure represented by the general formula (I) are specifically the following structures:
  • the aryl group is preferably a phenyl group.
  • the substituted aryl group may be mono-substituted or poly-substituted.
  • the substituents on the aryl group can be halogen, nitro, cyano, amino, hydroxyl, C 1 -C 20 alkyl or alkenyl, C 1 -C 8 alkoxy, wherein each independently
  • the methylene group in the variable ie, each substituent may be optionally substituted with oxygen, sulfur, or imino groups.
  • the substituent on the aryl group can be fluorine, chlorine, bromine, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl or alkenyl, C 1 -C 5 alkoxy Group, wherein the methylene group in each independent variable can be optionally substituted with oxygen, sulfur, or imino groups.
  • At least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 is an aryl group containing a halogen substituent.
  • Halogen substituents can improve the discoloration effect during the curing process to enhance the recognition ability of the electronic eye during development (Note: The photosensitive resin layer will change color after exposure, and form a color difference with the unexposed area, which will be recognized by the electronic eye. The invention can make the chromatic aberration more obvious), thereby improving the quality of the application product.
  • the halogen substituent is chlorine.
  • the substituents on the aromatic ring have little influence on the absorption of HABI compounds near 265 nm, but have little effect on HABI.
  • the absorption of the compound near 365nm has a greater influence.
  • the conjugated system When the conjugated system is introduced into the HABI structure, it will cause the ultraviolet absorption wavelength to move toward the long wavelength (ie, produce a red shift phenomenon) and increase the ultraviolet absorption intensity (ie, the molar extinction coefficient).
  • the photopolymerization initiator A1 is used as the initiator, and the generated active radicals undergo chain transfer through the hydrogen donor, which can effectively promote hardening of the exposed area without deactivation. This is beneficial for improving the sensitivity and brightness of the color filter.
  • HABI compounds shown in general formula (I) also have 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1', 5-3' and so on.
  • the photopolymerization initiator A1 as defined above is the most preferable for solving the technical problem of the present invention.
  • the performance of a single substance of any kind of linking site is far less than that of the photopolymerization initiator A1, and if the total content of these four linking sites is less than 92%, the performance will obviously deteriorate.
  • bisimidazole compounds satisfying the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 of the structure represented by the general formula (I) are preferred.
  • the total mass percentage in it is 95% or more, and it is particularly preferred to have four link positions that satisfy the structure represented by the general formula (I): 2-1', 2-3', 2'-1 and 2'-3 Composition of bisimidazole compound.
  • HABI photoinitiators are well-known photoinitiators in the photoresist field. They can be prepared by oxidative coupling of triarylimidazoles or substituted triarylimidazoles. The specific preparation process can be referred to, for example, US3784557, US4622286 and US4311783. There are technical records (the full text is hereby incorporated as a reference). On the basis of the existing technology, adding a solvent recrystallization process can conveniently obtain the photopolymerization initiator A1 meeting the above composition requirements of the present invention.
  • the solvent may be one or a combination of two or more of toluene, methanol, ethyl acetate, dichloromethane, and water.
  • the preparation of the photopolymerization initiator A1 can also refer to the content described in the applicant's previous application (application number 201811451262.4) (the entire text is incorporated herein by reference).
  • the photopolymerization initiator A1 is selected from or includes at least one of the following combinations :
  • the content of the photopolymerization initiator A1 is preferably 0.1 to 10 parts by mass based on 100 parts by mass in total.
  • At least one oxime ester photoinitiator A2 is contained.
  • Adding an oxime lipid photoinitiator to the system is beneficial to improve the sensitivity and resolution of the composition.
  • oxime lipid photoinitiators are introduced in the presence of photopolymerization initiator A1 It can significantly improve the sensitivity and developability of the composition, and at the same time, it is also beneficial to improve the resolution.
  • oxime ester photoinitiator there is no particular limitation on the type of oxime ester photoinitiator, and conventionally known photoinitiators containing oxime ester groups in the structure can be used. Exemplarily, it may be selected from at least one of the following: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-[6-( 2-methylbenzoyl)-9-ethylcarbazol-3-yl]-ethane-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethyl Carbazol-3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-propane-1 -Ketone-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-y
  • the mass ratio of the photopolymerization initiator A1 and the oxime ester photoinitiator A2 in the composition is 1:5-5:5.
  • the content of the photopolymerization initiator (A) is 0.1-20 parts by mass, preferably 1-10 parts by mass. If the content of the photopolymerization initiator (A) 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 type of alkali-soluble resin (B) is not particularly limited, but it is preferably selected from the viewpoints of heat resistance, developability, and availability.
  • Alkali-soluble resins having acidic groups such as carboxyl groups and phenolic hydroxyl groups are preferred, alkali-soluble resins containing carboxyl group copolymers are more preferred, and ethylenically unsaturated monomers having carboxyl groups are particularly preferred [hereinafter referred to as "carboxyl-containing unsaturated monomers" (P )] and other copolymerizable ethylenically unsaturated monomer [hereinafter referred to as "copolymerizable unsaturated monomer" (Q)] copolymer [hereinafter referred to as "carboxyl group-containing copolymer” (R)].
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid
  • maleic acid, maleic anhydride, and Malic acid itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or their anhydrides
  • Mono(meth)acryloyloxyalkyl esters of polycarboxylic acids with more than two valences such as mono(2-methacryloyloxy
  • the following compounds may be mentioned: methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, Allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and other (meth)acrylate compounds; styrene, ⁇ -methylstyrene, o-ethylene Methyl toluene, m-vinyl toluene, p-vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl Aromatic vinyl compounds such as benzyl methyl ether,
  • Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide, etc.; acrylamide , Methacrylamide, ⁇ -chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide and other unsaturated amides; maleimide, N-phenyl horse Unsaturated imides such as methimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; polyphenylene Ethylene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane and other polymer mole
  • the carboxyl group-containing copolymer (R) is obtained by polymerizing (P) and (Q). More preferably, the (P) contains acrylic acid and/or methacrylic acid as essential components, and further contains succinic acid mono(2-acryloyloxyethyl) ester, succinic acid mono(2-methyl) At least one compound selected from the group consisting of acryloyloxyethyl) ester, ⁇ -carboxy polycaprolactone monoacrylate and ⁇ -carboxy polycaprolactone monomethacrylate; said (Q) is selected from styrene , Methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate , Glycerin monoacrylate, glycerol monomethacrylate, N
  • carboxyl group-containing copolymer (R) examples include: (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/(meth)acrylic acid benzyl ester copolymer, Base) acrylic acid/(meth)acrylic acid-2-hydroxyethyl/(meth)acrylic acid benzyl ester copolymer, (meth)acrylic acid/(meth)acrylic acid methyl ester/polystyrene macromonomer copolymer, (Meth)acrylic acid/(meth)acrylate/polymethylmethacrylate macromonomer copolymer, (meth)acrylic acid/(meth)acrylate/polystyrene macromonomer copolymer , (Meth) acrylic acid/(meth)acrylic acid benzyl ester/polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid/(meth)acrylic acid-2
  • the alkali-soluble resin (B) can be used alone or in combination of two or more.
  • the alkali-soluble resin is preferably a polymer having a weight average molecular weight (a polystyrene conversion value measured by the GPC method) of 1,000 to 200,000, and more preferably a polymer of 2,000 to 100,000 , The most preferred polymer is 5000-50000.
  • the content of the component (B) is 5-60 parts by mass, preferably 10-50 parts by mass. If the content of the alkali-soluble resin is too small, there is a defect that the adhesion to the substrate becomes poor or the alkali developability of the photocured portion is reduced; if the content of the alkali-soluble resin is too much, there is a defect that the light shielding performance is deteriorated.
  • the compound (C) having at least one polymerizable unsaturated bond described in the present invention may be in chemical forms such as monomers, oligomers, and polymers.
  • Examples of such compounds having at least one polymerizable unsaturated bond include: acrylates, methacrylates, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and other unsaturated carboxylic acids and Free radical polymerizable compounds such as salt, ester, urethane, amide, acid anhydride, acrylonitrile, styrene, vinyl ether, unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated polyurethane, etc. .
  • acrylic compounds include: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acrylic acid Octyl ester, decyl acrylate, dodecyl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-acrylate Allyloxypropyl ester, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2,2,2-trifluoroethyl acrylate
  • methacrylate compounds include: methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, twelve methacrylate Alkyl ester, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate Ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenyl
  • the compound (C) having at least one polymerizable unsaturated bond can also include allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, iso Triallyl cyanurate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide , Acryloyl morpholine, styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate , Vinyl butyrate, vinyl laurate, divinyl adipate and other compounds.
  • the compound (C) having at least one polymerizable unsaturated bond in the present invention may be used in only one type, and two or more types may be mixed and used in an arbitrary ratio in order to improve desired characteristics.
  • the content of the component (C) is 5-50 parts by mass, preferably 10-30 parts by mass. If the content of component (C) is too small, there is a defect that the photosensitivity is reduced; if the content of component (C) is too large, there is a defect that the photoresist pattern tends to become wider than the line width of the photomask.
  • the type of the colorant (D) is not particularly limited, and may include pigments and dyes.
  • the pigment may include any organic pigments, inorganic pigments, or mixtures thereof commonly used in related fields.
  • Organic pigments are not particularly limited, and may include any general-purpose pigments used in printing inks, inkjet inks, and the like. More specifically, it may be water-soluble azo pigments, water-insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrene Ketone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthraquinone pyrimidine pigments, anthraquinone pigments, indanthrone pigments, flavone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments Wait. These organic pigments can be used alone or in combination of two or more.
  • the inorganic pigment is not particularly limited, and may include metal compounds (such as metal oxides or metal complexes) and carbon black. More specifically, it may be an oxide of at least one metal selected from iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. These inorganic pigments can be used alone or in combination of two or more kinds.
  • Organic pigments and inorganic pigments may also include compounds classified as pigments according to the Color Index (published by the British Society of Colourists). More specifically, CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154 can be used , 166, 173, 180, 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71; CI Pigment Red 9, 97, 105, 122 , 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, 76; CI Pigment
  • These pigments can be used alone or in combination of two or more.
  • the average particle diameter of the pigment is preferably 0.01-0.1 ⁇ m, more preferably 0.01-0.05 ⁇ m.
  • the content of the pigment is not particularly limited, but based on the total amount of 100 parts by mass of the colorant, the content of the pigment ranges preferably from 5 to 95 parts by weight, more preferably from 10 to 90 parts by weight. If the content of the pigment is within the above range, the color filter manufactured using the pigment can have a sufficient color area and excellent light transmittance, and ensure the desired sensitivity.
  • the dye is not particularly limited, and may include: acid dyes with acid groups (such as sulfonic acid, carboxylic acid, etc.); salts of nitrogen-containing compounds and salts of the acid dyes; sulfonamides of the acid dyes and their derivatives; Acid dyes based on azo, xanthene, and/or phthalocyanine and their derivatives, etc.
  • acid dyes with acid groups such as sulfonic acid, carboxylic acid, etc.
  • salts of nitrogen-containing compounds and salts of the acid dyes such as sulfonic acid, carboxylic acid, etc.
  • sulfonamides of the acid dyes and their derivatives such as sulfonamides of the acid dyes and their derivatives
  • the dye is preferably a compound classified as a dye in the Color Index (Color Index, published by the British Society of Dyers), or a red dye, a blue dye and a purple dye among the dyes listed in the dyeing opinion (Color Dyeing Company).
  • CI solvent dyes including: yellow dyes, such as CI solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94 , 98, 99, 151, 162, 163, etc.; red dyes, such as CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, etc.; orange dyes, such as CI solvent orange 2 , 7, 11, 15, 26, 41, 45, 56, 62, etc.; blue dyes, such as CI solvent blue 5, 35, 36, 37, 44, 59, 67, 70, etc.; purple dyes, such as CI solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.; green dyes, such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.
  • yellow dyes such as CI solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82,
  • CI acid dyes including: yellow dyes, such as CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65 , 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161 ,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232 , 235, 238, 240, 242, 243, 251, etc.; red dyes, such as CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44 , 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103,
  • CI direct dyes including: yellow dyes, such as CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc.; red dyes, such as CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, etc.; orange dyes, such as CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107
  • CI mordant dyes including: yellow dyes, such as CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 Etc.; red dyes, such as CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37 , 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, etc.; orange dyes, such as CI Mordant Orange 3, 4, 5 , 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.; blue dyes, such as CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc.;
  • the above-mentioned dyes can be used alone or in combination of two or more of them.
  • the content of the dye is not particularly limited, but based on the total amount of 100 parts by mass of the colorant, the content of the dye ranges preferably from 5 to 95 parts by weight, more preferably from 10 to 90 parts by weight. If the content of the dye is within the above range, it is possible to prevent deterioration in reliability (elution of the dye due to an organic solvent after pattern formation) while obtaining excellent sensitivity.
  • the content of the colorant is not particularly limited, but in 100 parts by mass of the photosensitive resin composition, the content of the colorant (D) is usually 5-60 parts by mass, preferably 10-45 parts by mass. If the content of the colorant is within the above range, the pixel has a sufficient color density, and during development, the absence of non-pixel portions is not reduced, and the occurrence of residues can be reduced.
  • the photosensitive resin composition of the present invention further includes a hydrogen donor (E) in order to improve sensitivity.
  • E hydrogen donor
  • HABI compounds are cleaved after exposure to light, and the monoimidazole radicals produced are large in volume, and the steric hindrance makes it less active. It is difficult to initiate monomer polymerization alone, but monoimidazole radicals are easy to deprive the active hydrogen on the hydrogen donor to produce New living free radicals initiate monomer polymerization.
  • it is a hydrogen donor having the above-mentioned characteristics, there is no particular limitation in terms of specific types.
  • it may be an amine compound, a carboxylic acid compound, an organosulfur compound containing a mercapto group, or an alcohol compound. These compounds can be used alone or in combination of two or more of them.
  • the applicable amine compounds may be: aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as methyl 4-dimethylaminobenzoate, 4 -Ethyl 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.
  • aromatic amine compounds such as methyl 4-dimethylaminobenzoate, 4 -Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-
  • suitable carboxylic acid compounds may be: aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, Dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.
  • suitable organic sulfur compounds containing mercapto groups may be: 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-mercapto Butyrate), 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 two Alcohol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butaned
  • suitable alcohol compounds can be: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-ethanol, cyclohexanol, ethylene glycol , 1,2-propanediol, 1,2,3-propanetriol, benzyl alcohol, phenethyl alcohol, etc.
  • the content of the hydrogen donor (E) is 0.01-20 parts by weight, preferably 0.01-10 parts by weight. If the content of the hydrogen donor is within the above range, the sensitivity of the colored photosensitive resin composition can be further secured.
  • the photosensitive resin composition of the present invention can also optionally add other auxiliary agents commonly used in the art, including other photoinitiators and/or sensitizers, organic solvents, organic carboxylic acids, pigment dispersants, adhesives Reinforcing agent, leveling agent, development improver, antioxidant, thermal polymerization inhibitor, etc.
  • auxiliary agents commonly used in the art, including other photoinitiators and/or sensitizers, organic solvents, organic carboxylic acids, pigment dispersants, adhesives Reinforcing agent, leveling agent, development improver, antioxidant, thermal polymerization inhibitor, etc.
