WO2016124127A1 - 一种感光性树脂组合物及其应用 - Google Patents

一种感光性树脂组合物及其应用 Download PDF

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WO2016124127A1
WO2016124127A1 PCT/CN2016/073119 CN2016073119W WO2016124127A1 WO 2016124127 A1 WO2016124127 A1 WO 2016124127A1 CN 2016073119 W CN2016073119 W CN 2016073119W WO 2016124127 A1 WO2016124127 A1 WO 2016124127A1
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group
acrylate
meth
independently represent
bond
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PCT/CN2016/073119
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English (en)
French (fr)
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钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Publication of WO2016124127A1 publication Critical patent/WO2016124127A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the invention belongs to the field of organic chemistry, and in particular relates to a photosensitive resin composition and an optical color filter thereof, a phtospacer and a rib in a color television set, a liquid crystal display element, a solid-state image sensor, and a camera. Applications in other aspects.
  • the photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an unsaturated bond, and is mainly polymerized and cured by irradiation with an energy ray, which plays a decisive role in the production of an optical color filter.
  • a photosensitive composition for forming a color filter image to have high resolution and a substrate. Good adhesion and less development residue.
  • a coloring material such as a pigment or a carbon black is often high, and an increase in the concentration of the coloring material adversely affects resolution, substrate adhesion, and development residue. It is necessary to increase the exposure amount in the exposure process or to lengthen the exposure time, and also to reduce the accuracy of the color filter.
  • an object of the present invention is to provide a novel photosensitive resin composition which has good exposure sensitivity (i.e., high sensitivity) and developability, in the case where the system contains an opacifier or a low exposure dose. After curing, the pattern is complete and the development is clear, the resolution is high, and the adhesion to the substrate is excellent.
  • a photosensitive resin composition comprising the following components:
  • X, Y each independently represent a carbonyl group (-CO-) or a single bond;
  • A represents N, O, S or CH;
  • R 1 may be empty or represent hydrogen, C 1 -C 20 linear or branched alkyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkylalkyl or C 4 -C 20 Alkylcycloalkyl;
  • R 2 and R 3 each independently represent hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group, C 4 - An alkylcycloalkyl group of C 20 , a C 7 -C 20 aralkyl group or a C 2 -C 20 heterocyclic group, -OR 11 , -COR 11 , -COOR 11 , -SR 11 , -SO 2 R 11 Or -CONR 11 R 12 , wherein R 11 and R 12 each independently represent hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 ring An alkylalkyl group, a C 4 -C 20 alkylcycloalkyl group, a C 7 -C 20 aralkyl group or a C 2
  • R 4 and R 5 each independently represent a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group, a C 4 -C 20 group.
  • An alkylcycloalkyl group, a C 3 -C 20 heteroaryl group, a C 6 -C 20 aryl group; optionally, the hydrogen in these groups may be selected from the group consisting of halogen, phenyl, nitro, hydroxy, a group substituted with a carboxyl group, a sulfonic acid group, an amino group, a cyano group, and an alkoxy group;
  • R 6 and R 7 each independently represent hydrogen or a nitro group.
  • Another object of the present invention is to provide an application of the above photosensitive resin composition in the production of a color filter film, a black matrix, a photo spacer, and a rib grid.
  • the component (C) photoinitiator has good compatibility with the components (A), (B) and (D).
  • the composition has a very high sensitivity and can be cross-linked and cured at a very low exposure dose, and the curing effect is excellent.
  • the film made of the composition has a flat edge without defects, no scum, a clear and clear pattern, and high hardness.
  • the prepared filter has high optical transparency, no light leakage, and is produced at a very low exposure dose, and has high precision, flatness and durability.
  • the compositions of the present invention are also excellent materials for making photo spacers, black matrices and rib gates.
  • the photosensitive resin composition of the present invention has high sensitivity and good developability, high resolution, and excellent adhesion to a substrate, and is very suitable for preparing a black matrix (BM) having high light-shielding properties, high definition and high quality.
  • BM black matrix
  • the color filter and the liquid crystal display device are also applicable to photo spacers and rib gates.
  • the photosensitive resin composition of the present invention contains the components (A) to (D), and each component will be described in more detail below.
  • component (A) is preferably an epoxy acrylate resin having a carboxyl group such as a homopolymer of (meth)acrylic acid, itaconic acid, crotonic acid and partially esterified maleic acid.
  • component (A) is preferably an epoxy acrylate resin having a carboxyl group such as a homopolymer of (meth)acrylic acid, itaconic acid, crotonic acid and partially esterified maleic acid.
