WO2016058545A1 - 感光性树脂组成物、彩色滤光片及其液晶显示元件 - Google Patents

感光性树脂组成物、彩色滤光片及其液晶显示元件 Download PDF

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WO2016058545A1
WO2016058545A1 PCT/CN2015/092009 CN2015092009W WO2016058545A1 WO 2016058545 A1 WO2016058545 A1 WO 2016058545A1 CN 2015092009 W CN2015092009 W CN 2015092009W WO 2016058545 A1 WO2016058545 A1 WO 2016058545A1
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Prior art keywords
group
alkyl
substituted
phenyl
formula
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PCT/CN2015/092009
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English (en)
French (fr)
Inventor
廖豪伟
蔡宇杰
周泓佳
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奇美实业股份有限公司
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Priority to US15/518,767 priority Critical patent/US10591816B2/en
Priority to CN201580020653.9A priority patent/CN106233203B/zh
Publication of WO2016058545A1 publication Critical patent/WO2016058545A1/zh

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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
    • G03F7/0005—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
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a photosensitive resin composition, a color filter, and a liquid crystal display element thereof.
  • a photosensitive resin composition for a black matrix which is excellent in reliability under high resolution and high-temperature and high-humidity conditions, a color filter, and a liquid crystal display element thereof.
  • the materials used for the black matrix are mainly vapor-deposited films containing chromium or chromium oxide.
  • the vapor deposited film described above is used as a material of a black matrix, there are disadvantages such as a complicated manufacturing process and expensive materials.
  • a technique of forming a black matrix by photolithography using a photosensitive resin composition has been proposed.
  • Japanese Laid-Open Patent Publication No. 2006-259716 discloses a photosensitive resin composition for a black matrix comprising a high-usage black pigment, an alkali-soluble resin, a photopolymerization initiator, and a difunctional group. Reactive monomer and organic solvent. It is noted that a reactive monomer having a difunctional group can improve the reaction between the compounds to form a fine pattern. Thereby, in the photosensitive resin composition, the sensitivity of the photosensitive resin composition can be maintained while increasing the light-shielding property so as to increase the amount of the black pigment used.
  • Japanese Laid-Open Patent Publication No. 2008-268854 discloses a photosensitive resin composition for a black matrix.
  • the photosensitive resin composition contains an alkali-soluble resin having a carboxylic acid group and an unsaturated group, a photopolymerizable monomer having an ethylenically unsaturated group, a photopolymerization initiator, and a high usage amount. Black pigment.
  • the resolution of the photosensitive resin composition of the high-use black pigment is improved by using a specific alkali-soluble resin.
  • the photosensitive resin composition in which the amount of the black pigment used is increased in the prior art the light-shielding property can be increased.
  • the conventional photosensitive resin composition described above still has poor resolution, poor heat resistance, high temperature, and high temperature. Problems such as poor reliability under wet conditions.
  • the present invention provides a photosensitive resin composition, a color filter, and a liquid crystal display element thereof, and the photosensitive resin composition has good resolution, heat resistance resistance, and reliability under high temperature and high humidity. .
  • the present invention provides a photosensitive resin composition
  • a photosensitive resin composition comprising an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment (E).
  • the compound (B) having an ethylenically unsaturated group contains the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups.
  • the photoinitiator (C) includes a photoinitiator (C-1) represented by the formula (1).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 20 alkyl, COR 16 , OR 17 , halogen, NO 2 ,
  • the group represented by the formula (2) is a group represented by the formula (3),
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (4). Substituted C 2 -C 10 alkenyl,
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently taken as —(CH 2 ) p —Y— (CH 2 ) q —;
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5) ,
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5).