  • surfactants, fluorescent whitening agents, plasticizers, flame retardants, ultraviolet absorbers, foaming agents, bactericides, antistatic agents, magnetic substances, conductive materials, anti-fungal or anti-bacteria can also be added according to the application. Materials, porous adsorbents, aromatic materials, etc.
  • the other photoinitiator and/or sensitizer are different from the photopolymerization initiator A1 and the oxime ester photoinitiator A2 described above. Without limitation, it can be selected from: bisimidazole compounds, triazine compounds, coumarin compounds, acridine compounds, oxadiazole compounds, aromatic ketone compounds, benzoin and benzoin alkane Base ether compounds, anthraquinone compounds, thioxanthone compounds, etc. These compounds can be used alone or in combination of two or more.
  • 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'
  • 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.
  • 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.
  • oxadiazole compounds include: 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthoyl-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-( 4-styryl)styryl-1,3,4-oxadiazole and the like. These oxadiazole compounds can be used alone or in combination of two or more.
  • 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
  • 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.
  • 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
  • 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.
  • the organic solvent is not particularly limited as long as it can dissolve the aforementioned components, and may include, for example, glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, and chlorine-containing solvents. It is preferable to select particularly in consideration of the solubility, coatability, safety, etc. of the colorant and alkali-soluble resin.
  • Preferred ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutane Alcohol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl Ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybut
  • organic carboxylic acid is not particularly limited, and may include, for example: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, caprylic acid and other aliphatic monomers.
  • Carboxylic acid oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, Aliphatic dicarboxylic acids such as ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; 1,2,3-propanetricarboxylic acid, aconitic acid, Aliphatic tricarboxylic acids such as norbornoic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumene acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid; o-benzene Dicarboxylic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid, 1,2,3,5-benzenetetracarboxylic acid
  • the type of dispersant is not particularly limited, and may include, for example, polymer dispersants such as polyamide-type amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified poly Ester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate, polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative Wait.
  • polymer dispersants such as polyamide-type amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified poly Ester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate, polyoxyethylene alkyl phosphate, polyoxyethylene alky
  • the type of adhesion enhancer is not particularly limited, and may include, for example, vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N- (2-Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanate propy
  • the thermal polymerization inhibitor may include, for example, p-methoxyphenol, hydroquinone, catechol, tert-butylcatechol, phenothiazine, p-methoxyphenol, and the like. These thermal polymerization inhibitors are used alone or in combination of two or more of them.
  • the types of surfactants are not particularly limited, and may include, for example, fluorosurfactants, silicon surfactants, or mixtures thereof. These surfactants are used alone or in combination of two or more of them.
  • the type of plasticizer is not particularly limited, and may include, for example, dioctyl phthalate, di(dodecyl) phthalate, triethylene glycol dicaprylate, and dimethyl ethylene phthalate.
  • Alcohol esters tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol, etc. These plasticizers are used alone or in combination of two or more of them.
  • this invention also relates to the color filter using the said photosensitive resin composition, and its manufacturing method.
  • the color filter of the present invention is characterized by having a colored pattern formed using the above-mentioned photosensitive resin composition on a support.
  • 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 carried out 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 photosensitive resin composition applied on the support is usually dried at 70-110°C for about 2-4 minutes to form a photosensitive resin layer.
  • the exposure step is to expose the photosensitive resin layer formed in the aforementioned photosensitive resin layer forming step through a mask. In this process, only the portion of the coating film irradiated with light is cured.
  • 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 it 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.
  • the photosensitive resin composition of the present invention has excellent sensitivity and good developability, high brightness after curing, and excellent adhesion to a substrate.
  • the manufacturing method can manufacture high-performance color filters with high production efficiency.
  • Figure 1 is a high performance liquid chromatogram of product a1.
  • Figure 2 is a high performance liquid chromatogram of T1.
  • Figure 3 is a high performance liquid chromatogram of T2.
  • Figure 4 is a high performance liquid chromatogram of T3.
  • Figure 5 is a structure spectrum obtained by single crystal diffraction of T1.
  • M2 4-(3,4-Dimethoxyphenyl)-imidazole (M2), 4.2g 30% liquid caustic soda, 4.0g tetrabutylammonium bromide and 300g toluene, heated and stirred, and dropped at 60-65°C Add 85 g of sodium hypochlorite (11% aqueous solution), after the dripping is completed, the reaction is incubated, and sampling is controlled by HPLC until M1 and M2 are both less than 1%, the reaction is complete, and the incubation is terminated.
  • M2 4-(3,4-Dimethoxyphenyl)-imidazole
  • the product a1 was analyzed by high performance liquid chromatography, and the results are shown in Figure 1. The analysis results show that the total peak content of the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 is 92.5%.
  • the product a1 is a mixture of two different monoimidazoles (ie, M1, M2) through self-coupling and mutual coupling, including T1, T2 and T3.
  • T1, T2 and T3 were verified and analyzed.
  • pure T1, T2 and T3 were obtained, and the structure was confirmed respectively.
  • Figures 2-4 are respectively the high performance liquid chromatograms of T1, T2 and T3.
  • T1 has only one peak in the liquid phase, but two peak shapes are obtained by single crystal diffraction, see Figure 5. Combining the structural characteristics, it can be determined that the main product of the coupling of two monoimidazoles is a mixture of hydrogen-containing N on one imidazole and C on the 2 position of the other imidazole, which indicates that the structure of T1 is the present invention.
  • the monoimidazole used to synthesize T1 is M1, which is a symmetrical imidazole, so the 2'-1 and 2'-3 obtained by coupling are similar in polarity, and it is difficult to separate the liquid phase.
  • M1 the structure of the product obtained by coupling itself has the same structure of 2'-1 and 2-1', and the structure of 2'-3 and 2-3' are also the same, so the main structure of T1 is 2' -1 and 2'-3 are the products of two attachment positions, respectively T1-1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2 '-Diimidazole; T1-2: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole.
  • the structural formula is as follows:
  • Synthetic monoimidazole M2 of T2 belongs to asymmetric monoimidazole, M2 has two configurations, M2-1 and M2-2, the structural formula is as follows:
  • T2 Analyze the separated pure T2, the main structure is the four link products, and the structure is confirmed by LCMS. Mass spectrometry analysis uses the software attached to the instrument to obtain 849 and 850 molecular fragment peaks. The molecular weight of the product is 848, which is consistent with T+1 and T+2, which proves that the four products have similar structures and the same molecular weight.
  • T2 is synthesized by asymmetric monoimidazole coupling.
  • T2 there are theoretically eight main structures connected by 1-2 and 2-3 connection positions, but for self-coupled monoimidazole, the 2'-1 and 2-1' structures in the structure are the same , 2'-3 and 2-3' have the same structure, so for T2, there are actually four main structures connected by 1-2 and 2-3 connection positions, and their composition is: T2-1: 2 ,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole; T2-2: 2, 2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole; T2-3: 2,2 ',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole; T2-4: 2,2'
  • T3 is formed by the coupling of M1 and M2.
  • the main structure of the separated pure T3 in the liquid phase is the product of four connection positions, and the LCMS confirms the structure of the product of the four connection positions.
  • Mass spectrometry analysis The 755 and 756 molecular fragment peaks are obtained with the aid of the software attached to the instrument.
  • the molecular weight of the product is 754, which is consistent with T+1 and T+2, which proves that the four products have similar structures and the same molecular weight.
  • T3 is formed by two-by-two connection of symmetric imidazole M1 and asymmetric imidazole M2. There are four main structures connected by 1-2 and 2-3 connection positions.
  • composition is respectively: T3-1: 2, 2', 5 -Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole; T3-2: 2,2' ,5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole; T3-3: 2, 2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole; T3-4: 2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole.
  • the structural formula is as follows:
  • the product a1 is composed of T1 (T1-1, T1-2), T2 (T2-1, T2-2, T2-3, T2-4) and T3 (T3-1, T3-2, T3-3, T3-4) are combined, in which the content of the bisimidazole compound composed of 2-1', 2-3', 2'-1 and 2'-3 four connection positions in a1 is 92.5% .
  • the product a9 is a mixture of two different monoimidazoles (ie, M2, M3) through self-coupling and mutual coupling, including T2, T4 and T5.
  • M2, M3 monoimidazoles
  • T2, T4 and T5 were verified and analyzed.
  • T2, T4 and T5 were obtained respectively, and the structure was confirmed respectively.
  • T2 is consistent with the structure T2 in compound a1.
  • T4 is formed by self-coupling of asymmetric monoimidazole M3. There are four main structures connected by 1-2 and 2-3 connection positions.
  • the composition is respectively: T4-1: 2,2'-bis(4-chlorobenzene Yl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole; T4-2: 2,2 '-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole ; T4-3: 2,2'-bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) -1,2'-diimidazole; T4-4: 2,2'-bis(4-
  • T5 is formed by the two-by-two coupling of asymmetric M2 and asymmetric M3. There are four main structures connected by 1-2 and 2-3 connection positions.
  • the composition is respectively: T5-1: 2-(4-chlorobenzene Group)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole; T5-2: 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'- Diimidazole; T5-3: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) )-2',3-diimidazole; T5-4: 2'-(4-chlorophen
  • the product a9 is composed of T2 (T2-1, T2-2, T2-3, T2-4), T4 (T4-1, T4-2, T4-3, T4-4) and T5 ( T5-1, T5-2, T5-3, T5-4) are a combination of bisimidazole compounds composed of 2-1', 2-3', 2'-1 and 2'-3
  • the content in a9 is 93.2%.
  • a17 is a BCIM produced by Changzhou Qiangli Electronic New Materials Co., Ltd., which contains bisimidazole compounds with four connection positions of 2-1', 2-3', 2'-1 and 2'-3 (due to the symmetrical structure, it is 2-1' and 2'-1 are the same structure, 2-3' and 2'-3 are the same structure), and the total mass percentage of the four connected bisimidazole compounds in A1 is 99 %, the molar extinction coefficient at the wavelength of 365nm (i-line) is 26L ⁇ mol -1 ⁇ cm -1 .
  • the structural formula is as follows:
  • the photosensitive resin composition prepared in each of the Examples and Comparative Examples was coated on glass (#1737, manufactured by Corning Corporation) using a spin coating method, and then the photosensitive resin composition was applied at 100°C. The volatile component is volatilized in 3 minutes to form a photosensitive resin layer. After cooling, the photosensitive resin layer was exposed using an ultra-high pressure mercury lamp, and the irradiation light amount was set to 100 mJ/cm 2 . Then, post-baking was performed at 230°C for 20 minutes to obtain a glass substrate having a colored layer with a film thickness of 2 ⁇ m.
  • the Y value is determined according to the following criteria:
  • Y value is 57 or more
  • Y value is 55 or more and less than 57
  • ⁇ : Y value is less than 55.
  • the photosensitive resin composition prepared in each of the Examples and Comparative Examples was coated on glass (#1737, manufactured by Corning Corporation) using a spin coating method, and then the photosensitive resin composition was applied at 100°C. The volatile component is volatilized in 3 minutes to form a photosensitive resin layer. After cooling, using an i-line reduction projection exposure device, the coating film was irradiated with a wavelength of 365 nm through a mask of 20 ⁇ m in length ⁇ 20 ⁇ m in width so that the exposure amount became 50 mJ/cm 2 . After the irradiation, using a developer (trade name: CD-2000, 60%, manufactured by Fujifilm Electronic Materials), the coating film was developed at 23° C. for 60 seconds.
  • a developer trade name: CD-2000, 60%, manufactured by Fujifilm Electronic Materials
  • 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 liquid composition was 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 ;
  • the coating process can be completed once or in multiple times; the substrate with the coating film is cooled to room temperature, attached with a mask, and passed through the RW-UV equipped with a high-pressure mercury lamp .70201 crawler aerator, radiation wavelength 250-450nm, the energy received by a single exposure is about 80mJ/cm 2 , the coating film is exposed under ultraviolet radiation through the gap of the mask plate; at a temperature of 25 °C, use 1% Developed with NaOH aqueous solution, then washed with ultrapure water, and air-dried; finally, post-baked in an oven at 240°C for 30 minutes to obtain the pattern transferred from the mask.
  • the pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability.
  • SEM scanning electron microscope

Abstract

A photosensitive resin composition for a color filter, the color filter and manufacturing method therefor. The photosensitive resin composition comprises a photopolymerization initiator, an alkali soluble resin, a compound having at least one polymerized unsaturated bond, a colorant, and a hydrogen donor. When applied to prepare the color filter, the photosensitive resin composition exhibits excellent sensitivity and good developability, the brightness is high after solidification, and the tightness to the substrate is excellent.

Description

用于彩色滤光片的感光性树脂组合物及彩色滤光片Photosensitive resin composition for color filter and color filter 技术领域Technical field
本发明属于有机化学和光固化技术领域，具体涉及一种用于彩色滤光片的感光性树脂组合物，使用该感光性树脂组成物的彩色滤光片及其制造方法。The invention belongs to the technical field of organic chemistry and photocuring, and specifically relates to a photosensitive resin composition used for a color filter, a color filter using the photosensitive resin composition, and a manufacturing method thereof.
背景技术Background technique
彩色滤光片通常由染色法、印刷法、颜料分散法等方法将红、绿、蓝等色素形成于透明基板上而制得。颜料分散法是目前工业上的主流方法，在透明基片上涂布含有着色剂的感光性树脂组合物，然后进行图像曝光、显影和视情况需要的后固化，通过重复这些过程形成彩色滤光片。该方法具有高耐热性、不需染色等优点，并且可形成高精度的着色层。Color filters are usually made by forming red, green, and blue pigments on a transparent substrate by dyeing, printing, and pigment dispersion methods. The pigment dispersion method is currently the mainstream method in the industry. A photosensitive resin composition containing a colorant is coated on a transparent substrate, and then the image is exposed, developed, and post-cured as necessary. The color filter is formed by repeating these processes . This method has the advantages of high heat resistance, no need for dyeing, etc., and can form a high-precision colored layer.
近年来，对彩色滤光片在色度、对比度等方面的要求逐步提高。为了实现显示元件的高色纯度化或光接收元件的高色分辨率，组合物中着色剂的浓度有变高的倾向，但由此也带来了问题，包括：在显影过程中未曝光部分的基底或者遮光层上容易产生残留物或污点，与基板的粘附变得不充分，无法获得充分的硬化，或者在曝光部图案形成性不良等。In recent years, the requirements for color filters in terms of chroma and contrast have gradually increased. In order to achieve high color purity of the display element or high color resolution of the light receiving element, the concentration of the colorant in the composition tends to become higher, but this also brings problems, including: unexposed parts during the development process Residues or stains are prone to occur on the base or the light-shielding layer, the adhesion to the substrate becomes insufficient, sufficient curing cannot be obtained, or the pattern formation in the exposed part is poor.
时至今日，针对感光性树脂组合物中组分的组合/选配仍然是获得具有更优应用性能的产品的主要手段。Up to now, the combination/selection of components in the photosensitive resin composition is still the main means to obtain products with better application performance.
发明内容Summary of the invention
针对现有技术发展的需求，本发明的目的主要在于提供一种用于彩色 滤光片的感光性树脂组合物，该组合物应用时具有优异的感光度和良好的显影性，固化后亮度高，且与基板密合性优异。In response to the needs of the development of the prior art, the main purpose of the present invention is to provide a photosensitive resin composition for color filters, which has excellent sensitivity and good developability when applied, and has high brightness after curing. , And excellent adhesion to the substrate.