  • the copolymers more preferably an epoxy acrylate prepolymer, an acrylate prepolymer, a urethane acrylate prepolymer, an aliphatic urethane acrylate prepolymer, an aromatic urethane acrylate prepolymer, One or a mixture of two or more of the polyester acrylate prepolymers.
  • the component (A) ultraviolet photosensitive prepolymer resin is methacrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, ethyl (meth) acrylate, hydroxy (meth) acrylate
  • methacrylic acid methyl (meth) acrylate, benzyl (meth) acrylate, ethyl (meth) acrylate, hydroxy (meth) acrylate
  • benzyl (meth) acrylate ethyl (meth) acrylate
  • ethyl (meth) acrylate hydroxy (meth) acrylate
  • the weight average molecular weight (Mw) of the polymer used as the component (A) is preferably from 5,000 to 250,000, more preferably from 10,000 to 50,000.
  • the amount of the component (A) used in the photosensitive resin composition is preferably from 25 to 60 parts by mass, more preferably from 40 to 50 parts by mass.
  • the component (B) active diluent monomer is one or two or more acrylate monomers, and the acrylate monomer is preferably ethylene glycol.
  • (meth) acrylate of alkylene glycol such as propylene glycol
  • (meth) acrylate of polyalkylene glycol such as polyethylene glycol or polypropylene glycol
  • glycerin trimethylolpropane, pentaerythritol, dipentaerythritol, etc.
  • the component (B) active diluent monomer is trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris((meth)acryloylethoxy)phosphate
  • pentaerythritol tetra(meth)acrylate dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
  • the amount of the component (B) used in the photosensitive resin composition is preferably from 15 to 40 parts by mass, more preferably from 25 to 35 parts by mass.
  • the component (C) photoinitiator is preferably one or a combination of two or more of the oxime ester photoinitiators represented by the formula (II),
  • R 1 represents hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 15 cycloalkylalkyl group or a C 4 -C 15 alkyl ring. alkyl;
  • R 2 and R 3 each independently represent hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 3 -C 15 cycloalkyl group, a C 4 -C 15 cycloalkylalkyl group, C 4 - alkyl C 15 cycloalkyl, C 7 -C 15 aralkyl or C 2 -C 15 heterocyclyl group is, -OR 11, -COR 11, -COOR 11, -SR 11, -SO 2 R 11 And -CONR 11 R 12 , wherein R 11 and R 12 each independently represent hydrogen, C 1 -C 10 linear or branched alkyl, C 3 -C 15 cycloalkyl, C 4 -C 15 ring An alkylalkyl group, a C 4 -C 15 alkylcycloalkyl group, a C 7 -C 15 aralkyl group or a C 2 -C 15 heterocyclic group; optionally, the hydrogen in R 2 and R 3 may be
  • R 4 and R 5 each independently represent a C 1 -C 10 linear or branched alkyl group, a C 3 -C 15 cycloalkyl group, a C 4 -C 15 cycloalkylalkyl group, a C 4 -C 15 group.
  • R 6 and R 7 each independently represent hydrogen or a nitro group.
  • R 1 represents a C 1 -C 8 linear or branched alkyl group, particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, 6-methylheptyl;
  • R 2 and R 3 each independently represent a C 3 -C 5 linear or branched alkyl group, -O-CH 2 -R 31 , -CH 2 -OR 31 , -CH 2 -SR 31 , -CH 2 - OCO-CH 2 -R 31 , -CO-CH 2 -R 31 , -CH 2 -CH 2 -R 31 , or -OCO-R 31 , wherein R 31 represents a C 4 -C 6 cycloalkyl or heterocyclic ring Particularly preferably, the linear or branched alkyl group is selected from n-propyl, n-butyl, isobutyl, and R 31 represents cyclopentyl, cyclohexyl, 2-furyl, 2-tetrahydrofuranyl, or 1-tetrahydropyrrole; and, at least one of R 2 and R 3 is the above-mentioned R 31 -containing group;
  • R 4 and R 5 each independently represent a C 1 -C 5 linear or branched alkyl group, particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl;
  • R 6 and R 7 each independently represent hydrogen or a nitro group.
  • the photoinitiator described in the component (C) is preferably one or a combination of two or more of the compounds shown in the following structures:
  • the photosensitive resin composition of the present invention may further contain a component (D) colorant.
  • a component (D) colorant can be used to form a color filter of a liquid crystal display by containing a colorant; and when an opacifier is used as a colorant, the composition can be used to form a black matrix in a color filter of a display device. Picture tube.