  • R 9, R 10, R 11 and R 12 are independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups to one another: halo, Phenyl, CN, OH, SH, C 1 -C 4 -alkoxy, -(CO)OH or -(CO)O-(C 1 -C 4 alkyl);
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted by one or more of the following groups: C 1 -C 6 alkyl, halogen, CN, OR 17 , SR 18 or NR 19 R 20 ;
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, halogen, CN, OR 17 , SR 18 , SOR 18 , SO 2 R 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R 17 , R 18 , R 19 and/or R 20 ;
  • R 9 , R 10 , R 11 and R 12 are each independently a group represented by COR 16 , NO 2 or formula (2),
  • Y represents O, S, NR 26 or a direct bond
  • p represents an integer of 0, 1, 2 or 3;
  • q represents an integer of 1, 2 or 3;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 or a group represented by the formula (6)
  • R 13 represents a C 2 -C 20 alkyl group, interspersed with one or more of O, S, SO, SO 2 , NR 26 or CO, or a C 2 -C 12 alkenyl group which is unintercalated or heterozygous Or a plurality of O, CO or NR 26 , wherein the meta-hetero C 2 -C 20 alkyl group and the unmeta- or inter-hetero C 2 -C 12 alkenyl group are unsubstituted or substituted by one or more halogens ;
  • R 13 represents C 4 -C 8 cycloalkenyl, C 2 -C 12 alkynyl or C 3 -C 10 cycloalkyl having no or hetero or one or more O, S, CO or NR 26 ;
  • R 13 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , COR 16 , CN, NO 2 , halogen, C 1 a C 2 alkyl group, a C 1 -C 4 haloalkyl group, a C 2 -C 20 alkyl group having one or more O, S, CO or NR 26 or a group represented by the formula (7),
  • Each warp or C 3 -C 10 cycloalkyl, or interrupted by one or more O, S, CO or NR C 3 26 -C 10 cyclic group is unsubstituted;
  • k represents an integer from 1 to 10;
  • R 14 represents hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkoxy or C 1 -C 20 alkyl, which is unsubstituted or one or more Substituted by: halogen, phenyl, C 1 -C 20 alkylphenyl or CN;
  • R 14 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, halogen, CN, OR 17 , SR 18 and / or NR 19 R 20 ;
  • R 14 represents a C 3 -C 20 heteroaryl group, a C 1 -C 8 alkoxy group, a benzyloxy group or a phenoxy group, the benzyloxy group and the phenoxy group being unsubstituted or having one or more of the following groups Substituted: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl and/or halogen;
  • R 15 represents C 6 -C 20 aryl or C 3 -C 20 heteroaryl, each of which is unsubstituted or Substituted by one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, interrupted by one or more O, S or
  • R 15 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 8 cycloalkyl having no or hetero or one or more O, CO or NR 26 ; or R 15 represents C 1 -C 20 alkyl , which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxy a group represented by a carbonyl group, a C 3 -C 20 heteroaryloxycarbonyl group, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO(OC k H 2k+1 ) 2 , a phenyl group, and a formula (6) Or a group represented by the formula (8),
  • C 1 -C 20 alkyl group is substituted by a phenyl group which is substituted by halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents a C 2 -C 20 alkyl group in which one or more O, SO or SO 2 are heterogeneous, and the inter-hetero C 2 -C 20 alkyl group is unsubstituted or has one or more of the following groups Substituted: halogen, OR 17 , COOR 17 , CONR 19 R 20 , phenyl or phenyl substituted by OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents a C 2 -C 20 alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, phenyl, OR 17 , SR 18 Or NR 19 R 20 ; or R 15 represents a naphthoyl group which is unsubstituted or substituted with one or more OR 17 or a C 3 -C 14 heteroarylcarbonyl group;
  • R 15 represents a C 2 -C 12 alkoxycarbonyl group which is undoped or inter-hetero-doped with one or more O and the inter- or un-doped C 2 -C 12 alkoxycarbonyl group is unsubstituted or One or more hydroxyl substitutions;
  • R 15 represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents CN, CONR 19 R 20 , NO 2 , C 1 -C 4 haloalkyl, S(O) m -C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl or SO 2- C 1 -C 6 alkyl-substituted S(O) m -phenyl;