为了实现上述目的，采用的具体技术方案如下。In order to achieve the above objectives, the specific technical solutions adopted are as follows.
一种用于彩色滤光片的感光性树脂组合物，包含下列组分：A photosensitive resin composition for color filters, comprising the following components:
(A)光聚合引发剂，包括光聚合引发剂A1和至少一种肟酯类光引发剂A2；(A) Photopolymerization initiator, including photopolymerization initiator A1 and at least one oxime ester photoinitiator A2;
(B)碱可溶性树脂；(B) Alkali-soluble resin;
(C)具有至少一个聚合性不饱和键的化合物；(C) A compound having at least one polymerizable unsaturated bond;
(D)着色剂；(D) Coloring agent;
(E)供氢体；(E) Hydrogen donor;
其中，光聚合引发剂A1为六芳基双咪唑(即HABI)类混合光引发剂，具有如通式(I)所示结构，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，且该四种连接位的双咪唑化合物在A1中的总质量百分含量为92％以上，Among them, the photopolymerization initiator A1 is a hexaarylbisimidazole (ie HABI) type mixed photoinitiator, which has a structure as shown in the general formula (I), which contains 2-1', 2-3', 2'-1 And 2'-3 four bisimidazole compounds at the connection position, and the total mass percentage of the four bisimidazole compounds at the connection position in A1 is more than 92%,
Figure PCTCN2020081284-appb-000001
Figure PCTCN2020081284-appb-000001
通式(I)中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基； In the general formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group;
且光聚合引发剂(A)在i线(365nm)处摩尔消光系数在5000-10000之间。And the molar extinction coefficient of the photopolymerization initiator (A) at the i-line (365nm) is between 5000-10000.
本发明的另一个目的在于提供一种使用上述感光性树脂组成物的彩色滤光片及其制造方法。Another object of the present invention is to provide a color filter using the above-mentioned photosensitive resin composition and a manufacturing method thereof.
发明详述Detailed description of the invention
以下，将对本发明的感光性树脂组合物、彩色滤光片及其制造方法做更加详细的说明。Hereinafter, the photosensitive resin composition, color filter and manufacturing method thereof of the present invention will be described in more detail.
<光聚合引发剂(A)><Photoinitiator (A)>
光聚合引发剂A1Photopolymerization initiator A1
如上文所述，本发明的光聚合引发剂A1为HABI类混合光引发剂，具有如通式(I)所示结构，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，且该四种连接位的双咪唑化合物在光聚合引发剂A1中的总质量百分含量为92％以上，As mentioned above, the photopolymerization initiator A1 of the present invention is a HABI-based mixed photoinitiator, having a structure as shown in the general formula (I), which contains 2-1', 2-3', 2'-1 and 2 '-3 Four kinds of bisimidazole compounds with connection positions, and the total mass percentage of the four kinds of bisimidazole compounds with connection positions in the photopolymerization initiator A1 is 92% or more,
Figure PCTCN2020081284-appb-000002
Figure PCTCN2020081284-appb-000002
通式(I)中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基； In the general formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group;
且光聚合引发剂(A)在i线(365nm)处摩尔消光系数在5000-10000之间。And the molar extinction coefficient of the photopolymerization initiator (A) at the i-line (365nm) is between 5000-10000.
满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，具体为下列结构：The bisimidazole compounds satisfying the four connection positions 2-1', 2-3', 2'-1 and 2'-3 of the structure represented by the general formula (I) are specifically the following structures:
Figure PCTCN2020081284-appb-000003
Figure PCTCN2020081284-appb-000003
通式(I)中，所述芳基优选是苯基。In the general formula (I), the aryl group is preferably a phenyl group.
所述取代的芳基可以是单取代的，也可以是多取代的。The substituted aryl group may be mono-substituted or poly-substituted.
优选地，芳基上的取代基可以为卤素、硝基、氰基、胺基、羟基、C 1-C 20的烷基或链烯基、C 1-C 8的烷氧基，其中各独立变量(即，各取代基)中的亚甲基可以任选地被氧、硫、亚胺基所取代。 Preferably, the substituents on the aryl group can be halogen, nitro, cyano, amino, hydroxyl, C 1 -C 20 alkyl or alkenyl, C 1 -C 8 alkoxy, wherein each independently The methylene group in the variable (ie, each substituent) may be optionally substituted with oxygen, sulfur, or imino groups.
更优选地，芳基上的取代基可以为氟、氯、溴、硝基、氰基、胺基、羟基、C 1-C 10的烷基或链烯基、C 1-C 5的烷氧基，其中各独立变量中的亚甲基可以任选地被氧、硫、亚胺基所取代。 More preferably, the substituent on the aryl group can be fluorine, chlorine, bromine, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl or alkenyl, C 1 -C 5 alkoxy Group, wherein the methylene group in each independent variable can be optionally substituted with oxygen, sulfur, or imino groups.
进一步优选地，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6中至少一个是含有卤素取代基的芳基。通过卤素取代基可以提高固化过程中的变色效果，以增强在显影时电子眼的识别能力(注：感光性树脂层经曝光后会发生颜色变化，与未曝光区域形成色差，从而被电子眼识别，本发明可以使色差更明显)， 进而提高应用产品的质量。特别优选地，卤素取代基为氯。 More preferably, at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 is an aryl group containing a halogen substituent. Halogen substituents can improve the discoloration effect during the curing process to enhance the recognition ability of the electronic eye during development (Note: The photosensitive resin layer will change color after exposure, and form a color difference with the unexposed area, which will be recognized by the electronic eye. The invention can make the chromatic aberration more obvious), thereby improving the quality of the application product. Particularly preferably, the halogen substituent is chlorine.
申请人研究发现，HABI类化合物的光引发活性受其芳香环上取代基的电子效应和立体效应的影响，芳香环上的取代基对HABI类化合物在265nm附近的吸收影响较小，但对HABI类化合物在365nm附近的吸收影响较大。当HABI结构中引入共轭体系时，会使得紫外吸收波长向着长波长的方向移动(即产生红移现象)和增加紫外吸收强度(即摩尔消光系数)。The applicant’s research found that the photoinitiation activity of HABI compounds is affected by the electronic and steric effects of the substituents on the aromatic ring. The substituents on the aromatic ring have little influence on the absorption of HABI compounds near 265 nm, but have little effect on HABI. The absorption of the compound near 365nm has a greater influence. When the conjugated system is introduced into the HABI structure, it will cause the ultraviolet absorption wavelength to move toward the long wavelength (ie, produce a red shift phenomenon) and increase the ultraviolet absorption intensity (ie, the molar extinction coefficient).
在本发明的感光性树脂组成物中，光聚合引发剂A1作为起始剂，产生的活性自由基通过供氢体发生链转移，能够不失活且有效地促使曝光区域硬化。这对提高彩色滤光片的感光度和亮度是有利的。In the photosensitive resin composition of the present invention, the photopolymerization initiator A1 is used as the initiator, and the generated active radicals undergo chain transfer through the hydrogen donor, which can effectively promote hardening of the exposed area without deactivation. This is beneficial for improving the sensitivity and brightness of the color filter.
除了上文所述的2-1’、2-3’、2’-1、2’-3四种连接位外，如通式(I)所示的HABI类化合物还存在1-4’、1-5’、3-4’、3-5’、1-1’、1-3’、3-1’、3-3’、4-1’、4-3’、5-1’、5-3’等连接位。然而申请人研究发现，具有如上要求限定的光聚合引发剂A1对解决本发明的技术问题是最为优选的。任一种连接位的单一物质的性能均远远小于光聚合引发剂A1，而如果这四种连接位的总含量低于92％，则性能有明显变差的趋势。In addition to the four connection positions 2-1', 2-3', 2'-1, and 2'-3 described above, HABI compounds shown in general formula (I) also have 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1', 5-3' and so on. However, the applicant found that the photopolymerization initiator A1 as defined above is the most preferable for solving the technical problem of the present invention. The performance of a single substance of any kind of linking site is far less than that of the photopolymerization initiator A1, and if the total content of these four linking sites is less than 92%, the performance will obviously deteriorate.
作为本发明中使用的光聚合引发剂A1，优选满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物在其中的总质量百分含量为95％以上，特别优选由满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物组成。As the photopolymerization initiator A1 used in the present invention, bisimidazole compounds satisfying the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 of the structure represented by the general formula (I) are preferred The total mass percentage in it is 95% or more, and it is particularly preferred to have four link positions that satisfy the structure represented by the general formula (I): 2-1', 2-3', 2'-1 and 2'-3 Composition of bisimidazole compound.
申请人研究发现，当光聚合引发剂在i线(365nm)处摩尔消光系数在5000-10000之间，具有适宜的感光度，不会由于感光度不足而降低固化速度，也不会由于感光度过高而引起底切的发生。The applicant’s research found that when the photopolymerization initiator has a molar extinction coefficient between 5000-10000 at the i-line (365nm), it has a suitable sensitivity and will not reduce the curing speed due to insufficient sensitivity, nor will it be due to sensitivity. Too high and cause undercutting.
HABI类光引发剂是光刻胶领域公知的一类光引发剂，可通过三芳基咪 唑类或取代三芳基咪唑类化合物的氧化偶合来制备，具体制备工艺可参照例如US3784557、US4622286和US4311783等现有技术中的记载(在此将其全文引入以作为参考)。在现有工艺的基础上，增加溶剂重结晶工艺，即可方便地获得满足本发明上述组成要求的光聚合引发剂A1。所述溶剂可以是甲苯、甲醇、乙酸乙酯、二氯甲烷、水中的一种或两种以上的组合物。非限制性地，光聚合引发剂A1的制备同样可以借鉴申请人的在先申请(申请号为201811451262.4)中记载的内容(在此将其全文引入以一并作为参考)。HABI photoinitiators are well-known photoinitiators in the photoresist field. They can be prepared by oxidative coupling of triarylimidazoles or substituted triarylimidazoles. The specific preparation process can be referred to, for example, US3784557, US4622286 and US4311783. There are technical records (the full text is hereby incorporated as a reference). On the basis of the existing technology, adding a solvent recrystallization process can conveniently obtain the photopolymerization initiator A1 meeting the above composition requirements of the present invention. The solvent may be one or a combination of two or more of toluene, methanol, ethyl acetate, dichloromethane, and water. In a non-limiting manner, the preparation of the photopolymerization initiator A1 can also refer to the content described in the applicant's previous application (application number 201811451262.4) (the entire text is incorporated herein by reference).
示例性地，对应于2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，光聚合引发剂A1选自或包含下列组合中的至少一种：Exemplarily, corresponding to the bisimidazole compound at the four attachment positions of 2-1', 2-3', 2'-1 and 2'-3, the photopolymerization initiator A1 is selected from or includes at least one of the following combinations :
Figure PCTCN2020081284-appb-000004
Figure PCTCN2020081284-appb-000004
Figure PCTCN2020081284-appb-000005
Figure PCTCN2020081284-appb-000005
Figure PCTCN2020081284-appb-000006
Figure PCTCN2020081284-appb-000006
Figure PCTCN2020081284-appb-000007
Figure PCTCN2020081284-appb-000007
在本发明的感光性树脂组合物中，以总量100质量份计，光聚合引发剂A1的含量优选为0.1-10质量份。In the photosensitive resin composition of the present invention, the content of the photopolymerization initiator A1 is preferably 0.1 to 10 parts by mass based on 100 parts by mass in total.
肟酯类光引发剂A2Oxime ester photoinitiator A2
作为本发明所述感光性树脂组合物中的光聚合引发剂，除了上述光聚合引发剂A1之外，还含有至少一种肟酯类光引发剂A2。As the photopolymerization initiator in the photosensitive resin composition of the present invention, in addition to the photopolymerization initiator A1 described above, at least one oxime ester photoinitiator A2 is contained.
体系中加入肟脂类光引发剂对提升组合物的感光度、解析度等是有利的。相比于不添加肟脂类光引发剂或添加其它类别的光引发剂(如苯乙酮类化合物、三嗪类化合物等)，在光聚合引发剂A1的存在下引入肟脂类光引发剂能够显著提升组合物的感光度和显影性，同时对提高解析度也是有利的。Adding an oxime lipid photoinitiator to the system is beneficial to improve the sensitivity and resolution of the composition. Compared with not adding oxime lipid photoinitiators or adding other types of photoinitiators (such as acetophenone compounds, triazine compounds, etc.), oxime lipid photoinitiators are introduced in the presence of photopolymerization initiator A1 It can significantly improve the sensitivity and developability of the composition, and at the same time, it is also beneficial to improve the resolution.
对肟酯类光引发剂的种类没有特别的限定，可使用结构中含有肟酯基团的现有已知光引发剂。示例性地，可选自下列中的至少一种：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。There is no particular limitation on the type of oxime ester photoinitiator, and conventionally known photoinitiators containing oxime ester groups in the structure can be used. Exemplarily, it may be selected from at least one of the following: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-[6-( 2-methylbenzoyl)-9-ethylcarbazol-3-yl]-ethane-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethyl Carbazol-3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-propane-1 -Ketone-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-benzene Thiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane -1,2-Dione-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-benzoic acid oxime ester, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-ortho Methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(4-benzoyldiphenyl sulfide)- 3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane -1,2-Dione-2-O-methylbenzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-ring Hexyl oxime carboxylate, 1-(4-thenoyl-diphenylsulfide-4'-yl)-3-cyclopentyl-propane-1-one-acetoxime ester, 1-(4-benzoyl di Phenyl sulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazol-3-yl)-3 -Cyclohexyl-propane-1-one-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propane-1-one-acetic acid Oxime ester, 1-(6-thenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanfuroyl-9 -Ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-oxime acetate, 1 -(6-furoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1-(4-phenylthiobenzene Yl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1 -(6-furanfurfuryl-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-propanedi Ketone-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-(thiophene-2 -Formyl)phenylthio]phenyl)-3-cyclopentylpropane-1,2-dione-2-oxime acetate, 1-[9,9-dibutyl-2-yl]-3- Cyclohexylpropylpropane-1,2-dione-2-oxime acetate, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-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-propan-1-one- Oxime benzoate, 1-[7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-acetic acid Oxime ester, 1-[6-(furan-2-formyl)-9-ethylcarbazol-3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxycarbonyl oxime ester And its analogues. These oxime ester compounds can be used alone or in combination of two or more.
基于性能方面的考虑，光聚合引发剂A1与肟酯类光引发剂A2在组合物中的质量比为1:5-5:5。Based on performance considerations, the mass ratio of the photopolymerization initiator A1 and the oxime ester photoinitiator A2 in the composition is 1:5-5:5.
在100质量份感光性树脂组合物中，光聚合引发剂(A)的含量为0.1-20质量份，优选1-10质量份。若光聚合引发剂(A)的含量过小，存在光致灵敏度下降的缺陷；若含量过大，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 photopolymerization initiator (A) is 0.1-20 parts by mass, preferably 1-10 parts by mass. If the content of the photopolymerization initiator (A) 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.