  • the kind of the component (D) coloring agent is not particularly limited, and may be those classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), preferably having the following Color number of CI:
  • CI Pigment Yellow 1 (hereinafter, since "CI Pigment Yellow” is the same, only the serial number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61 , 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120 125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,166,167,168,175,180,185;
  • CI Pigment Orange 1 (hereinafter, "CI Pigment Orange” is the same, only the serial number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55 , 59, 61, 63, 64, 71, 73;
  • C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet” is the same, so only the serial number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
  • CI Pigment Red 1 (hereinafter, since "CI Pigment Red” is the same, only the serial number is described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17 , 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2 , 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1 , 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207,
  • C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue” is the same, so only the serial number), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66;
  • a black pigment As an opacifier, it is preferred to use a black pigment as an opacifier.
  • the black pigment include carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, and metal sulfuric acid. Salt or metal carbonate, etc.
  • carbon black having high light-shielding property is preferably used, and it may be a common carbon black such as channel black, furnace black, thermal black, or lampblack, and it is preferable to use a grooved carbon having excellent light shielding properties. Black; carbon black can also be coated with a resin.
  • the organic pigments listed above may be suitably added as an auxiliary pigment. It has been found that even when a black pigment having a high light-shielding property is used in the photosensitive resin composition of the present invention, it is possible to exhibit excellent developability and pattern integrity.
  • auxiliaries commonly used in the art including but not limited to sensitizers, dispersants, surfactants, solvents and the like, may optionally be added to the photosensitive resin composition of the present invention in accordance with the needs of product application.
  • the photosensitive resin composition of the present invention can be obtained by weighing each component by weight and uniformly mixing it, which is a well-known conventional technique to those skilled in the art.
  • a coater such as a spin coater, a wire bar coater, a shaft coater or a spray coater
  • a photoresist film containing a black pigment is a black matrix BM
  • a photoresist film containing red, green, and blue pigments is a corresponding R, G, and B photoresist.
  • the liquid composition was coated on a glass substrate by a spin coater, and then the solvent was removed by drying at 100 ° C for 5 minutes to form a coating film having a film thickness of 8 ⁇ m; in order to obtain the coating film of the above thickness, the coating process may be completed once. Can also be divided into multiple times;
  • LED light source Ilethora LED UV curing irradiation device, maximum irradiation intensity 400mW/cm 2 ), pass the gap of the mask plate at the wavelength of 370-420nm Exposing the coating film under ultraviolet irradiation;
  • the minimum exposure amount at which the residual film ratio is 90% or more after development in the light irradiation region in the exposure step is evaluated as the exposure demand amount, and the smaller the exposure demand amount, the higher the sensitivity.
  • the pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability and pattern integrity.
  • the developability was evaluated according to the following criteria:
  • Pattern integrity is evaluated according to the following criteria:
  • Evaluation is carried out in accordance with GB/T 6739-1996 "Coating film hardness pencil measurement method". Use a film pencil scratch hardness tester to observe the scratch marks of the paint film, and use a pencil with no scratches as the pencil hardness of the coating film.
  • the filter photoresists produced by the compositions of Examples 1-8 have good developability and pattern integrity, and are superior in adhesion and hardness to general initiators. Comparative Examples 1-4 are clearly insufficient in these respects. It is to be noted that the exposure doses of Examples 1-8 were all less than 45 mJ/cm 2 , which was far lower than Comparative Examples 1-4, and showed extremely excellent photosensitivity.
  • the photosensitive resin composition of the present invention exhibits very excellent application properties and has broad application prospects.