  • R 15 represents an SO 2 O-phenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; or a diphenylphosphono group or a di-(C 1 -C 4 alkoxy)-phosphono group ;
  • n 1 or 2;
  • R' 14 has one of the meanings given for R 14 ;
  • R' 15 has one of the meanings given for R 15 ;
  • X 1 represents O, S, SO or SO 2 ;
  • X 2 represents O, CO, S or a direct bond
  • R 16 represents a C 6 -C 20 aryl group or a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or a C 1 -C 20 alkyl group having one or more O, S or NR 26 ; or each of one or more C 1 -C 20 alkane Substituted, the C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19
  • R 16 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted one or more of the following groups: halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 )alkyl, O(CO)-(C 1 -C 4 alkyl), O(CO) -phenyl, (CO)OH or (CO)O(C 1 -C 4 alkyl);
  • R 16 represents a C 2 -C 12 alkyl group in which one or more O, S or NR 26 are heterogeneous; or R 16 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n ( CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl;
  • R 16 represents a phenyl substituted with SR 18 , wherein the group R 18 represents a direct bond to the phenyl or naphthyl ring of the oxazole moiety to which the COR 16 group is attached;
  • n 1 to 20;
  • R 17 represents hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl), O(CO) -(C 2 -C 4 )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl, SO 2 - (C 1- C 4 haloalkyl), O(C 1 -C 4 haloalkyl) or a C 3 -C 20 cycloalkyl having one or more O;
  • R 17 represents C 2 -C 20 alkyl, in which one or more O, S or NR 26 are heterogeneous;
  • R 17 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 1 -C 8 alkanoyl, C 2 -C a 12 -alkenyl, C 3 -C 6 enoyl group or a C 3 -C 20 cycloalkyl group having no or hetero or one or more O, S, CO or NR 26 ;
  • R 17 represents a C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl group which is undoped or hetero-has one or more O;
  • R 17 represents a benzoyl group which is unsubstituted or substituted by one or more C 1 -C 6 alkyl groups, halogen, OH or C 1 -C 3 alkoxy groups;
  • R 17 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 Alkyl) 2 , a diphenyl-amine group or a group represented by the formula (7),
  • R 17 forms a direct bond bonded to one of the carbon atoms of the phenyl or naphthyl ring in which the group represented by the formula (2) or the group represented by the formula (7) is bonded,
  • R 18 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl, wherein the C 2 -C 12 alkenyl, C 3 -C 20 naphthenic Or a phenyl-C 1 -C 3 alkyl group which has no or hetero or one or more O, S, CO, NR 26 or COOR 17 ; or R 18 is a C 1 -C 20 alkyl group which is not Substituted or substituted with one or more of the following groups: OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O (C 1 -C 4 alkyl) , O(CO)-(C 2 -C 4 )alkenyl, O(CO)-(C 1 -C 4 alkyl), O(CO)-phenyl or (CO)OR 17 ;
  • R 18 represents a C 2 -C 20 alkyl group with one or more O, S, CO, NR 26 or COOR 17 interspersed therebetween;
  • R 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 8 alkanoyl or C 3 -C 6 olefin Acyl group
  • R 18 represents a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy or C 1 -C 4 Alkylthio group;
  • R 18 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 12 alkyl, C 1 -C 4- haloalkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenylamino, (CO)O(C 1 -C 8 alkyl), (CO)-C 1 -C 8 alkyl, (CO)N (C 1 -C 8 alkyl) 2 or a group represented by the formula (7),
  • R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3 - C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkanoyl, C 1 -C 8 alkanoyloxy, C 3 -C 12 alkenoyl, SO 2 -(C 1 - C 4 haloalkyl) or benzoyl;
  • R 19 and R 20 represent phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 4 haloalkyl, C 1- C 20 alkoxy, C 1 -C 12 alkyl, benzoyl or C 1 -C 12 alkoxy;
  • R 21 and R 22 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl;