<碱可溶性树脂(B)><Alkali-soluble resin (B)>
本发明的感光性树脂组合物中，对碱可溶性树脂(B)的种类没有特别限定，但较佳的是从耐热性、显影性及获取性等方面出发来进行选择。优选具有羧基、酚羟基等酸性基团的碱可溶性树脂，进一步优选含羧基共聚物的碱可溶性树脂，特别优选具有羧基的烯属不饱和单体[以下简称“含羧基不饱和单体”(P)]和其它可共聚的烯属不饱和单体[以下简称“共聚性不饱和单体”(Q)]的共聚物[以下简称“含羧基共聚物”(R)]。In the photosensitive resin composition of the present invention, the type of alkali-soluble resin (B) is not particularly limited, but it is preferably selected from the viewpoints of heat resistance, developability, and availability. Alkali-soluble resins having acidic groups such as carboxyl groups and phenolic hydroxyl groups are preferred, alkali-soluble resins containing carboxyl group copolymers are more preferred, and ethylenically unsaturated monomers having carboxyl groups are particularly preferred [hereinafter referred to as "carboxyl-containing unsaturated monomers" (P )] and other copolymerizable ethylenically unsaturated monomer [hereinafter referred to as "copolymerizable unsaturated monomer" (Q)] copolymer [hereinafter referred to as "carboxyl group-containing copolymer" (R)].
作为含羧基不饱和单体(P)，可例举如下化合物：丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸等不饱和单羧酸类；马来酸、马来酸酐、富马酸、衣康酸、衣康酸酐、柠康酸、柠康酸酐、中康酸等不饱和二羧酸 或其酸酐类；三元以上的不饱和多元羧酸或其酸酐类；琥珀酸单(2-丙烯酰氧基乙基)酯、琥珀酸单(2-甲基丙烯酰氧基乙基)酯、邻苯二甲酸单(2-丙烯酰氧基乙基)酯、邻苯二甲酸单(2-甲基丙烯酰氧基乙基)酯等二元以上的多元羧酸的单(甲基)丙烯酰氧基烷基酯类；ω-羧基聚己内酯单丙烯酸酯、ω-羧基聚己内酯单甲基丙烯酸酯等在两末端具有羧基和羟基的聚合物的单(甲基)丙烯酸酯类等。这些含羧基不饱和单体可以单独使用或两种以上组合使用。As the carboxyl group-containing unsaturated monomer (P), the following compounds may be mentioned: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and Malic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or their anhydrides; unsaturated polycarboxylic acids or their anhydrides with more than three valence; succinic acid mono (2-acryloyloxyethyl) ester, mono(2-methacryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) phthalate, phthalic acid Mono(meth)acryloyloxyalkyl esters of polycarboxylic acids with more than two valences such as mono(2-methacryloyloxyethyl) ester; ω-carboxy polycaprolactone monoacrylate, ω- Carboxylic polycaprolactone monomethacrylate and the like are mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends. These carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.
作为共聚性不饱和单体(Q)，可例举如下化合物：丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、甘油单丙烯酸酯、甘油单甲基丙烯酸酯等(甲基)丙烯酸酯类化合物；苯乙烯、α-甲基苯乙烯、邻乙烯基甲苯、间乙烯基甲苯、对乙烯基甲苯、对氯苯乙烯、邻甲氧基苯乙烯、间甲氧基苯乙烯、对甲氧基苯乙烯、邻乙烯基苄基甲醚、间乙烯基苄基甲醚、对乙烯基苄基甲醚、邻乙烯基苄基缩水甘油醚、间乙烯基苄基缩水甘油醚、对乙烯基苄基缩水甘油醚等芳香族乙烯基化合物；茚、1-甲基茚等茚类丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯等不饱和羧酸缩水甘油酯类；醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯类；乙烯基甲醚、乙烯基乙醚、烯丙基缩水甘油醚等不饱和醚类；丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化乙烯叉等氰化乙烯基化合物；丙烯酰胺、甲基丙烯酰胺、α-氯丙烯酰胺、N-2-羟乙基丙烯酰胺、N-2-羟乙基甲基丙烯酰胺等不饱和酰胺类；马来酰亚胺、N-苯基马来酰亚胺、N-环己基马来酰亚胺等不饱和酰亚胺类；1,3-丁二烯、异戊二烯、氯丁二烯等脂肪族共轭二烯类；聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯、聚硅氧烷等聚合物分子链的末端具有单丙烯酰 基或单甲基丙烯酰基的大分子单体类等。这些共聚性不饱和单体可以单独使用或两种以上组合使用。As the copolymerizable unsaturated monomer (Q), the following compounds may be mentioned: methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, Allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and other (meth)acrylate compounds; styrene, α-methylstyrene, o-ethylene Methyl toluene, m-vinyl toluene, p-vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl Aromatic vinyl compounds such as benzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; indene, 1- Unsaturated glycidyl carboxylates such as indene glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Class; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, etc.; acrylamide , Methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide and other unsaturated amides; maleimide, N-phenyl horse Unsaturated imides such as methimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; polyphenylene Ethylene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane and other polymer molecular chain ends with a monoacryl or monomethacryloyl group Macromonomers, etc. These copolymerizable unsaturated monomers can be used alone or in combination of two or more kinds.
作为优选的碱可溶性树脂(B)，含羧基共聚物(R)是由(P)和(Q)聚合而得。更优选地，所述(P)是以丙烯酸和/或甲基丙烯酸作为必要成分，根据情况进一步含有选自琥珀酸单(2-丙烯酰氧基乙基)酯、琥珀酸单(2-甲基丙烯酰氧基乙基)酯、ω-羧基聚己内酯单丙烯酸酯和ω-羧基聚己内酯单甲基丙烯酸酯等中的至少1种化合物；所述(Q)选自苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、甘油单丙烯酸酯、甘油单甲基丙烯酸酯、N-苯基马来酰亚胺、聚苯乙烯大分子单体和聚甲基丙烯酸甲酯大分子等单体中的至少1种。As the preferred alkali-soluble resin (B), the carboxyl group-containing copolymer (R) is obtained by polymerizing (P) and (Q). More preferably, the (P) contains acrylic acid and/or methacrylic acid as essential components, and further contains succinic acid mono(2-acryloyloxyethyl) ester, succinic acid mono(2-methyl) At least one compound selected from the group consisting of acryloyloxyethyl) ester, ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylate; said (Q) is selected from styrene , Methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate , Glycerin monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromer and polymethyl methacrylate macromer and other monomers.
作为含羧基共聚物(R)的具体例，可举出：(甲基)丙烯酸/(甲基)丙烯酸甲酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羟基乙酯/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/聚苯乙烯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/聚甲基丙烯酸甲酯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/聚苯乙烯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/聚甲基丙烯酸甲酯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羟基乙酯/(甲基)丙烯酸苄酯/聚苯乙烯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羟基乙酯/(甲基)丙烯酸苄酯/聚甲基丙烯酸甲酯大分子单体共聚物、甲基丙烯酸/苯乙烯/(甲基)丙烯酸苄酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/琥珀酸单[2-(甲基)丙烯酰氧基乙基]酯/苯乙烯/(甲基)丙烯酸苄酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/琥珀酸单[2-(甲基)丙烯酰氧基乙基]酯/苯乙烯/(甲基)丙烯酸烯丙酯 /N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸苄酯/甘油单(甲基)丙烯酸酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/ω-羧基聚己内酯单(甲基)丙烯酸酯/苯乙烯/(甲基)丙烯酸苄酯/甘油单(甲基)丙烯酸酯/N-苯基马来酰亚胺共聚物等。Specific examples of the carboxyl group-containing copolymer (R) include: (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/(meth)acrylic acid benzyl ester copolymer, Base) acrylic acid/(meth)acrylic acid-2-hydroxyethyl/(meth)acrylic acid benzyl ester copolymer, (meth)acrylic acid/(meth)acrylic acid methyl ester/polystyrene macromonomer copolymer, (Meth)acrylic acid/(meth)acrylate/polymethylmethacrylate macromonomer copolymer, (meth)acrylic acid/(meth)acrylate/polystyrene macromonomer copolymer , (Meth) acrylic acid/(meth)acrylic acid benzyl ester/polymethyl methacrylate macromonomer copolymer, (meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl/(meth) Benzyl acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/-2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/polymethyl methacrylate macromonomer Copolymer, methacrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono[2-(meth)acryloyloxy Ethyl]ester/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono[2-(meth)acryloyloxyethyl ]Ester/styrene/(meth)acrylic acid allyl ester/N-phenylmaleimide copolymer, (meth)acrylic acid/styrene/(meth)acrylic acid benzyl ester/glycerol mono(meth) Acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/ω-carboxypolycaprolactone mono(meth)acrylate/styrene/benzyl(meth)acrylate/glycerol mono( Meth)acrylate/N-phenylmaleimide copolymer, etc.
本发明中，碱可溶性树脂(B)可以单独使用或两种以上组合使用。In the present invention, the alkali-soluble resin (B) can be used alone or in combination of two or more.
就显影性以及液黏度等观点而言，碱可溶性树脂优选为重均分子量(以GPC法测定而得的聚苯乙烯换算值)为1000-200000的聚合物，进一步优选为2000-100000的聚合物，最优选为5000-50000的聚合物。From the viewpoints of developability and liquid viscosity, the alkali-soluble resin is preferably a polymer having a weight average molecular weight (a polystyrene conversion value measured by the GPC method) of 1,000 to 200,000, and more preferably a polymer of 2,000 to 100,000 , The most preferred polymer is 5000-50000.
在100质量份感光性树脂组合物中，组分(B)的含量为5-60质量份，优选为10-50质量份。若碱可溶性树脂的含量过少，存在与基体的粘附变差或光固化部分的碱性显影能力下降的缺陷；若碱可溶性树脂的含量过多，则存在光屏蔽性能变差的缺陷。In 100 parts by mass of the photosensitive resin composition, the content of the component (B) is 5-60 parts by mass, preferably 10-50 parts by mass. If the content of the alkali-soluble resin is too small, there is a defect that the adhesion to the substrate becomes poor or the alkali developability of the photocured portion is reduced; if the content of the alkali-soluble resin is too much, there is a defect that the light shielding performance is deteriorated.
<具有至少一个聚合性不饱和键的化合物(C)><Compound (C) having at least one polymerizable unsaturated bond>
本发明中所述的具有至少一个聚合性不饱和键的化合物(C)可以是单体、低聚物、聚合物等化学形态。The compound (C) having at least one polymerizable unsaturated bond described in the present invention may be in chemical forms such as monomers, oligomers, and polymers.
作为这种具有至少一个聚合性不饱和键的化合物，可例举出：丙烯酸酯类，甲基丙烯酸酯类，衣康酸、巴豆酸、异巴豆酸、马来酸等不饱和羧酸及其盐、酯，氨基甲酸酯，酰胺，酸酐，丙烯腈，苯乙烯，乙烯基醚，不饱和聚酯、不饱和聚醚、不饱和聚酰胺、不饱和聚氨酯等自由基聚合性化合物，等等。Examples of such compounds having at least one polymerizable unsaturated bond include: acrylates, methacrylates, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and other unsaturated carboxylic acids and Free radical polymerizable compounds such as salt, ester, urethane, amide, acid anhydride, acrylonitrile, styrene, vinyl ether, unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated polyurethane, etc. .
示例性地，丙烯酸酯类化合物包括：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸异戊酯、丙烯酸己酯、丙烯酸-2-乙基己酯、丙烯酸辛酯、丙烯酸癸酯、丙烯酸十二烷酯、丙烯酸十八 烷酯、丙烯酸异冰片酯、丙烯酸环己酯、丙烯酸二环戊烯酯、丙烯酸二环戊烯基氧乙酯、丙烯酸苄酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、丙烯酸-2-羟基-3-氯丙酯、丙烯酸-2-羟基-3-苯氧基丙酯、丙烯酸-2-羟基-3-烯丙氧基丙酯、2-丙烯酰氧基乙基-2-羟基丙基邻苯二甲酸酯、丙烯酸-2,2,2-三氟乙酯、1,3-丁二醇甲基醚丙烯酸酯、丙烯酸丁氧基乙酯、丙烯酸-β-羧基乙酯、琥珀酸单丙烯酰氧基乙酯、ω-羧基聚己内酯单丙烯酸酯、三甲基甲硅烷氧基乙基丙烯酸酯、二苯基-2-丙烯酰氧基乙基磷酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、双酚A二丙烯酸酯、EO改性双酚A二丙烯酸酯、PO改性双酚A二丙烯酸酯、氢化双酚A二丙烯酸酯、EO改性氢化双酚A二丙烯酸酯、PO改性氢化双酚A二丙烯酸酯、双酚F二丙烯酸酯、EO改性双酚F二丙烯酸酯、PO改性双酚F二丙烯酸酯、EO改性四溴双酚A二丙烯酸酯、三环癸烷二羟甲基二丙烯酸酯、甘油PO改性三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯单丙酸酯、二季戊四醇六丙烯酸酯、四羟甲基甲烷四丙烯酸酯等。Exemplarily, acrylic compounds include: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acrylic acid Octyl ester, decyl acrylate, dodecyl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-acrylate Allyloxypropyl ester, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2,2,2-trifluoroethyl acrylate, 1,3-butanediol methyl Ether acrylate, butoxyethyl acrylate, β-carboxyethyl acrylate, monoacryloxyethyl succinate, ω-carboxypolycaprolactone monoacrylate, trimethylsiloxyethyl acrylate Ester, diphenyl-2-acryloyloxyethyl phosphate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A diacrylate, EO modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified Bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol diacrylate, glycerol PO modified triacrylate, three Hydroxymethyl propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, etc.
示例性地，甲基丙烯酸酯类化合物包括：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异戊酯、甲基丙烯酸己酯、甲基丙烯酸-2-己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸辛酯、甲基丙烯酸癸酯、甲基丙烯酸十二烷酯、甲基丙烯酸十八烷酯、甲基丙烯酸异冰片酯、甲基丙烯酸环己酯、甲基丙烯酸二环戊烯酯、甲基丙烯酸二环戊烯基氧乙酯、甲基丙烯酸苄酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基-3-氯丙酯、甲基丙烯酸-2-羟基-3-苯氧基丙酯、甲基丙烯酸-2,2,2-三氟乙 酯、甲基丙烯酸-2,2,3,3-四氟丙酯、甲基丙烯酸-1H-六氟异丙酯、甲基丙烯酸-2-甲氧基乙酯、1,3-丁二醇甲基醚甲基丙烯酸酯、甲基丙烯酸丁氧基乙酯、甲氧基三乙二醇甲基丙烯酸酯、甲氧基聚乙二醇#400甲基丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、甲氧基三丙二醇甲基丙烯酸酯、甲氧基聚丙二醇甲基丙烯酸酯、乙氧基二乙二醇甲基丙烯酸酯、甲基丙烯酸-2-乙基己基卡必醇酯、甲基丙烯酸四氢糠酯、甲基丙烯酸苯氧基乙酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五甲基丙烯酸酯单丙酸酯、二季戊四醇六甲基丙烯酸酯等。Exemplarily, methacrylate compounds include: methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, Isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, twelve methacrylate Alkyl ester, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate Ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate Ester, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, -1H-hexafluoroisopropyl methacrylate, methacrylic acid- 2-Methoxy ethyl, 1,3-butanediol methyl ether methacrylate, butoxy ethyl methacrylate, methoxy triethylene glycol methacrylate, methoxy polyethylene Alcohol #400 Methacrylate, Methoxy Dipropylene Glycol Methacrylate, Methoxy Tripropylene Glycol Methacrylate, Methoxy Polypropylene Glycol Methacrylate, Ethoxy Diethylene Glycol Methacrylate, 2-Ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, Dipentaerythritol hexamethacrylate, etc.