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Abstract

一种感光性树脂组合物，其包含紫外感光预聚物树脂、活性稀释单体、式(I)所示肟酯类光引发剂和着色剂。该组合物具有良好的曝光灵敏度和显影性，在体系含有遮光剂或曝光剂量很低的情况下，固化后图案完整且显影清晰，分辨率高，与基板密合性优异，在光学滤色器、光间隔物和肋栅等方面有很好的应用前景。

Description

一种感光性树脂组合物及其应用 技术领域
本发明属于有机化学领域，具体涉及一种感光性树脂组合物及其在彩色电视机、液晶显示元件、固态摄像元件和相机等光学滤色器以及光间隔物(phtospacer)和肋栅(rib)等方面中的应用。
背景技术
感光性组合物是在具有不饱和键的聚合性化合物中加入光聚合引发剂而得到的，主要通过照射能量射线而使其聚合固化，其在光学滤色器的生产中起着决定性作用。近年来，随着人们对生活质量要求的提高，对液晶显示屏画面清晰度的要求也越来越高，这就需要用于形成滤色器图像的感光性组合物具有分辨率高、与基板密合性好、显影残渣少等特点。在实际使用中，光学浓度高的像素及树脂底层体系中往往颜料、炭黑等着色材料含量较高，而着色材料浓度的增加会对分辨率、基板密合性、显影残渣产生不利影响，不仅需要提高曝光工序中的曝光量或延长曝光时间，而且还会降低滤色器的精度。
发明概述
鉴于上述情况，本发明的目的在于提供一种新的感光性树脂组合物，它具有良好的曝光灵敏度(即，高感光度)和显影性，在体系含有遮光剂或曝光剂量很低的情况下，固化后图案完整且显影清晰，分辨率高，与基板密合性优异。
为了实现上述目的，采用如下技术方案。
一种感光性树脂组合物，其特征在于，包含下列组分：
(A)20-60质量份紫外感光预聚物树脂；
(B)10-40质量份活性稀释单体；
(C)1-5质量份光引发剂，该光引发剂选自式(I)所示肟酯类光引发剂中的一种或两种以上的组合，
Figure PCTCN2016073119-appb-000001
其中，
X、Y各自独立地代表羰基(-CO-)或单键；
A表示N、O、S或CH；
R1可为空或表示氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基；
R2和R3各自独立地表示氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C7-C20的芳烷基或C2-C20的杂环基、-OR11、-COR11、-COOR11、-SR11、-SO2R11或-CONR11R12，其中R11和R12各自独立地表示氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C7-C20的芳烷基或C2-C20的杂环基；任选地，R2和R3中的氢可以被选自-OR21、-COR21、-SR21、-NR22R23、-CONR22R23、-NR22-OR23、-NCOR22-OCOR23、-C(＝N-OR21)-R22、 -C(-N-OCOR21)-R22、CN、卤原子、-CR21＝CR22R23、-CO-CR21＝CR22R23、羧基和环氧基中的基团取代，其中R21、R22和R23各自独立地表示氢、C1-C20的烷基、C6-C30的芳基、C7-C30的芳烷基或C2-C20的杂环基；任选地，R11、R12、R21、R22和R23中的亚甲基可以被不饱和键、醚键、硫醚键、酯键、硫酯键、酰胺键或氨基甲酸酯键中断1-5次；上述取代基的烷基部分可以具有分支侧链，也可以是环烷基，上述取代基的烷基末端也可以是不饱和键，而且R11、R12、以及R21、R22、R23也可以彼此任意相连以形成环。
R4和R5各自独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C3-C20的杂芳基、C6-C20的芳基；任选地，这些基团中的氢可以被选自卤素、苯基、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团取代；
R6和R7各自独立地表示氢或硝基。
(D)0-50质量份的着色剂。
本发明的另一个目的在于提供上述感光性树脂组合物在制备彩色滤光片膜、黑色矩阵、光间隔物和肋栅中的应用。
本发明所述的感光性组合物中，组分(C)光引发剂与组分(A)、(B)和(D)具有很好的适配性。组合物具有非常高的感光度，在很低的曝光剂量下就可以很好的交联固化，且固化效果极佳。由该组合物制成的膜边缘平整无缺陷，没有浮渣，图案完整清晰，且硬度高。制成的滤光片光学透明度高，不漏光，在很低的曝光剂量下完成制作，并且精度好、平坦、耐久。同时，本发明的组合物还是制作光间隔物、黑色矩阵和肋栅的优异材料。
发明详述
本发明的上述感光性树脂组合物具有高感光度和良好的显影性，分辨率高且与基板密合性优异，非常适合用以制备高遮光性的黑色矩阵(BM)、高精细且高品质的滤色器和液晶显示装置，并且也能够在光间隔物和肋栅等方面得到应用。