  • R 21 and R 22 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 26 and which is either 5- or 6-membered saturated or unsaturated The ring is unfused or the 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring;
  • R 23 represents hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, intervening one or more O, CO or NR 26 C 2 -C 20 alkyl, uninter or hetero-O a C 3 -C 20 cycloalkyl group of S, CO or NR 26 , or R 23 represents phenyl, naphthyl, phenyl-C 1 -C 4 alkyl, OR 17 , SR 18 or NR 21 R 22 ;
  • R 24 represents (CO)OR 17 , CONR 19 R 20 , (CO)R 17 ; or R 24 has one of the meanings given for R 19 and R 20 ;
  • R 25 represents COOR 17 , CONR 19 R 20 , (CO)R 17 ; or R 25 has one of the meanings given for R 17 ;
  • R 26 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl with one or more O or CO in between; or phenyl-C 1 -C 4 alkane a C 3 -C 8 cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R 19 ; or a phenyl group which is unsubstituted or one or more Substituted by: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or a group represented by formula (7);
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 20 alkyl, COR 16 , NO 2 or a group represented by the formula (2);
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5) ;
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5). a group represented;
  • X represents CO or a direct bond
  • R -13 represents C -1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, OR- 17 , SR 18 , COOR 17 , CONR 19 R 20 or PO (OC k H 2k+1 ) 2 ;
  • R 13 represents a C 2 -C 20 alkyl group, interspersed with one or more O, S, NR 26 or CO;
  • R 13 represents a phenyl or naphthyl group, and the two are unsubstituted or substituted by COR 16 or substituted by one or more groups represented by formula (7);
  • R - 14 represents a C 1 -C 20 alkyl group, a phenyl group or a C 1 -C 8 alkoxy group
  • R 15 represents a phenyl group, a naphthyl group, a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 An SR 18 or C 2 -C 20 alkyl group having one or more O or S hetero; or each of which is substituted by one or more C 1 -C 20 alkyl groups, the C 1 -C 20 alkyl group being unsubstituted Substituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxy Alkylcarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 , NR 19 R 20 or PO(OC
  • R 15 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl Base, NR 19 R 20 , COOR 17 , CONR 19 R 20 or PO(OC k H 2k+1 ) 2 ;
  • R' 14 has one of the meanings given for R 14 ;
  • R' 15 has one of the meanings given for R 15 ;
  • R 16 represents a phenyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or a C 2 -C 20 having one or more O, S or NR 26 interstitial alkyl;
  • R 16 represents phenyl which is substituted with one or more C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following radicals: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 16 represents C 1 -C 20 alkyl, which is unsubstituted or substituted by halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl) or (CO)O(C 1 -C 4 alkyl);
  • R -17 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O ( C 1 -C 4 alkyl), (CO) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl interrupted by one or more O or a C 3 -C 20 cycloalkyl;
  • R 17 represents a C 2 -C 20 alkyl group, in which one or more O;
  • R 18 represents a methyl group substituted by COOR 17 ;
  • R 19 and R 20 are each independently hydrogen, phenyl, C 1 -C 20 alkyl, C 1 -C 8 alkanoyl or C 1 -C 8 alkanoyloxy;
  • R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted via a group represented by formula (7);
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, or R 1 and R 2 , R 3 and R 4 or R 5 and R 6 independently of each other are a group represented by the formula (5);
  • R 1 and R 2 , R 3 and R 4 or R 5 and R 6 is a group represented by the formula (5);
  • R 2 represents COR 16 , NO 2 or a group represented by formula (2) or a group represented by formula (3);
  • R 7 represents COR 16 or a group represented by formula (2)
  • R 9 , R 11 and R 12 represent hydrogen
  • R- 10 represents hydrogen, OR 17 or COR 16 ;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , OR 17 , SR 18 or PO(OC k H 2k+1 ) 2 ;
  • R 13 represents a C 2 -C 20 alkyl group, in which one or more O;