非限制性地，所述具有至少一个聚合性不饱和键的化合物(C)还可列举出烯丙基缩水甘油醚、邻苯二甲酸二烯丙酯、偏苯三酸三烯丙酯、异氰尿酸三烯丙酯、丙烯酰胺、N-羟甲基丙烯酰胺、二丙酮丙烯酰胺、N,N-二甲基丙烯酰胺、N,N-二乙基丙烯酰胺、N-异丙基丙烯酰胺、丙烯酰基吗啉、苯乙烯、对羟基苯乙烯、对氯苯乙烯、对溴苯乙烯、对甲基苯乙烯、醋酸乙烯酯、单氯醋酸乙烯酯、苯甲酸乙烯酯、特戊酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、己二酸二乙烯酯等化合物。Without limitation, the compound (C) having at least one polymerizable unsaturated bond can also include allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, iso Triallyl cyanurate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide , Acryloyl morpholine, styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate , Vinyl butyrate, vinyl laurate, divinyl adipate and other compounds.
本发明中的具有至少一个聚合性不饱和键的化合物(C)可以仅使用一种，为了提高期望的特性也可以按任意比率混合两种或两种以上而使用。The compound (C) having at least one polymerizable unsaturated bond in the present invention may be used in only one type, and two or more types may be mixed and used in an arbitrary ratio in order to improve desired characteristics.
在100质量份感光性树脂组合物中，组分(C)的含量为5-50质量份，优选为10-30质量份。若组分(C)的含量过小，存在光致灵敏度下降的缺陷；若组分(C)的含量过大，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 component (C) is 5-50 parts by mass, preferably 10-30 parts by mass. If the content of component (C) is too small, there is a defect that the photosensitivity is reduced; if the content of component (C) is too large, there is a defect that the photoresist pattern tends to become wider than the line width of the photomask.
<着色剂(D)><Colorant (D)>
本发明对于着色剂(D)的种类没有特别限定，可以包括颜料和染料。In the present invention, the type of the colorant (D) is not particularly limited, and may include pigments and dyes.
颜料可以包括在相关领域中常用的任何有机颜料、无机颜料或它们的混合物。The pigment may include any organic pigments, inorganic pigments, or mixtures thereof commonly used in related fields.
有机颜料没有特别限制，可以包括用于印刷墨水、喷墨墨水等的任何通用颜料。更具体地，可以是水溶性偶氮颜料、不溶于水的偶氮颜料、酞菁颜料、喹吖啶酮颜料、异吲哚啉酮颜料、异吲哚啉颜料、二萘嵌苯颜料、芘酮颜料、二恶嗪颜料、蒽醌颜料、二蒽醌基颜料、蒽素嘧啶颜料、蒽嵌蒽醌颜料、阴丹酮颜料、黄士酮颜料、皮蒽酮颜料、吡咯并吡咯二酮颜料等。这些有机颜料可以单独使用或两种以上组合使用。Organic pigments are not particularly limited, and may include any general-purpose pigments used in printing inks, inkjet inks, and the like. More specifically, it may be water-soluble azo pigments, water-insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, pyrene Ketone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthraquinone pyrimidine pigments, anthraquinone pigments, indanthrone pigments, flavone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments Wait. These organic pigments can be used alone or in combination of two or more.
无机颜料没有特别限制，可以包括金属化合物(如金属氧化物或金属络合物)和炭黑。更具体地，可选自铁、钴、铝、镉、铅、铜、钛、镁、铬、锌和锑中的至少一种金属的氧化物。这些无机颜料可以单独使用或两种以上组合使用。The inorganic pigment is not particularly limited, and may include metal compounds (such as metal oxides or metal complexes) and carbon black. More specifically, it may be an oxide of at least one metal selected from iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. These inorganic pigments can be used alone or in combination of two or more kinds.
有机颜料和无机颜料还可以包括根据显色指数(Color Index，由英国染色家学会公布)归类为颜料的化合物。更具体地，可以使用C.I.颜料黄13、20、24、31、53、83、86、93、94、109、110、117、125、137、138、139、147、148、150、153、154、166、173、180、185；C.I.颜料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71；C.I.颜料红9、97、105、122、123、144、149、166、168、176、177、180、192、208、215、216、224、242、254、255、264；C.I.颜料紫14、19、23、29、32、33、36、37、38；C.I.颜料蓝15(15:3、15:4、15:6等)、21、28、60、64、76；C.I.颜料绿7、10、15、25、36、47、58；C.I.颜料棕28；C.I.颜料黑1、7等。其中，优选使用C.I.颜料黄138、139、150、185；C.I.颜料橙38；C.I.颜料红122、166、177、208、242、254、255；C.I.颜料紫23；C.I.颜料蓝15:3、15:6； C.I.颜料绿7、36、58等。这些颜料可以单独使用或两种以上组合使用。Organic pigments and inorganic pigments may also include compounds classified as pigments according to the Color Index (published by the British Society of Colourists). More specifically, CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154 can be used , 166, 173, 180, 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71; CI Pigment Red 9, 97, 105, 122 , 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, 38; CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, 76; CI Pigment Green 7, 10, 15, 25, 36, 47, 58; CI Pigment Brown 28; CI Pigment Black 1, 7, etc. Among them, it is preferable to use CI Pigment Yellow 138, 139, 150, 185; CI Pigment Orange 38; CI Pigment Red 122, 166, 177, 208, 242, 254, 255; CI Pigment Violet 23; CI Pigment Blue 15: 3, 15 :6; CI Pigment Green 7, 36, 58, etc. These pigments can be used alone or in combination of two or more.
无论是无机颜料还是有机颜料，若考虑到最好具有高透射率，则优选使用尽可能细的颜料，颜料的平均粒径优选为0.01-0.1μm，更优选为0.01-0.05μm。Regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment as fine as possible in consideration of the best transmittance, and the average particle diameter of the pigment is preferably 0.01-0.1 μm, more preferably 0.01-0.05 μm.
颜料的含量没有特别限制，但以总量100质量份的着色剂计，颜料的含量范围优选5-95重量份，进一步优选10-90重量份。如果颜料的含量在上述范围内，则利用该颜料制造的滤色器可具有充分的色彩区域和优异的透光率，且确保了所期望的感光度。The content of the pigment is not particularly limited, but based on the total amount of 100 parts by mass of the colorant, the content of the pigment ranges preferably from 5 to 95 parts by weight, more preferably from 10 to 90 parts by weight. If the content of the pigment is within the above range, the color filter manufactured using the pigment can have a sufficient color area and excellent light transmittance, and ensure the desired sensitivity.
染料没有特别限制，可以包括：具有酸基(如磺酸、羧酸等)的酸性染料；含氮化合物的盐和所述酸性染料的盐；所述酸性染料的磺酰胺和它们的衍生物；基于偶氮、氧杂蒽和/或酞菁的酸性染料和它们的衍生物等。The dye is not particularly limited, and may include: acid dyes with acid groups (such as sulfonic acid, carboxylic acid, etc.); salts of nitrogen-containing compounds and salts of the acid dyes; sulfonamides of the acid dyes and their derivatives; Acid dyes based on azo, xanthene, and/or phthalocyanine and their derivatives, etc.
染料优选是在显色指数(Color Index，由英国染色家学会公布)归类为染料的化合物，或者列于染色意见(Color Dyeing公司)中的染料中的红色染料、蓝色染料和紫色染料。The dye is preferably a compound classified as a dye in the Color Index (Color Index, published by the British Society of Dyers), or a red dye, a blue dye and a purple dye among the dyes listed in the dyeing opinion (Color Dyeing Company).
示例性地，可以是C.I.溶剂染料，包括：黄色染料，如C.I.溶剂黄4、14、15、16、21、23、24、38、56、62、63、68、79、82、93、94、98、99、151、162、163等；红色染料，如C.I.溶剂红8、45、49、89、111、122、125、130、132、146、179等；橙色染料，如C.I.溶剂橙2、7、11、15、26、41、45、56、62等；蓝色染料，如C.I.溶剂蓝5、35、36、37、44、59、67、70等；紫色染料，如C.I.溶剂紫8、9、13、14、36、37、47、49等；绿色染料，如C.I.溶剂绿1、3、4、5、7、28、29、32、33、34、35等。其中，优选C.I.溶剂黄14、16、21、56、151、79、93；C.I.溶剂红8、49、89、111、122、132、146、179；C.I.溶剂橙41、45、62；C.I.溶剂蓝35、36、44、45、70； C.I.溶剂紫13等。Exemplarily, it can be CI solvent dyes, including: yellow dyes, such as CI solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94 , 98, 99, 151, 162, 163, etc.; red dyes, such as CI solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, etc.; orange dyes, such as CI solvent orange 2 , 7, 11, 15, 26, 41, 45, 56, 62, etc.; blue dyes, such as CI solvent blue 5, 35, 36, 37, 44, 59, 67, 70, etc.; purple dyes, such as CI solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.; green dyes, such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. Among them, CI solvent yellow 14, 16, 21, 56, 151, 79, 93; CI solvent red 8, 49, 89, 111, 122, 132, 146, 179; CI solvent orange 41, 45, 62; CI solvent Blue 35, 36, 44, 45, 70; CI solvent violet 13, etc.
示例性地，可以是C.I.酸性染料，包括：黄色染料，如C.I.酸性黄1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251等；红色染料，如C.I.酸性红1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422、426等；橙色染料，如C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173等；蓝色染料，如C.I.酸性蓝1、7、9、15、18、23、25、27、29、40、42、45、51、62、70、74、80、83、86、87、90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、267、278、280、285、290、296、315、324:1、335、340等；紫色染料，如C.I.酸性紫6B、7、9、17、19、66等；绿色染料，如C.I.酸性绿1、3、5、9、16、25、27、50、58、63、65、80、104、105、106、109等。其中，优选C.I.酸性黄42；C.I.酸性红92；C.I.酸性蓝80、90；C.I.酸性紫66；C.I.酸性绿27等。Exemplarily, it can be CI acid dyes, including: yellow dyes, such as CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65 , 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161 ,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232 , 235, 238, 240, 242, 243, 251, etc.; red dyes, such as CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44 , 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158 ,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195 , 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc.; orange dyes, such as CI acid orange 6, 7, 8 , 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc.; blue dyes, such as CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340 etc.; purple Dyes, such as CI Acid Violet 6B, 7, 9, 17, 19, 66, etc.; green dyes, such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. Among them, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 and the like are preferred.
示例性地，可以是C.I.直接(direct)染料，包括：黄色染料，如C.I.直 接黄2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141等；红色染料，如C.I.直接红79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250等；橙色染料，如C.I.直接橙34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107等；蓝色染料，如C.I.直接蓝38、44、57、70、77、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275、293等；紫色染料，如C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104等；绿色染料，如C.I.直接绿25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等。Exemplarily, it may be CI direct dyes, including: yellow dyes, such as CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, etc.; red dyes, such as CI direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, etc.; orange dyes, such as CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc.; blue Color dyes, such as CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108 , 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173 , 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245 , 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc.; purple dyes, such as CI direct violet 47, 52, 54, 59, 60, 65, 66, 79 , 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, etc.; green dyes, such as CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67 , 68, 69, 72, 77, 79, 82, etc.
示例性地，可以是C.I.媒染染料，包括：黄色染料，如C.I.媒染黄5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65等；红色染料，如C.I.媒染红1、2、3、4、9、11、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95等；橙色染料，如C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48等；蓝色染料，如C.I.媒染蓝1、2、3、7、8、9、12、13、15、 16、19、20、21、22、23、24、26、30、31、32、39、40、41、43、44、48、49、53、61、74、77、83、84等；紫色染料，如C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58等；绿色染料，如C.I.媒染绿1、3、4、5、10、15、19、26、29、33、34、35、41、43、53等。Exemplarily, it may be CI mordant dyes, including: yellow dyes, such as CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 Etc.; red dyes, such as CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37 , 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, etc.; orange dyes, such as CI Mordant Orange 3, 4, 5 , 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc.; blue dyes, such as CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc.; purple dyes, such as CI mordant violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc.; green dyes, such as CI mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. .
上述染料可单独使用或以其中的两种以上的组合使用。The above-mentioned dyes can be used alone or in combination of two or more of them.
染料的含量没有特别限制，但以总量100质量份的着色剂计，染料的含量范围优选5-95重量份，进一步优选10-90重量份。如果染料的含量在上述范围内，则可以防止可靠性变差(在图案形成之后由有机溶剂导致的染料的洗脱)的同时获得优异的感光度。The content of the dye is not particularly limited, but based on the total amount of 100 parts by mass of the colorant, the content of the dye ranges preferably from 5 to 95 parts by weight, more preferably from 10 to 90 parts by weight. If the content of the dye is within the above range, it is possible to prevent deterioration in reliability (elution of the dye due to an organic solvent after pattern formation) while obtaining excellent sensitivity.
着色剂的含量没有特别限制，但在100质量份感光性树脂组合物中，着色剂(D)的含量通常为5-60质量份，优选为10-45质量份。如果着色剂的含量在上述范围内，则像素具有充分的色彩浓度，且在显影期间，非像素部分的缺失不减少，可以降低残留物的出现。The content of the colorant is not particularly limited, but in 100 parts by mass of the photosensitive resin composition, the content of the colorant (D) is usually 5-60 parts by mass, preferably 10-45 parts by mass. If the content of the colorant is within the above range, the pixel has a sufficient color density, and during development, the absence of non-pixel portions is not reduced, and the occurrence of residues can be reduced.
<供氢体(E)><Hydrogen Donor (E)>
本发明感光性树脂组合物还包括供氢体(E)，以便提升感光度。HABI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，但是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而引发单体聚合。The photosensitive resin composition of the present invention further includes a hydrogen donor (E) in order to improve sensitivity. HABI compounds are cleaved after exposure to light, and the monoimidazole radicals produced are large in volume, and the steric hindrance makes it less active. It is difficult to initiate monomer polymerization alone, but monoimidazole radicals are easy to deprive the active hydrogen on the hydrogen donor to produce New living free radicals initiate 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，示例性地，可以是胺类化合物、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，或以其中的两种或两种以上的组合使用。As long as it is a hydrogen donor having the above-mentioned characteristics, there is no particular limitation in terms of specific types. Illustratively, it may be an amine compound, a carboxylic acid compound, an organosulfur compound containing a mercapto group, or an alcohol compound. These compounds can be used alone or in combination of two or more of them.
示例性地，适用的胺类化合物可以是：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。Exemplarily, the applicable amine compounds may be: aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as methyl 4-dimethylaminobenzoate, 4 -Ethyl 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.
示例性地，适用的羧酸类化合物可以是：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。Exemplarily, suitable carboxylic acid compounds may be: aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, Dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, benzene Oxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.
示例性地，适用的含有巯基的有机硫化合物可以是：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。Exemplarily, suitable organic sulfur compounds containing mercapto groups may be: 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-mercapto Butyrate), 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 two Alcohol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octyl Glycol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(2-mercaptopropionate), Ethylene glycol bis(3-mercaptoisobutyrate), 1,2-propanediol bis(3-mercaptoisobutyrate), diethylene glycol bis(3-mercaptoisobutyrate), butanediol bis( 3-mercaptoisobutyrate), octanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), pentaerythritol tetra(3-mercaptoisobutyrate) , Dipentaerythritol hexa(3-mercaptoisobutyrate), ethylene glycol bis(2-mercaptoisobutyrate), 1,2-propanediol bis(2-mercaptoisobutyrate), diethylene glycol bis( 2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane tris(2-mercaptoisobutyrate) Ester), pentaerythritol tetra (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1,2-propanediol bis (4- Mercapto isovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylol Propane 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) Esters), 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-mercaptobutyl) , Phthalic acid bis (3-mercapto isobutyl ester) and so on.