本发明的感光性树脂组合物包含组分(A)-(D)，以下将对各组分进行更加详细的说明。
在本发明的说明书中，除非另有说明，术语“…(甲基)丙烯酸…”及其同类表述均涉及“…丙烯酸…”和“…甲基丙烯酸…”两种情形。
<组分(A)紫外感光预聚物树脂>
本发明的感光性树脂组合物中，组分(A)优选使用具有羧基的环氧丙烯酸酯树脂，如(甲基)丙烯酸、衣康酸、巴豆酸和部分酯化马来酸的均聚物或共聚物中的至少一种，更优选环氧丙烯酸酯预聚物、丙烯酸酯预聚物、聚氨酯丙烯酸酯预聚物、脂肪族聚氨酯丙烯酸酯预聚物、芳香族聚氨酯丙烯酸酯预聚物、聚酯丙烯酸酯预聚物中的一种或两种以上的混合物。
进一步优选地，组分(A)紫外感光预聚物树脂是甲基丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸异丁基酯中的一种或两种以上的均聚物或共聚物。
作为组分(A)使用的聚合物的重均分子量(Mw)优选为5000-250000，更优选为10000-50000。
组分(A)在感光性树脂组合物中的用量优选为25-60质量份，更优选为40-50质量份。
<组分(B)活性稀释单体>
在本发明的感光性树脂组合物中，适宜地，组分(B)活性稀释单体是一种或两种以上的丙烯酸酯类单体，所述丙烯酸酯类单体优选：乙二醇、丙二醇等亚烷基二醇的(甲基)丙烯酸酯；聚乙二醇、聚丙二醇等聚亚烷基二醇的(甲基)丙烯酸酯；甘油、三羟甲基丙烷、季戊四醇、二季戊四醇等三元以上多元醇的聚(甲基)丙烯酸酯或其二羧酸改性物；聚酯、环氧树脂、脲烷树脂、醇酸树脂、硅氧烷树脂、螺烷树脂等低聚(甲基)丙烯酸酯；两末端羟基聚异戊二烯、两末端羟基聚己内酯、两末端羟基聚-1,3-丁二烯等两末端羟基化聚合物的(甲基)丙烯酸酯等。
进一步优选地，组分(B)活性稀释单体是三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三((甲基)丙烯酰乙氧基)磷酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等中的一种或两种以上的混合。
组分(B)在感光性树脂组合物中的用量优选为15-40质量份，更优选为25-35质量份。
<组分(C)光引发剂>
组分(C)光引发剂优选式(II)所示肟酯类光引发剂中的一种或两种以上的组合，
Figure PCTCN2016073119-appb-000002
其中，
R1表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C15的环烷基烷基或C4-C15的烷基环烷基；
R2和R3各自独立地表示氢、C1-C10的直链或支链烷基、C3-C15的环烷基、C4-C15的环烷基烷基、C4-C15的烷基环烷基、C7-C15的芳烷基或C2-C15的杂环基、-OR11、-COR11、-COOR11、-SR11、-SO2R11、-CONR11R12，其中R11和R12各自独立地表示氢、C1-C10的直链或支链烷基、C3-C15的环烷基、C4-C15的环烷基烷基、C4-C15的烷基环烷基、C7-C15的芳烷基或C2-C15的杂环基；任选地，R2和R3中的氢可以被选自-OR21、-COR21、-SR21、-NR22R23、-CONR22R23、-NR22-OR23、-NCOR22-OCOR23、-C(＝N-OR21)-R22、-C(-N-OCOR21)-R22、-CN、卤原子、-CR21＝CR22R23、-CO-CR21＝CR22R23、羧基和环氧基的基团取代，其中R21、R22和R23各自独立地表示氢原子、C1-C20的烷基、C6-C15的芳基、C7-C15的芳烷基或C2-C15的杂环基；任选地，R11、R12、R21、R22和R23中的亚甲基可以被不饱和键、醚键、硫醚键、酯键、硫酯键、酰胺键或氨基甲酸酯键中断1-5次；上述取代基的烷基部分可以具有分支侧链，也可以是环烷基，上述取代基的烷基末端也可以是不饱和键，而且R11、R12以及R21、R22、R23也可以彼此任意相连以形成环；
R4和R5各自独立地表示C1-C10的直链或支链烷基、C3-C15的环烷基、C4-C15的环烷基烷基、C4-C15的烷基环烷基、C3-C15的杂芳基或C6-C15的芳基；
R6和R7各自独立地表示氢或硝基。
进一步优选地，式(II)所示肟酯类光引发剂中：
R1表示C1-C8的直链或支链烷基，特别是甲基、乙基、正丙基、异丙基、正丁基、6-甲基庚基；
R2和R3各自独立地表示C3-C5的直链或支链烷基、-O-CH2-R31、-CH2-O-R31、-CH2-S-R31、-CH2-OCO-CH2-R31、-CO-CH2-R31、-CH2-CH2-R31、或-OCO-R31，其中R31表示C4-C6的环烷基或杂环基；特别优选地，所述直链或支链烷基选自正丙基、正丁基、异丁基，R31表示环戊基、环己基、2-呋喃基、2-四氢呋喃基、或1-四氢吡咯基；并且，R2和R3中的至少一个是上述含有R31的基团；