  • R 13 represents a phenyl group
  • k represents an integer 2;
  • R 14 represents a C 1 -C 20 alkyl group or a thienyl group
  • R 15 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more OR 17 or C 1 -C 20 alkyl groups;
  • R 15 represents a thiophene group, hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: OR 17, SR 18, C 3 -C 8 -cycloalkyl, NR 19 R 20 or COOR 17 ;
  • R 15 represents a C 2 -C 20 alkyl group, interspersed with SO 2 ;
  • R 16 represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl;
  • R 16 represents a thienyl group
  • R 17 represents hydrogen, C 1 -C 8 alkanoyl, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: halo, O (CO) -(C 1 -C 4 alkyl), O(CO)-(C 2 -C 4 alkenyl) or a C 3 -C 20 cycloalkyl group having one or more O;
  • R 17 represents a C 2 -C 20 alkyl group, in which one or more O;
  • R 18 represents a C 3 -C 20 cycloalkyl group, a C 1 -C 20 alkyl group which is unsubstituted or via one or more OH, O(CO)-(C 2 -C 4 alkenyl) or (CO) ) OR 17 replaced;
  • R 18 represents a phenyl group which is unsubstituted or substituted with one or more halogens
  • R 19 and R 20 are each independently a C 1 -C 8 alkanoyl group or a C 1 -C 8 alkanoyloxy group;
  • R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated ring interspersed with O;
  • the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1), wherein the alkali-soluble resin (A-1) is obtained by polymerizing a mixture, and the mixture includes : a diol compound (a-1-1) containing a polymerizable unsaturated group; a tetracarboxylic acid or an acid dianhydride thereof (a-1-2); and a dicarboxylic acid or an anhydride thereof (a-1-3).
  • the polymerizable unsaturated group-containing diol compound (a-1-1) is reacted with an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group.
  • the epoxy compound having at least two epoxy groups includes a structure represented by the formula (a-1), a structure represented by the formula (a-2) or both of the above structures.
  • W 1 , W 2 , W 3 and W 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and carbon.
  • the number is 6 to 12 aryl or 6 to 12 aralkyl.
  • W 5 to W 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and s represents an integer of 0 to 10.
  • the alkali-soluble resin (A-1) has a number average molecular weight of 1,000 to 8,000.
  • At least one of the tetracarboxylic acid or its acid dianhydride (a-1-2) and the dicarboxylic acid or its anhydride (a-1-3) contains a fluorine atom.
  • the alkali-soluble resin (A) comprises an alkali-soluble resin (A-2) synthesized by polycondensation of a silane monomer, or It is formed by polycondensation using a silane monomer and another compound for polymerizable.
  • the photosensitive resin composition further includes a multi-branched polymer (F).
  • the multi-branched polymer (F) is formed by reacting a polyfluorenyl compound represented by the formula (F2) with a polyfunctional (meth) acrylate represented by the formula (F1).
  • M 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • M 2 represents a residue after esterification of g hydroxyl groups in the hydroxyl group-containing compound having h hydroxyl groups, wherein h ⁇ g, and g represents an integer of 2 to 20. It is M 3 (OH) h or M 3 (OH) h propylene oxide, epichlorohydrin, alkyl, alkoxy or hydroxypropyl acrylate modified compounds of the hydroxyl group-containing compound via.
  • M 3 (OH) h is a polyol having a carbon number of 2 to 18, a polyol ether formed of the polyol, an ester formed by reacting the polyol with an acid, or a silicone.
  • M 4 represents a single bond, a hydrocarbon group having 1 carbon number, or a linear or branched hydrocarbon group having 2 to 22 carbon atoms.
  • the skeleton of M 4 may further include a sulfur atom or an oxygen atom constituting the ester group.
  • i represents an integer of 2 to 6, wherein when M 4 represents a single bond, i represents 2; when M 4 represents a hydrocarbon group having a carbon number of 1, i represents an integer of 2 to 4; and when M 4 represents a carbon number of 2 When it is a linear or branched hydrocarbon group of 22, i represents an integer of 2 to 6.