示例性地，适用的醇类化合物可以是：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、新戊醇、正乙醇、环已醇、乙二醇、1,2-丙二醇、1,2,3-丙三醇、苯甲醇、苯乙醇等。Exemplarily, suitable alcohol compounds can be: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-ethanol, 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(E)的含量为0.01-20重量份，优选0.01-10重量份。如果供氢体的含量在上述范围内，可以进一步确保着色感光性树脂组合物的感光度。In 100 parts by mass of the photosensitive resin composition, the content of the hydrogen donor (E) is 0.01-20 parts by weight, preferably 0.01-10 parts by weight. If the content of the hydrogen donor is within the above range, the sensitivity of the colored photosensitive resin composition can be further secured.
<其它任选地添加剂(F)><Other optional additives (F)>
本发明的感光性树脂组合物中还可选择性地加入本领域中常用的其它助剂，包含其它的光引发剂和/或增感剂、有机溶剂、有机羧酸、颜料分散剂、粘附增强剂、均化剂、显影改进剂、抗氧化剂、热聚合抑制剂等。另外，根据用途还可以加入表面活性剂、荧光增白剂、增塑剂、阻燃剂、紫外线吸收剂、发泡剂、杀菌剂、抗静电剂、磁性物质、导电材料、抗真菌 或抗细菌材料、多孔吸附剂、芳香材料等。The photosensitive resin composition of the present invention can also optionally add other auxiliary agents commonly used in the art, including other photoinitiators and/or sensitizers, organic solvents, organic carboxylic acids, pigment dispersants, adhesives Reinforcing agent, leveling agent, development improver, antioxidant, thermal polymerization inhibitor, etc. In addition, surfactants, fluorescent whitening agents, plasticizers, flame retardants, ultraviolet absorbers, foaming agents, bactericides, antistatic agents, magnetic substances, conductive materials, anti-fungal or anti-bacteria can also be added according to the application. Materials, porous adsorbents, aromatic materials, etc.
所述其它的光引发剂和/或增感剂与上述光聚合引发剂A1和肟酯类光引发剂A2不同。非限制性地，可选自：双咪唑类化合物、三嗪类化合物、香豆素类化合物、吖啶类化合物、噁二唑类化合物、芳香族酮类化合物、苯偶姻和苯偶姻烷基醚类化合物、蒽醌类化合物、噻吨酮类化合物等。这些化合物可以单独使用或两种以上组合使用。The other photoinitiator and/or sensitizer are different from the photopolymerization initiator A1 and the oxime ester photoinitiator A2 described above. Without limitation, it can be selected from: bisimidazole compounds, triazine compounds, coumarin compounds, acridine compounds, oxadiazole compounds, aromatic ketone compounds, benzoin and benzoin alkane Base ether compounds, anthraquinone compounds, thioxanthone compounds, etc. These compounds can be used alone or in combination of two or more.
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，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，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.
示例性地，噁二唑类化合物包括：2-三氯甲基-5-苯乙烯基-1,3,4-噁二唑、2-三氯甲基-5-(氰基苯乙烯基)-1,3,4-噁二唑、2-三氯甲基-5-(萘甲酰-1-基)-1,3,4-噁二唑、2-三氯甲基-5-(4-苯乙烯基)苯乙烯基-1,3,4-噁二唑等。这些噁二唑类化合物可以单独使用或两种以上组合使用。Exemplarily, oxadiazole compounds include: 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthoyl-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-( 4-styryl)styryl-1,3,4-oxadiazole and the like. These oxadiazole 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，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，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，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，有机溶剂只要可溶解前述各组分，则没有特别限制，可以包括例如：二醇醚系溶剂、醇系溶剂、酯系溶剂、酮系溶剂、酰胺系溶剂及含氯溶剂等。优选特别考虑着色剂、碱可溶性树脂的溶解性、涂布性、安全性等来进行选择。优选乙基溶纤剂(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。这些溶剂单独使用，或以其中的两种或两种以上的组合使用。Exemplarily, the organic solvent is not particularly limited as long as it can dissolve the aforementioned components, and may include, for example, glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, and chlorine-containing solvents. It is preferable to select particularly in consideration of the solubility, coatability, safety, etc. of the colorant and alkali-soluble resin. Preferred ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutane Alcohol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl Ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate) Ester), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5, 5-trimethyl-2-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 are used alone or in combination of two or more of them.
示例性地，有机羧酸的种类没有特别限制，可以包括例如：甲酸、乙酸、丙酸、丁酸、戊酸、特戊酸、己酸、二乙基乙酸、庚酸、辛酸等脂肪 族单羧酸；乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸壬二酸、癸二酸、十三烷二酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基丁二酸、四甲基丁二酸、柠康酸等脂肪族二羧酸；1,2,3-丙三甲酸、乌头酸、降莰三酸等脂肪族三羧酸；苯甲酸、甲苯甲酸、异丙苯甲酸、2,3-二甲基苯甲酸、3,5-二甲基苯甲酸等芳香族单羧酸；邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三甲酸、均苯三甲酸、1,2,3,5-苯四甲酸、1,2,4,5-苯四甲酸等芳香族多元羧酸；以及苯基乙酸、氢化阿托酸、氢化桂皮酸、苦杏仁酸、苯基丁二酸、阿托酸、桂皮酸、桂皮酸甲酯、桂皮酸苄酯、亚桂皮基乙酸、香豆酸、伞形酸等其它的羧酸。这些有机羧酸单独使用，或以其中的两种或两种以上的组合使用。Exemplarily, the type of organic carboxylic acid is not particularly limited, and may include, for example: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, caprylic acid and other aliphatic monomers. Carboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, Aliphatic dicarboxylic acids such as ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; 1,2,3-propanetricarboxylic acid, aconitic acid, Aliphatic tricarboxylic acids such as norbornoic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumene acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid; o-benzene Dicarboxylic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid and other aromatic polybasic Carboxylic acid; and phenylacetic acid, hydrogenated atoric acid, hydrogenated cinnamic acid, mandelic acid, phenylsuccinic acid, atoric acid, cinnamic acid, methyl cinnamate, benzyl cinnamic acid, cinnamic acid, incense Soybean acid, umbrella acid and other carboxylic acids. These organic carboxylic acids are used alone or in combination of two or more of them.
示例性地，分散剂的种类没有特别限制，可以包括例如：高分子分散剂如聚酰胺型胺及其盐、聚羧酸及其盐、高分子量不饱和酸酯、改性聚氨酯、改性聚酯、改性聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、萘磺酸甲醛缩合物，聚氧乙烯烷基磷酸酯，聚氧乙烯烷基胺，烷醇胺，颜料衍生物等。这些分散剂单独使用，或以其中的两种或两种以上的组合使用。Exemplarily, the type of dispersant is not particularly limited, and may include, for example, polymer dispersants such as polyamide-type amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified poly Ester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate, polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative Wait. These dispersants are used alone or in combination of two or more of them.
示例性地，粘附增强剂的种类没有特别限制，可以包括例如：乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基二甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三甲氧基硅烷、3-异氰酸酯丙基三甲氧基硅烷、3-异氰酸酯丙基三乙氧基硅烷等。这些粘附增强剂单独使用，或以其中的两种 或两种以上的组合使用。Exemplarily, the type of adhesion enhancer is not particularly limited, and may include, for example, vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N- (2-Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, etc. These adhesion enhancers can be used alone or in combination of two or more of them.
示例性地，热聚合抑制剂可以包括例如：对甲氧基苯酚、氢醌、邻苯二酚、叔丁基邻苯二酚、酚噻嗪和对甲氧基苯酚等。这些热聚合抑制剂单独使用，或以其中的两种或两种以上的组合使用。Exemplarily, the thermal polymerization inhibitor may include, for example, p-methoxyphenol, hydroquinone, catechol, tert-butylcatechol, phenothiazine, p-methoxyphenol, and the like. These thermal polymerization inhibitors are used alone or in combination of two or more of them.
示例性地，表面活性剂的种类没有特别限制，可以包括例如：氟表面活性剂、硅表面活性剂或它们的混合物。这些表面活性剂单独使用，或以其中的两种或两种以上的组合使用。Illustratively, the types of surfactants are not particularly limited, and may include, for example, fluorosurfactants, silicon surfactants, or mixtures thereof. These surfactants are used alone or in combination of two or more of them.
示例性地，增塑剂的种类没有特别限制，可以包括例如：酞酸二辛酯、酞酸二(十二烷基)酯、三乙二醇二辛酸酯、酞酸二甲基乙二醇酯、磷酸三甲苯酯、己二酸二辛酯、癸二酸二丁酯、三乙酰基甘油等。这些增塑剂单独使用，或以其中的两种或两种以上的组合使用。Exemplarily, the type of plasticizer is not particularly limited, and may include, for example, dioctyl phthalate, di(dodecyl) phthalate, triethylene glycol dicaprylate, and dimethyl ethylene phthalate. Alcohol esters, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol, etc. These plasticizers are used alone or in combination of two or more of them.
<彩色滤光片及其制造方法><Color filter and its manufacturing method>
如上文所述，本发明还涉及使用上述感光性树脂组合物的彩色滤光片及其制造方法。As mentioned above, this invention also relates to the color filter using the said photosensitive resin composition, and its manufacturing method.
本发明的彩色滤光片，其特征在于，在支撑体上具有使用上述感光性树脂组合物形成的着色图案。The color filter of the present invention is characterized by having a colored pattern formed using the above-mentioned photosensitive resin composition on a support.
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 carried out 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就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通常在70-110℃下、2-4分钟左右的条件下被干燥，形成感光性树脂层。The photosensitive resin composition applied on the support is usually dried at 70-110°C for about 2-4 minutes to form a photosensitive resin layer.
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。在此过程中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. In this process, only the portion of the coating film irradiated with light is cured.
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.
作为显影温度，通常为20-30℃，显影时间为20-90秒。As the developing temperature, it 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.
本发明的感光性树脂组合物具有优异的感光度和良好的显影性，固化后亮度高，且与基板密合性优异。所述制造方法能够以高的生产效率来制造高性能的彩色滤光片。The photosensitive resin composition of the present invention has excellent sensitivity and good developability, high brightness after curing, and excellent adhesion to a substrate. The manufacturing method can manufacture high-performance color filters with high production efficiency.
附图说明Description of the drawings
附图1是产物a1的高效液相色谱图。Figure 1 is a high performance liquid chromatogram of product a1.
附图2是T1的高效液相色谱图。Figure 2 is a high performance liquid chromatogram of T1.
附图3是T2的高效液相色谱图。Figure 3 is a high performance liquid chromatogram of T2.
附图4是T3的高效液相色谱图。Figure 4 is a high performance liquid chromatogram of T3.
附图5是T1经单晶衍射得到的结构谱图。Figure 5 is a structure spectrum obtained by single crystal diffraction of T1.
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、HABI类混合光引发剂的制备1. Preparation of HABI mixed photoinitiator
1.1 HABI类混合光引发剂a1的制备1.1 Preparation of HABI-type mixed photoinitiator a1
氮气保护下，向1L的四口烧瓶中投入31.8g 2-(邻氯苯基)-4,5-二苯基-咪唑(M1)、51.3g 2,5-二(邻氯苯基)-4-(3,4-二甲氧基苯基)-咪唑(M2)、4.2g 30％液碱、4.0g四丁基溴化铵和300g甲苯，加热搅拌，并在60-65℃时滴加85g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M1和M2均小于1％，反应完全，结束保温。保温反应结束后，用100g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70g甲醇，加热搅拌至溶清，再将溶清液滴加至由30g甲醇和50g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79.1g产物a1。Under the protection of nitrogen, put 31.8g 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1) and 51.3g 2,5-bis(o-chlorophenyl)- into a 1L four-necked flask. 4-(3,4-Dimethoxyphenyl)-imidazole (M2), 4.2g 30% liquid caustic soda, 4.0g tetrabutylammonium bromide and 300g toluene, heated and stirred, and dropped at 60-65℃ Add 85 g of sodium hypochlorite (11% aqueous solution), after the dripping is completed, the reaction is incubated, and sampling is controlled by HPLC until M1 and M2 are both less than 1%, the reaction is complete, and the incubation is terminated. After the completion of the heat preservation reaction, it was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was subjected to vacuum distillation. Add 70g of methanol to the material obtained by distillation, heat and stir until it is dissolved, and then add the dissolved solution dropwise to a solution of 30g of methanol and 50g of pure water, and filter, rinse, and dry after the addition is complete , 79.1g 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。分析结果显示，2-1’、2-3’、2’-1和2’-3四种连接位的产品峰总含量为92.5％。产物a1是由两个不同的单咪唑(即M1、M2)经两两自身偶合和相互偶合得到的混合物，包括T1、T2和T3。The product a1 was analyzed by high performance liquid chromatography, and the results are shown in Figure 1. The analysis results show that the total peak content of the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 is 92.5%. The product a1 is a mixture of two different monoimidazoles (ie, M1, M2) through self-coupling and mutual coupling, including T1, T2 and T3.
为精确验证产物的结构组成，分别对成分T1、T2和T3进行验证分析。通过单咪唑自身偶合、柱层析、色谱分离等手段，分别得到纯的T1、T2和T3，分别进行结构确认。In order to accurately verify the structure and composition of the product, the components T1, T2 and T3 were verified and analyzed. By means of monoimidazole self-coupling, column chromatography, chromatographic separation, etc., pure T1, T2 and T3 were obtained, and the structure was confirmed respectively.
附图2-4分别是T1、T2和T3的高效液相色谱图。Figures 2-4 are respectively the high performance liquid chromatograms of T1, T2 and T3.
T1在液相中只有一个峰，但通过单晶衍射得到两个峰形，见附图5。 结合结构特征可以确定，两个单咪唑偶合其主要产物是其中一个咪唑上的含有氢的N与另一个咪唑上2位的C连接而成的混合物，由此表明T1的结构为本发明中所述的2’-1和2’-3两种连接位。T1 has only one peak in the liquid phase, but two peak shapes are obtained by single crystal diffraction, see Figure 5. Combining the structural characteristics, it can be determined that the main product of the coupling of two monoimidazoles is a mixture of hydrogen-containing N on one imidazole and C on the 2 position of the other imidazole, which indicates that the structure of T1 is the present invention. The 2'-1 and 2'-3 two connection positions mentioned above.