R4和R5各自独立地表示C1-C5的直链或支链烷基，特别是甲基、乙基、正丙基、异丙基、正丁基、异丁基；
R6和R7各自独立地表示氢或硝基。
更为具体地，组分(C)所述的光引发剂优选自下列结构所示化合物中的一种或两种以上的组合：
Figure PCTCN2016073119-appb-000003
Figure PCTCN2016073119-appb-000004
Figure PCTCN2016073119-appb-000005
<组分(D)着色剂>
本发明的感光性树脂组合物可进一步含有组分(D)着色剂。非限制性地，通过含有着色剂，本发明的组合物可用于形成液晶显示器的滤色器；并且在以遮光剂作为着色剂时，组合物可用于形成显示装置的滤色器中的黑底显像管。
对于组分(D)着色剂的种类没有特别限定，可以是颜色指数(color index)(C.I.；The Society of Dyers and Colourists社发行)中被分类成颜料(Pigment)的那些化合物，优选具有下述C.I.序号的着色剂：
C.I.颜料黄1(以下由于“C.I.颜料黄”是相同的所以仅记载序号)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、185；
C.I.颜料橙1(以下由于“C.I.颜料橙”是相同的所以仅记载序号)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、73；
C.I.颜料紫1(以下由于“C.I.颜料紫”是相同的所以仅记载序号)、19、23、29、30、32、36、37、38、39、40、50；
C.I.颜料红1(以下由于“C.I.颜料红”是相同的所以仅记载序号)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、 83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、265；
C.I.颜料蓝1(以下由于“C.I.颜料蓝”是同样的所以仅记载序号)、2、15、15:3、15:4、15:6、16、22、60、64、66；
C.I.颜料绿7、C.I.颜料绿36、C.I.颜料绿37；
C.I.颜料棕23、C.I.颜料棕25、C.I.颜料棕26、C.I.颜料棕28；
C.I.颜料黑1、C.I.颜料黑7。
在选用遮光剂作为着色剂时，优选使用黑色颜料作为遮光剂。作为黑色颜料，可列举：炭黑，钛黑(titanium black)，铜、铁、锰、钴、铬、镍、锌、钙、银等的金属氧化物、复合氧化物、金属硫化物、金属硫酸盐或金属碳酸盐等。这些黑色颜料中，优选使用具有高遮光性的炭黑，可以是槽法炭黑、炉法炭黑、热裂炭黑、灯烟炭黑等常见炭黑，优选使用遮光性优异的槽法炭黑；还可使用树脂涂覆炭黑。此外，为了调整炭黑的色调，可适宜添加上面列出的有机颜料作为辅助颜料。实践表明，即使本发明的感光性树脂组合物中使用遮光性高的黑色颜料，也能够表现出非常好的显影性和图案完整性。
<其它任选组分>
根据产物应用需要，在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，包括但不限于敏化剂、分散剂、表面活性剂、溶剂等。
<制备及应用>
将各组分按量称取后混合均匀，即可获得本发明的感光性树脂组合物，这对于本领域技术人员来说属于公知的常规性技术。
本发明的目的还在于提供上述感光性树脂组合物在制备彩色滤光片膜、黑色矩阵、光间隔物和肋栅中的应用。
利用感光性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：
i)将感光性树脂组合物溶解在合适的有机溶剂中，混合均匀，获得液状组合物；
ii)利用涂布机，例如旋转涂布机、绕线棒涂布机、轴涂布机或喷涂布机等，将液状组合物均匀涂布在基板上；
iii)进行前烘烤干燥，除去溶剂；
iv)将掩膜板附在样品上进行曝光，随后显影除去未曝光区域；
v)进行后烘烤，得到具有所希望形状的光致抗蚀剂干膜。
含有黑色颜料的光致抗蚀剂膜就是黑色矩阵BM，含有红、绿、蓝色颜料的光致抗蚀剂膜就是对应的R、G、B光阻。
具体实施方式
以下通过实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。
制备实施例
按照表1所列配方，配制实施例1-8和比较例1-4的感光性树脂组合物，其中比较例1-4中的光引发剂A1-A4的结构如下所示：
Figure PCTCN2016073119-appb-000006
表1
Figure PCTCN2016073119-appb-000007
Figure PCTCN2016073119-appb-000008
将配制好的感光性树脂组合物溶解在100质量份的溶剂丙二醇单甲醚醋酸酯(PGMEA)中，混合均匀，形成液态组合物；