  • the photosensitive resin composition further includes the compound (H) represented by the formula (10).
  • Z 1 , Z 2 and Z 3 each independently represent a trialkoxysilane group bonded via an alkylene group or an arylene group.
  • the compound (B) having an ethylenically unsaturated group is used in an amount of 15 parts by weight to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups is used in an amount of 15 parts by weight to 150 parts by weight, and the photoinitiator (C) is used in an amount of 10 parts by weight to 80 parts by weight.
  • the photoinitiator (C-1) represented by the formula (1) is used in an amount of 10 parts by weight to 70 parts by weight, and the solvent (D) is used in an amount of 1000 parts by weight to 8000 parts by weight.
  • the black pigment (E) is used in an amount of from 150 parts by weight to 1200 parts by weight.
  • the alkali-soluble resin (A-1) is used in an amount of 50 parts by weight to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the alkali-soluble resin (A-2) is used in an amount of from 0 part by weight to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the multi-branched polymer (F) is used in an amount of from 3 parts by weight to 35 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the hot start agent (G) is used in an amount of from 4 parts by weight to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the compound (H) represented by the formula (10) is used in an amount of from 1 part by weight to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the present invention also provides a black matrix which is formed using the above-described photosensitive resin composition.
  • the present invention also provides a color filter comprising the above-described black matrix.
  • the present invention further provides a liquid crystal display comprising the above-described color filter.
  • the photosensitive resin composition of the present invention includes the compound (B) having an ethylenically unsaturated group and a photoinitiator (C) having a specific structure, thereby improving the resolution, heat resistance, and high temperature of the black matrix. And the problem of poor reliability under high humidity, and further applicable to color filters and liquid crystal display devices.
  • the present invention provides a photosensitive resin composition
  • a photosensitive resin composition comprising an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (C), a solvent (D), and a black pigment (E).
  • the photosensitive resin composition may further include a multi-branched polymer (F), a thermal initiator (G), and a compound (H) represented by the formula (10).
  • acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid
  • acrylate and/or methacrylate is represented by (meth) acrylate
  • (meth) The acryloyl group means an acryloyl group and/or a methacryloyl group.
  • the alkali-soluble resin (A) includes an alkali-soluble resin (A-1), an alkali-soluble resin (A-2), and other alkali-soluble resins (A-3).
  • Alkali soluble resin (A-1) Alkali soluble resin (A-1)
  • the alkali-soluble resin (A-1) is obtained by polymerizing a mixture.
  • the mixture includes a diol compound (a-1-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or its acid dianhydride (a-1-2), and a dicarboxylic acid or an anhydride thereof (a-1-3).
  • the diol compound (a-1-1) containing a polymerizable unsaturated group is obtained by reacting an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. .
  • the epoxy compound having at least two epoxy groups includes a structure represented by the formula (a-1), a structure represented by the formula (a-2), and a structure represented by the formula (a-3), or the above three structures. .
  • the structure represented by the formula (a-1), the structure represented by the formula (a-2), and the structure represented by the formula (a-3) will be specifically described.
  • W 1 , W 2 , W 3 and W 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and carbon.
  • the number is 6 to 12 aryl or 6 to 12 aralkyl.
  • the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-1) may include a bisphenol quinoid compound having an epoxy group obtained by reacting a bisphenol quinoid compound with a halogenated propylene oxide. .
  • the bisphenol quinoid compound examples include: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9 - bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis (4 -Hydroxy-3,5-dichlorophenyl)indole, 9,9-bis(4-hydroxy-3,5-dibromophenyl)indole or an analogue thereof, or a combination of the above compounds.
  • halogenated propylene oxide examples include 3-chloro-1,2-epoxypropane or 3-bromo-1,2-epoxypropane or the like, or a combination of the above compounds.
  • the bisphenol quinoid compound having an epoxy group examples include (1) a product manufactured by Nippon Steel Chemical Co., Ltd.: ESF-300 or the like; (2) a product manufactured by Osaka Gas: for example, PG-100, EG- 210 or the like; (3) Goods manufactured by SMS Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.