合成T1的单咪唑是M1，属于对称型咪唑，所以偶合得到的2’-1和2’-3极性相似，液相难以进行分离。并且由于M1的结构对称性，由其自身偶合得到的产物结构中2’-1与2-1’结构相同，2’-3与2-3’的结构也相同，所以T1主结构为2’-1和2’-3两种连接位的产物，分别为T1-1：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑；T1-2：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-2’,3-二咪唑。结构式如下所示：The monoimidazole used to synthesize T1 is M1, which is a symmetrical imidazole, so the 2'-1 and 2'-3 obtained by coupling are similar in polarity, and it is difficult to separate the liquid phase. And due to the structural symmetry of M1, the structure of the product obtained by coupling itself has the same structure of 2'-1 and 2-1', and the structure of 2'-3 and 2-3' are also the same, so the main structure of T1 is 2' -1 and 2'-3 are the products of two attachment positions, respectively T1-1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2 '-Diimidazole; T1-2: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole. The structural formula is as follows:
Figure PCTCN2020081284-appb-000008
Figure PCTCN2020081284-appb-000008
合成T2的单咪唑M2属于不对称的单咪唑，M2存在两种构型，M2-1和M2-2，结构式如下所示：Synthetic monoimidazole M2 of T2 belongs to asymmetric monoimidazole, M2 has two configurations, M2-1 and M2-2, the structural formula is as follows:
Figure PCTCN2020081284-appb-000009
Figure PCTCN2020081284-appb-000009
对分离得到的纯T2进行分析，主结构为四个连接位产品，进行LCMS 确认结构。质谱分析借助仪器附带软件得到849与850分子碎片峰，产品的分子量为848，与T+1和T+2吻合，证明这四个产物结构相仿，分子量相同。T2由不对称的单咪唑偶合合成，理论存在八种1-2和2-3连接位连接的主结构，但对于自身偶合的单咪唑，结构中的2’-1与2-1’结构相同，2’-3与2-3’的结构也相同，所以对于T2来说，其实际存在四种1-2和2-3连接位连接的主结构，其组成分别为：T2-1：2,2’,5,5’-四(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-2’,3-二咪唑；T2-2：2,2’,4,5’-四(邻氯苯基)-4’,5-双(3,4-二甲氧基苯基)-1,2’-二咪唑；T2-3：2,2’,5,5’-四(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-1,2’-二咪唑；T2-4：2,2’,4,5’-四(邻氯苯基)-4’,5-双(3,4-二甲氧基苯基)-2’,3-二咪唑。结构式如下所示：Analyze the separated pure T2, the main structure is the four link products, and the structure is confirmed by LCMS. Mass spectrometry analysis uses the software attached to the instrument to obtain 849 and 850 molecular fragment peaks. The molecular weight of the product is 848, which is consistent with T+1 and T+2, which proves that the four products have similar structures and the same molecular weight. T2 is synthesized by asymmetric monoimidazole coupling. There are theoretically eight main structures connected by 1-2 and 2-3 connection positions, but for self-coupled monoimidazole, the 2'-1 and 2-1' structures in the structure are the same , 2'-3 and 2-3' have the same structure, so for T2, there are actually four main structures connected by 1-2 and 2-3 connection positions, and their composition is: T2-1: 2 ,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole; T2-2: 2, 2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole; T2-3: 2,2 ',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole; T2-4: 2,2' ,4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole. The structural formula is as follows:
Figure PCTCN2020081284-appb-000010
Figure PCTCN2020081284-appb-000010
T3是由M1与M2两两偶合而成，分离得到的纯T3在液相中主结构为四种连接位的产品，对四种连接位的产品进行LCMS确认结构。质谱分析 借助仪器附带软件得到755与756分子碎片峰，产品的分子量为754，与T+1和T+2吻合，证明这四个产物结构相仿，分子量相同。T3由对称的咪唑M1与不对称的咪唑M2两两连接而成，存在四种1-2和2-3连接位连接的主结构，其组成分别为：T3-1：2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,2’-二咪唑；T3-2：2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-2’,3-二咪唑；T3-3：2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-2,3’-二咪唑；T3-4：2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1’,2-二咪唑。结构式如下所示：T3 is formed by the coupling of M1 and M2. The main structure of the separated pure T3 in the liquid phase is the product of four connection positions, and the LCMS confirms the structure of the product of the four connection positions. Mass spectrometry analysis The 755 and 756 molecular fragment peaks are obtained with the aid of the software attached to the instrument. The molecular weight of the product is 754, which is consistent with T+1 and T+2, which proves that the four products have similar structures and the same molecular weight. T3 is formed by two-by-two connection of symmetric imidazole M1 and asymmetric imidazole M2. There are four main structures connected by 1-2 and 2-3 connection positions. The composition is respectively: T3-1: 2, 2', 5 -Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole; T3-2: 2,2' ,5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole; T3-3: 2, 2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole; T3-4: 2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole. The structural formula is as follows:
Figure PCTCN2020081284-appb-000011
Figure PCTCN2020081284-appb-000011
综合上述实验分析确定，产物a1是由T1(T1-1、T1-2)、T2(T2-1、T2-2、T2-3、T2-4)和T3(T3-1、T3-2、T3-3、T3-4)组合而成，其中由2-1’、2-3’、2’-1和2’-3四种连接位构成的双咪唑化合物在a1中的含量为 92.5％。Based on the above experimental analysis, it is determined that the product a1 is composed of T1 (T1-1, T1-2), T2 (T2-1, T2-2, T2-3, T2-4) and T3 (T3-1, T3-2, T3-3, T3-4) are combined, in which the content of the bisimidazole compound composed of 2-1', 2-3', 2'-1 and 2'-3 four connection positions in a1 is 92.5% .
参照上述过程，制备得到a2-a8，各产品情况如下表1-1所示。With reference to the above process, a2-a8 was prepared. The conditions of each product are shown in Table 1-1 below.
表1-1Table 1-1
Figure PCTCN2020081284-appb-000012
Figure PCTCN2020081284-appb-000012
注：为了防止分子间缔合现象的发生，采用乙腈为溶剂，配成溶度为1×10 -4mol/L的溶液，在25℃下测量溶液的紫外吸收光谱，再根据公式ε＝A/CL(摩尔消光系数单位L×mol -1×cm -1)计算在365nm(i线)波长处的摩尔消光系数。 Note: In order to prevent the occurrence of intermolecular association phenomenon, use acetonitrile as the solvent to prepare a solution with a solubility of 1×10 -4 mol/L, measure the UV absorption spectrum of the solution at 25°C, and then use the formula ε=A /CL (molar extinction coefficient unit L×mol -1 ×cm -1 ) Calculate the molar extinction coefficient at the wavelength of 365nm (i line).
1.2 HABI类混合光引发剂a9的制备1.2 Preparation of HABI-type mixed photoinitiator a9
氮气保护下，向1L的四口烧瓶中投入50g 2-(4-氯苯基)-5-(6-氯苯基)-4-(3,4-二甲氧基苯基)-咪唑(M3)、51g 2,5-二(邻氯苯基)-4-(3,4-二甲氧基苯基)-咪唑(M2)、5.6g 30％液碱、4.0g四丁基溴化铵和300g甲苯，加热搅拌，并在60-65℃时滴加90g次氯酸钠(11％的水溶液)，滴加结束后保温反应，取样通过HPLC进行中控，至M2和M3均小于1％，反应完全，结束保温。保温反应结束后，用100g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70g甲醇，加热搅拌至溶清，再将溶清液滴加至由30g甲醇和50g纯水配置而成的溶液中，滴加结束后进行淋洗、抽干、烘料，得到98g产物a9。Under the protection of nitrogen, put 50g of 2-(4-chlorophenyl)-5-(6-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole ( M3), 51g 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole (M2), 5.6g 30% liquid caustic soda, 4.0g tetrabutyl bromide Ammonium and 300g toluene, heated and stirred, and 90g sodium hypochlorite (11% aqueous solution) was added dropwise at 60-65°C. After the dropwise addition was completed, the reaction was kept warm, sampling was carried out by HPLC for central control until both M2 and M3 were less than 1%. Completely, end the insulation. After the completion of the heat preservation reaction, it was washed four times with 100 g of pure water, and then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was subjected to vacuum distillation. Add 70g of 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 30g methanol and 50g pure water. After the addition is complete, rinse, drain and dry Material, to obtain 98 g of product a9.
分析结果显示，2-1’、2-3’、2’-1和2’-3四种连接位的产品峰总含量为93.2％。The analysis results show that the total peak content of the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 is 93.2%.
产物a9是由两个不同的单咪唑(即M2、M3)经两两自身偶合和相互偶合得到的混合物，包括T2、T4和T5。为精确验证产物的结构组成，分别对成分T2、T4和T5进行验证分析。通过单咪唑自身偶合、柱层析、色谱分离等手段，分别得到T2、T4和T5，分别进行结构确认。The product a9 is a mixture of two different monoimidazoles (ie, M2, M3) through self-coupling and mutual coupling, including T2, T4 and T5. In order to accurately verify the structural composition of the product, the components T2, T4 and T5 were verified and analyzed. Through monoimidazole self-coupling, column chromatography, chromatographic separation and other means, T2, T4 and T5 were obtained respectively, and the structure was confirmed respectively.
T2与化合物a1中的结构T2一致。T2 is consistent with the structure T2 in compound a1.
T4由不对称的单咪唑M3自身偶合而成，存在四种1-2和2-3连接位连接的主结构，其组成分别为：T4-1：2,2’-双(4-氯苯基)-5,5’-双(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-2,3’-二咪唑；T4-2：2,2’-双(4-氯苯基)-4,5’-双(邻氯苯基)-4’,5-双(3,4-二甲氧基苯基)-1,2’-二咪唑；T4-3：2,2’-双(4-氯苯基)-5,5’-双(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-1,2’-二咪唑；T4-4：2,2’-双(4-氯苯基)-4’,5–双(邻氯苯基)-4,5’-双(3,4-二甲氧基苯基)-2,3’-二咪唑。结构式如下所示：T4 is formed by self-coupling of asymmetric monoimidazole M3. There are four main structures connected by 1-2 and 2-3 connection positions. The composition is respectively: T4-1: 2,2'-bis(4-chlorobenzene Yl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole; T4-2: 2,2 '-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole ; T4-3: 2,2'-bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) -1,2'-diimidazole; T4-4: 2,2'-bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4 -Dimethoxyphenyl)-2,3'-diimidazole. The structural formula is as follows:
Figure PCTCN2020081284-appb-000013
Figure PCTCN2020081284-appb-000013
进行LCMS确认结构，四个结构谱图一致。质谱分析借助仪器附带软件得到849与850分子碎片峰，产品的分子量为848，与T+1和T+2吻合，证明这四个产物峰结构相仿，分子量相同。The structure was confirmed by LCMS, and the four structural spectra were consistent. Mass spectrometry analysis uses the software attached to the instrument to obtain 849 and 850 molecular fragment peaks. The molecular weight of the product is 848, which is consistent with T+1 and T+2, which proves that the four product peaks have similar structures and the same molecular weight.
T5由不对称的M2和不对称的M3两两偶合而成，存在四种1-2和2-3连接位连接的主结构，其组成分别为：T5-1：2-(4-氯苯基)-2’,5,5’-三(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-2,3’-二咪唑；T5-2：2’-(4-氯苯基)-2,5,5’-三(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-1,2’-二咪唑；T5-3：2-(4-氯苯基)-2’,5,5’-三(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-2’,3-二咪唑；T5-4：2’-(4-氯苯基)-2,5,5’-三(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-1’,2-二咪唑。结构式如下所示：T5 is formed by the two-by-two coupling of asymmetric M2 and asymmetric M3. There are four main structures connected by 1-2 and 2-3 connection positions. The composition is respectively: T5-1: 2-(4-chlorobenzene Group)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole; T5-2: 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'- Diimidazole; T5-3: 2-(4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) )-2',3-diimidazole; T5-4: 2'-(4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4 -Dimethoxyphenyl)-1',2-diimidazole. The structural formula is as follows:
Figure PCTCN2020081284-appb-000014
Figure PCTCN2020081284-appb-000014
进行LCMS确认结构，四个结构谱图一致。质谱分析借助仪器附带软件得到849与850分子碎片峰，产品的分子量为848，与T+1和T+2吻合，证明这四个产物峰结构相仿，分子量相同。The structure was confirmed by LCMS, and the four structural spectra were consistent. Mass spectrometry analysis uses the software attached to the instrument to obtain 849 and 850 molecular fragment peaks. The molecular weight of the product is 848, which is consistent with T+1 and T+2, which proves that the four product peaks have similar structures and the same molecular weight.
综合上述实验分析确定，产物a9是由T2(T2-1、T2-2、T2-3、T2-4)、T4(T4-1、T4-2、T4-3、T4-4)和T5(T5-1、T5-2、T5-3、T5-4)组合而成，其中由2-1’、2-3’、2’-1和2’-3四种连接位构成的双咪唑化合物在a9中的含量为93.2％。Based on the above experimental analysis, it is determined that the product a9 is composed of T2 (T2-1, T2-2, T2-3, T2-4), T4 (T4-1, T4-2, T4-3, T4-4) and T5 ( T5-1, T5-2, T5-3, T5-4) are a combination of bisimidazole compounds composed of 2-1', 2-3', 2'-1 and 2'-3 The content in a9 is 93.2%.
参照上述过程，分别制备得到a10-a16，各产品情况如下表1-2所示。Refer to the above process to prepare a10-a16 respectively, and the conditions of each product are shown in Table 1-2 below.
表1-2Table 1-2
Figure PCTCN2020081284-appb-000015
Figure PCTCN2020081284-appb-000015
Figure PCTCN2020081284-appb-000016
Figure PCTCN2020081284-appb-000016
注：为了防止分子间缔合现象的发生，采用乙腈为溶剂，配成溶度为1×10 -4mol/L的溶液，在25℃下测量溶液的紫外吸收光谱，再根据公式ε＝A/CL(摩尔消光系数单位L×mol -1×cm -1)计算在365nm(i线)波长处的摩尔消光系数。 Note: In order to prevent the occurrence of intermolecular association phenomenon, use acetonitrile as the solvent to prepare a solution with a solubility of 1×10 -4 mol/L, measure the UV absorption spectrum of the solution at 25°C, and then use the formula ε=A /CL (molar extinction coefficient unit L×mol -1 ×cm -1 ) Calculate the molar extinction coefficient at the wavelength of 365nm (i line).
1.3 HABI类混合光引发剂a171.3 HABI mixed photoinitiator a17
a17是常州强力电子新材料股份有限公司生产的BCIM，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物(由于是对称结构，故而2-1’与2’-1是同一种结构，2-3’与2’-3是同一种结构)，且该四种连接位的双咪唑化合物在A1中的总质量百分含量为99％，在365nm(i线)波长处的摩尔消光系数为26L×mol -1×cm -1。结构式如下所示： a17 is a BCIM produced by Changzhou Qiangli Electronic New Materials Co., Ltd., which contains bisimidazole compounds with four connection positions of 2-1', 2-3', 2'-1 and 2'-3 (due to the symmetrical structure, it is 2-1' and 2'-1 are the same structure, 2-3' and 2'-3 are the same structure), and the total mass percentage of the four connected bisimidazole compounds in A1 is 99 %, the molar extinction coefficient at the wavelength of 365nm (i-line) is 26L×mol -1 ×cm -1 . The structural formula is as follows:
Figure PCTCN2020081284-appb-000017
Figure PCTCN2020081284-appb-000017
2.感光性树脂组合物的制备2. Preparation of photosensitive resin composition
参照表2-1、2-2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 formulations shown in Tables 2-1 and 2-2, 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2-1table 2-1
Figure PCTCN2020081284-appb-000018
Figure PCTCN2020081284-appb-000018
表2-2Table 2-2
Figure PCTCN2020081284-appb-000019
Figure PCTCN2020081284-appb-000019
其中，表2-1和2-2中各组分代表的含义如表2-3中所示。Among them, the meaning of each component in Table 2-1 and 2-2 is shown in Table 2-3.