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8μm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，采用LED光源(依瓦塔LED UV固化照射装置，最大照射强度400mW/cm2)，通过掩膜板的缝隙在370-420nm波长的紫外线照射下对涂膜进行曝光；
在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。
性能评价
1、曝光灵敏度评价
将在曝光步骤中光辐照区域显影后残膜率在90％或以上的最小曝光量评价为曝光需求量，曝光需求量越小表示灵敏度越高。
2、显影性和图案完整性评价
用扫描电子显微镜(SEM)观察基板上图案，以评价显影性和图案完整性。
显影性根据以下标准评价:
○：在未曝光部分未观察到残留物；
◎：在未曝光部分观察到少量残留物，但残留量可以接受；
●：在未曝光部分观察到明显残留物。
图案完整性根据以下标准评价:
△：没有观察到图案缺陷；
□：观察到小部分图案有些许缺陷；
▲：明显观察到许多图案缺陷。
3、硬度评价
参照GB/T 6739-1996《涂膜硬度铅笔测定法》进行评价。使用涂膜铅笔划痕硬度仪,观察漆膜划痕痕迹,以未见划痕的铅笔为涂膜的铅笔硬度。
4、附着力评价
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。
评价结果如表2中所示。
表2
Figure PCTCN2016073119-appb-000009
Figure PCTCN2016073119-appb-000010
从表2的结果可以看出，实施例1-8的组合物所制得的滤光片光阻具有很好的显影性和图案完整性，附着力及硬度方面也高于一般的引发剂，而比较例1-4在这些方面明显存在不足。需要特别注意的是，实施例1-8在的曝光剂量均不足45mJ/cm2，远远低于比较实施例1-4，表现出了极其优异的感光灵敏度。
综上所述，本发明的感光性树脂组合物表现出了非常优异的应用性能，具有广阔的应用前景。

Claims (9)

  1. 一种感光性树脂组合物，其特征在于，包含下列组分：
    (A)20-60质量份紫外感光预聚物树脂；
    (B)10-40质量份活性稀释单体；
    (C)1-5质量份光引发剂，该光引发剂选自式(I)所示肟酯类光引发剂中的一种或两种以上的组合，
    Figure PCTCN2016073119-appb-100001
    其中，
    X、Y各自独立地代表羰基(-CO-)或单键；
    A表示N、O、S或CH；
    R1可为空或表示氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基；
    R2和R3各自独立地表示氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C7-C20的芳烷基或C2-C20的杂环基、-OR11、-COR11、-COOR11、-SR11、-SO2R11或-CONR11R12，其中R11和R12各自独立地表示氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C7-C20的芳烷基或C2-C20的杂环基；任选地，R2和R3中的氢可以被选自-OR21、-COR21、-SR21、-NR22R23、-CONR22R23、-NR22-OR23、-NCOR22-OCOR23、-C(＝N-OR21)-R22、-C(-N-OCOR21)-R22、CN、卤原子、-CR21＝CR22R23、-CO-CR21＝CR22R23、羧基和环氧基中的基团取代， 其中R21、R22和R23各自独立地表示氢、C1-C20的烷基、C6-C30的芳基、C7-C30的芳烷基或C2-C20的杂环基；任选地，R11、R12、R21、R22和R23中的亚甲基可以被不饱和键、醚键、硫醚键、酯键、硫酯键、酰胺键或氨基甲酸酯键中断1-5次；上述取代基的烷基部分可以具有分支侧链，也可以是环烷基，上述取代基的烷基末端也可以是不饱和键，而且R11、R12、以及R21、R22、R23也可以彼此任意相连以形成环；
    R4和R5各自独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C3-C20的杂芳基、C6-C20的芳基；任选地，这些基团中的氢可以被选自卤素、苯基、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团取代；
    R6和R7各自独立地表示氢或硝基。
    (D)0-50质量份的着色剂。
  2. 根据权利要求1所述的感光性树脂组合物，其特征在于：组分(A)紫外感光预聚物树脂选自环氧丙烯酸酯预聚物、丙烯酸酯预聚物、聚氨酯丙烯酸酯预聚物、脂肪族聚氨酯丙烯酸酯预聚物、芳香族聚氨酯丙烯酸酯预聚物、聚酯丙烯酸酯预聚物中的一种或两种以上的混合物。
  3. 根据权利要求1或2所述的感光性树脂组合物，其特征在于：组分(A)紫外感光预聚物树脂是甲基丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸羟乙酯、 (甲基)丙烯酸羟丙酯、(甲基)丙烯酸异丁基酯中的一种或两种以上的均聚物或共聚物。
  4. 根据权利要求1所述的感光性树脂组合物，其特征在于，组分(B)活性稀释单体是一种或两种以上的丙烯酸酯类单体，所述丙烯酸酯类单体选自：乙二醇、丙二醇等亚烷基二醇的(甲基)丙烯酸酯；聚乙二醇、聚丙二醇等聚亚烷基二醇的(甲基)丙烯酸酯；甘油、三羟甲基丙烷、季戊四醇、二季戊四醇等三元以上多元醇的聚(甲基)丙烯酸酯或其二羧酸改性物；聚酯、环氧树脂、脲烷树脂、醇酸树脂、硅氧烷树脂、螺烷树脂等低聚(甲基)丙烯酸酯；两末端羟基聚异戊二烯、两末端羟基聚己内酯、两末端羟基聚-1,3-丁二烯等两末端羟基化聚合物的(甲基)丙烯酸酯等。
  5. 根据权利要求1或4所述的感光性树脂组合物，其特征在于：组分(B)活性稀释单体是三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三((甲基)丙烯酰乙氧基)磷酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等中的一种或两种以上的混合。
  6. 根据权利要求1所述的感光性树脂组合物，其特征在于，组分(C)光引发剂选自式(II)所示肟酯类光引发剂中的一种或两种以上的组合，
    Figure PCTCN2016073119-appb-100002
    其中，
    R1表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C15的环烷基烷基或C4-C15的烷基环烷基；
    R2和R3各自独立地表示氢、C1-C10的直链或支链烷基、C3-C15的环烷基、C4-C15的环烷基烷基、C4-C15的烷基环烷基、C7-C15的芳烷基或C2-C15的杂环基、-OR11、-COR11、-COOR11、-SR11、-SO2R11、-CONR11R12，其中R11和R12各自独立地表示氢、C1-C10的直链或支链烷基、C3-C15的环烷基、C4-C15的环烷基烷基、C4-C15的烷基环烷基、C7-C15的芳烷基或C2-C15的杂环基；任选地，R2和R3中的氢可以被选自-OR21、-COR21、-SR21、-NR22R23、-CONR22R23、-NR22-OR23、-NCOR22-OCOR23、-C(＝N-OR21)-R22、-C(-N-OCOR21)-R22、-CN、卤原子、-CR21＝CR22R23、-CO-CR21＝CR22R23、羧基和环氧基的基团取代，其中R21、R22和R23各自独立地表示氢原子、C1-C20的烷基、C6-C15的芳基、C7-C15的芳烷基或C2-C15的杂环基；任选地，R11、R12、R21、R22和R23中的亚甲基可以被不饱和键、醚键、硫醚键、酯键、硫酯键、酰胺键或氨基甲酸酯键中断1-5次；上述取代基的烷基部分可以具有分支侧链，也可以是环烷基，上述取代基的烷基末端也可以是不饱和键，而且R11、R12以及R21、R22、R23也可以彼此任意相连以形成环；
    R4和R5各自独立地表示C1-C10的直链或支链烷基、C3-C15的环烷基、C4-C15的环烷基烷基、C4-C15的烷基环烷基、C3-C15的杂芳基或C6-C15的芳基；
    R6和R7各自独立地表示氢或硝基。
  7. 根据权利要求6所述的感光性树脂组合物，其特征在于，式(II)所示肟酯类光引发剂中：
    R1表示C1-C8的直链或支链烷基，特别是甲基、乙基、正丙基、异丙基、正丁基、6-甲基庚基；
    R2和R3各自独立地表示C3-C5的直链或支链烷基、-O-CH2-R31、-CH2-O-R31、-CH2-S-R31、-CH2-OCO-CH2-R31、-CO-CH2-R31、-CH2-CH2-R31、或-OCO-R31，其中R31表示C4-C6的环烷基或杂环基；特别优选地，所述直链或支链烷基选自正丙基、正丁基、异丁基，R31表示环戊基、环己基、2-呋喃基、2-四氢呋喃基、或1-四氢吡咯基；并且，R2和R3中的至少一个是上述含有R31的基团；
    R4和R5各自独立地表示C1-C5的直链或支链烷基，特别是甲基、乙基、正丙基、异丙基、正丁基、异丁基；
    R6和R7各自独立地表示氢或硝基。
  8. 根据权利要求1-7中任一项所述的感光性树脂组合物，其特征在于，组分(C)光引发剂选自下列结构所示化合物中的一种或两种以上的组合：
    Figure PCTCN2016073119-appb-100003
    Figure PCTCN2016073119-appb-100004
    Figure PCTCN2016073119-appb-100005
  9. 权利要求1-8中任一项所述的感光性树脂组合物在制备彩色滤光片膜、黑色矩阵、光间隔物和肋栅中的应用。
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