表2-3Table 2-3
Figure PCTCN2020081284-appb-000020
Figure PCTCN2020081284-appb-000020
Figure PCTCN2020081284-appb-000021
Figure PCTCN2020081284-appb-000021
参照上述摩尔消光系数的测试方法，实施例1-10和比较例1-12中光聚合引发剂在365nm(i线)波长处的摩尔消光系数如下表2-4所示。With reference to the above-mentioned testing method for molar extinction coefficient, the molar extinction coefficients of the photopolymerization initiators in Examples 1-10 and Comparative Examples 1-12 at a wavelength of 365 nm (i line) are shown in Table 2-4 below.
表2-4Table 2-4
实施例Example ε 365nm ε 365nm 比较例Comparative example ε 365nm ε 365nm
11 96839683 11 1009410094
22 97149714 22 98479847
33 97429742 33 96369636
44 96309630 44 95659565
55 96619661 55 95159515
66 96929692 66 93509350
77 99479947 77 93509350
88 91579157 88 95589558
99 83678367 99 95159515
1010 55135513 1010 95509550
 To  To 1111 57335733
 To  To 1212 1100011000
3.性能评价3. Performance evaluation
3.1亮度3.1 Brightness
对于各实施例和比较例中制备的感光性树脂组合物，使用旋转涂布法，在玻璃(#1737，康宁公司制造)上涂布上述所得的感光性树脂组合物，然后在100℃下花3分钟使挥发成分挥发而形成感光性树脂层。冷却后，使用超高压水银灯对该感光性树脂层进行曝光，照射光量设为100mJ/cm 2。接着在230℃下进行20分钟后烘烤，获得具有膜厚为2μm的着色层的玻璃基板。使用奥林巴斯(Olympus)制造的显微分光测定装置OSP-SP200，测定具有着色层的玻璃基板的色度，以C光源来测定x＝0.29、y＝0.59的色度时的Y值。Y值越高，作为液晶显示装置用的彩色滤光片显示越良好的性能。 For the photosensitive resin composition prepared in each of the Examples and Comparative Examples, the photosensitive resin composition obtained above was coated on glass (#1737, manufactured by Corning Corporation) using a spin coating method, and then the photosensitive resin composition was applied at 100°C. The volatile component is volatilized in 3 minutes to form a photosensitive resin layer. After cooling, the photosensitive resin layer was exposed using an ultra-high pressure mercury lamp, and the irradiation light amount was set to 100 mJ/cm 2 . Then, post-baking was performed at 230°C for 20 minutes to obtain a glass substrate having a colored layer with a film thickness of 2 μm. The chromaticity of the glass substrate having the colored layer was measured using a microscope OSP-SP200 manufactured by Olympus, and the Y value when the chromaticity of x=0.29 and y=0.59 was measured with a C light source. The higher the Y value, the better performance as a color filter for liquid crystal display devices.
Y值是根据下述判定基准来判定：The Y value is determined according to the following criteria:
○：Y值为57以上；○: Y value is 57 or more;
◎：Y值为55以上且小于57；◎: Y value is 55 or more and less than 57;
●：Y值小于55。●: Y value is less than 55.
3.2感光度3.2 Sensitivity
对于各实施例和比较例中制备的感光性树脂组合物，使用旋转涂布法，在玻璃(#1737，康宁公司制造)上涂布上述所得的感光性树脂组合物，然后在100℃下花3分钟使挥发成分挥发而形成感光性树脂层。冷却后，使用i线缩小投影曝光装置，以365nm的波长，通过纵20μm×横20μm的遮罩且以曝光量成为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。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： For the photosensitive resin composition prepared in each of the Examples and Comparative Examples, the photosensitive resin composition obtained above was coated on glass (#1737, manufactured by Corning Corporation) using a spin coating method, and then the photosensitive resin composition was applied at 100°C. The volatile component is volatilized in 3 minutes to form a photosensitive resin layer. After cooling, using an i-line reduction projection exposure device, the coating film was irradiated with a wavelength of 365 nm through a mask of 20 μm in length×20 μm in width so that the exposure amount became 50 mJ/cm 2 . After the irradiation, using a developer (trade name: CD-2000, 60%, manufactured by Fujifilm Electronic Materials), the coating film was developed at 23° C. for 60 seconds. 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 pixel pattern obtained is the higher sensitivity, so it is better. 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.
3.3显影性3.3 developability
对于各实施例和比较例中制备的感光性树脂组合物，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，附上掩膜板，通过装有高压汞灯的RW-UV.70201履带式曝机，辐射波长250-450nm，单次曝光接收的能量约为80mJ/cm 2，通过掩膜板的缝隙在紫外线照射下对涂膜进行曝光；25℃温度下，使用1％的NaOH水溶液显影，再用超纯水洗涤，风干；最后，在240℃的烘箱中后烘烤30min，得到掩膜板转移的图案。 For the photosensitive resin composition prepared in each example and comparative example, the liquid composition was 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 the above-mentioned thickness of the coating film, the coating process can be completed once or in multiple times; the substrate with the coating film is cooled to room temperature, attached with a mask, and passed through the RW-UV equipped with a high-pressure mercury lamp .70201 crawler aerator, radiation wavelength 250-450nm, the energy received by a single exposure is about 80mJ/cm 2 , the coating film is exposed under ultraviolet radiation through the gap of the mask plate; at a temperature of 25 ℃, use 1% Developed with NaOH aqueous solution, then washed with ultrapure water, and air-dried; finally, post-baked in an oven at 240°C for 30 minutes to obtain the pattern transferred from the mask.
用扫描电子显微镜(SEM)观察基板上图案，以评价显影性。判定基准如下：The pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability. The criteria are as follows:
○：在未曝光部分未观察到残留物；○: No residue is 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 residues are observed in unexposed parts.
3.4附着力评价3.4 Evaluation of adhesion
以3.3得到的图案为对象，参照GB9286-88《色漆和清漆漆膜的划格试验》，通过划格实验方法评价涂膜附着力好坏。根据破坏程度分为0-5级(共6个等级),其中最好为0级,膜面没有任一个小格脱落；5级为极差,膜面产生了严重的剥落。Taking the pattern obtained in 3.3 as the object, refer to GB9286-88 "Cross-cut test of paint and varnish film", and evaluate the adhesion of the coating film through the cross-cut test method. According to the degree of damage, it is divided into 0-5 grades (a total of 6 grades), among which the best grade is 0, and no small grids fall off the membrane surface; grade 5 is extremely poor, and the membrane surface has severe peeling.
评价结果如表3中所示。The evaluation results are shown in Table 3.
表3table 3
 To 亮度brightness 感光度Sensitivity 显影性Developability 附着力Adhesion
实施例1Example 1 ○○ ○○ ○○ 00
实施例2Example 2 ○○ ○○ ○○ 00
实施例3Example 3 ○○ ○○ ○○ 00
实施例4Example 4 ○○ ○○ ○○ 00
实施例5Example 5 ○○ ○○ ○○ 00
实施例6Example 6 ○○ ○○ ○○ 00
实施例7Example 7 ○○ ○○ ○○ 00
实施例8Example 8 ○○ ○○ ○○ 00
实施例9Example 9 ○○ ○○ ○○ 00
实施例10Example 10 ○○ ○○ ○○ 00
对比例1Comparative example 1 ●● ○○ ●● 33
对比例2Comparative example 2 ●● ○○ ●● 44
对比例3Comparative example 3 ○○ ◎◎ ○○ 11
对比例4Comparative example 4 ○○ ◎◎ ○○ 11
对比例5Comparative example 5 ○○ ◎◎ ○○ 11
对比例6Comparative example 6 ●● ○○ ●● 33
对比例7Comparative example 7 ●● ○○ ●● 33
对比例8Comparative example 8 ○○ ○○ ○○ 11
对比例9Comparative example 9 ○○ ○○ ○○ 11
对比例10Comparative example 10 ○○ ○○ ○○ 11
对比例11Comparative example 11 ◎◎ ◎◎ ○○ 22
对比例12Comparative example 12 ◎◎ ○○ ○○ 11
从表3的结果可以看出，实施例的组合物在应用于制备滤光片时，表现出了优异的感光度和良好的显影性，固化后亮度高，且与基板密合性优异。相较于比较例的感光性树脂组合物，本发明的综合应用性能优势显著。It can be seen from the results in Table 3 that when the composition of the example is applied to prepare a filter, it exhibits excellent sensitivity and good developability, high brightness after curing, and excellent adhesion to the substrate. Compared with the photosensitive resin composition of the comparative example, the present invention has significant advantages in comprehensive application performance.
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 (14)

  1. 一种用于彩色滤光片的感光性树脂组合物，包含下列组分：A photosensitive resin composition for color filters, comprising the following components:
    (A)光聚合引发剂，包括光聚合引发剂A1和至少一种肟酯类光引发剂A2；(A) Photopolymerization initiator, including photopolymerization initiator A1 and at least one oxime ester photoinitiator A2;
    (B)碱可溶性树脂；(B) Alkali-soluble resin;
    (C)具有至少一个聚合性不饱和键的化合物；(C) A compound having at least one polymerizable unsaturated bond;
    (D)着色剂；(D) Coloring agent;
    (E)供氢体；(E) Hydrogen donor;
    其中，光聚合引发剂A1为六芳基双咪唑类混合光引发剂，具有如通式(I)所示结构，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，且该四种连接位的双咪唑化合物在A1中的总质量百分含量为92％以上，Among them, the photopolymerization initiator A1 is a hexaarylbisimidazole-based mixed photoinitiator, having a structure as shown in the general formula (I), which contains 2-1', 2-3', 2'-1 and 2'- 3 There are four kinds of bisimidazole compounds at the connection position, and the total mass percentage of the four bisimidazole compounds at the connection position in A1 is more than 92%,
    Figure PCTCN2020081284-appb-100001
    Figure PCTCN2020081284-appb-100001
    通式(I)中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基； In the general formula (I), Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group;
    且光聚合引发剂(A)在i线(365nm)处摩尔消光系数在5000-10000之间。And the molar extinction coefficient of the photopolymerization initiator (A) at the i-line (365nm) is between 5000-10000.
  2. 根据权利要求1所述的组合物，其特征在于：光聚合引发剂A1与肟酯类光引发剂A2在组合物中的质量比为1:5-5:5。The composition according to claim 1, wherein the mass ratio of the photopolymerization initiator A1 and the oxime ester photoinitiator A2 in the composition is 1:5-5:5.
  3. 根据权利要求1所述的组合物，其特征在于：Ar 1、Ar 2、Ar 3、Ar 4、 Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基，且所述芳基是苯基。 The composition according to claim 1, wherein: Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group, and The aryl group is phenyl.
  4. 根据权利要求1-3中任一项所述的组合物，其特征在于：芳基上的取代基为卤素、硝基、氰基、胺基、羟基、C 1-C 20的烷基或链烯基、C 1-C 8的烷氧基，其中各独立变量(即，各取代基)中的亚甲基可以任选地被氧、硫、亚胺基所取代。 The composition according to any one of claims 1 to 3, wherein the substituents on the aryl group are halogen, nitro, cyano, amine, hydroxyl, C 1 -C 20 alkyl or chain Alkenyl, C 1 -C 8 alkoxy, wherein the methylene group in each independent variable (ie, each substituent) may be optionally substituted with oxygen, sulfur, or imino.
  5. 根据权利要求1-3中任一项所述的组合物，其特征在于：芳基上的取代基为氟、氯、溴、硝基、氰基、胺基、羟基、C 1-C 10的烷基或链烯基、C 1-C 5的烷氧基，其中各独立变量中的亚甲基可以任选地被氧、硫、亚胺基所取代。 The composition according to any one of claims 1-3, wherein the substituents on the aryl group are fluorine, chlorine, bromine, nitro, cyano, amine, hydroxyl, C 1 -C 10 Alkyl or alkenyl, C 1 -C 5 alkoxy, wherein the methylene group in each independent variable can be optionally substituted with oxygen, sulfur, or imino.
  6. 根据权利要求1-3中任一项所述的组合物，其特征在于：Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6中至少一个是含有卤素取代基的芳基；优选地，卤素取代基为氯。 The composition according to any one of claims 1-3, characterized in that: at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 is an aryl group containing a halogen substituent; preferably Ground, the halogen substituent is chlorine.
  7. 根据权利要求1-3中任一项所述的组合物，其特征在于：作为光聚合引发剂A1，满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物在其中的总质量百分含量为95％以上，优选由满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物组成。The composition according to any one of claims 1-3, characterized in that: as the photopolymerization initiator A1, it satisfies 2-1', 2-3', 2'- of the structure represented by general formula (I) The total mass percentage of the bisimidazole compounds at the four connection positions 1 and 2'-3 is more than 95%, preferably composed of 2-1', 2-3', and 2 that satisfy the structure shown in the general formula (I). '-1 and 2'-3 are composed of four kinds of bisimidazole compounds.
  8. 根据权利要求1所述的组合物，其特征在于：碱可溶性树脂(B)是含羧基共聚物的碱可溶性树脂，优选具有羧基的烯属不饱和单体和其它可共聚的烯属不饱和单体的共聚物。The composition according to claim 1, wherein the alkali-soluble resin (B) is an alkali-soluble resin containing a carboxyl group copolymer, preferably an ethylenically unsaturated monomer having a carboxyl group and other copolymerizable ethylenically unsaturated monomers. Body copolymer.
  9. 根据权利要求1所述的组合物，其特征在于：具有至少一个聚合性不饱和键的化合物(C)选自丙烯酸酯类化合物和甲基丙烯酸酯类化合物中的至少一种。The composition according to claim 1, wherein the compound (C) having at least one polymerizable unsaturated bond is selected from at least one of acrylate-based compounds and methacrylate-based compounds.
  10. 根据权利要求1所述的组合物，其特征在于：着色剂(D)选自颜料和/或染料。The composition according to claim 1, wherein the colorant (D) is selected from pigments and/or dyes.
  11. 根据权利要求1所述的组合物，其特征在于：供氢体(E)是胺类化合物、羧酸类化合物、含有巯基的有机硫化合物和醇类化合物中的至少一种。The composition according to claim 1, wherein the hydrogen donor (E) is at least one of an amine compound, a carboxylic acid compound, a mercapto group-containing organic sulfur compound, and an alcohol compound.
  12. 彩色滤光片，其特征在于：在支撑体上具有使用权利要求1-11中任一项所述的感光性树脂组合物形成的着色图案。A color filter is characterized by having a colored pattern formed using the photosensitive resin composition according to any one of claims 1-11 on a support.
  13. 彩色滤光片的制造方法，包括：在支撑体上涂布权利要求1-11中任一项所述的感光性树脂组合物来形成感光性树脂层的工序；将感光性树脂层通过掩模曝光的工序；和将曝光后的感光性树脂层显影来形成着色图案的工序。A method of manufacturing a color filter, comprising: applying the photosensitive resin composition according to any one of claims 1 to 11 on a support to form a photosensitive resin layer; and passing the photosensitive resin layer through a mask The process of exposing; and the process of developing the photosensitive resin layer after exposure to form a colored pattern.
  14. 根据权利要求13所述的制造方法，其特征在于：还包括通过加热及/或曝光使形成的着色图案进一步固化的后固化工序。The manufacturing method according to claim 13, further comprising a post-curing step of further curing the formed colored pattern by heating and/or exposure.
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