  • W 5 to W 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and s represents an integer of 0 to 10.
  • the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2) may include a compound having a structure of the following formula (a-2-I) and halogenated in the presence of an alkali metal hydroxide.
  • the propylene oxide is obtained by a reaction.
  • the formula is W 5 to W 18 (a-2) and the same definition of W s, respectively, and W 18 is defined to 5 s, and this is not described herein.
  • a method of synthesizing an epoxy compound having at least two epoxy groups having a structure represented by the formula (a-2) can be referred to the patent of Taiwan Publication No. TW201508418.
  • epoxy compound having at least two epoxy groups having the structure represented by the formula (a-2) include the trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P. Goods manufactured by medicine.
  • Ar 1 represents a naphthalene ring
  • Q 1 represents a cyano group, a halogen or a hydrocarbon group
  • Q 2 represents a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group or an alkylthio group.
  • J represents an alkyl group
  • xa represents an integer from 0 to 4
  • xb and xc represent 0 The above integer.
  • the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-3) include 9,9-bis(glycidoxynaphthyl)anthracene, and are, for example, 9,9 a compound such as bis(6-glycidoxy-2-naphthyl)anthracene or 9,9-bis(5-glycidoxy-1-naphthyl)anthracene.
  • the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the group consisting of the following (1) to (3):
  • Acrylic acid methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxybutyl succinic acid, 2-methacryloyloxyethyl adipate, 2- Methacryloyloxybutyl adipate, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxypropyl horse Acid, 2-methacryloyloxybutyl maleic acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl adipate, 2-methacryloyloxypropane Tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryloyloxybutyl phthalic acid, 2-methacryloyloxybutyl hydrogen phthalic acid or the like ;
  • a compound obtained by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound and specific examples of the dicarboxylic acid compound include adipic acid, succinic acid, maleic acid, ortho-benzene Formic acid or an analogue thereof;
  • a half ester compound obtained by reacting a (meth) acrylate having a hydroxyl group with a carboxylic anhydride compound and specific examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate or analog.
  • carboxylic anhydride compound described herein is the same as the tetracarboxylic dianhydride or the dicarboxylic acid anhydride described below, and will not be further described herein.
  • the tetracarboxylic acid or its acid dianhydride (a-1-2) includes a tetracarboxylic acid containing a fluorine atom or an acid dianhydride thereof, and a tetracarboxylic acid other than the fluorine atom-containing tetracarboxylic acid or its acid dianhydride.
  • the tetracarboxylic acid containing a fluorine atom or an acid dianhydride thereof is selected from the group consisting of a fluorine atom-containing tetracarboxylic acid compound represented by formula (K-1) and a fluorine atom-containing tetracarboxylic dianhydride compound represented by formula (K-2).
  • the group of people formed Specifically, the fluorine atom-containing tetracarboxylic acid compound represented by the formula (K-1) and the fluorine atom-containing tetracarboxylic dianhydride compound represented by the formula (K-2) are as follows.
  • L 2 is a tetravalent aromatic group having fluorine, and preferably has a benzene ring. Specifically, it is preferably one selected from the group consisting of the formula (L-1) to the formula (L-6).
  • E each independently represents a fluorine atom or a trifluoromethyl group, and * represents a position bonded to a carbon atom.
  • tetracarboxylic acid or acid dianhydride containing a fluorine atom examples include 4,4'-hexafluoroisopropylidene diphthalic acid, 1,4-difluorobenzenetetracarboxylic acid, and 1- A fluorine-containing aromatic tetracarboxylic acid such as monofluorobenzenetetracarboxylic acid or 1,4-bis(trifluoromethyl)benzenetetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or a combination of the above compounds.
  • tetracarboxylic acid or the acid dianhydride containing a fluorine atom further include 3,3'-hexafluoroisopropylidene diphthalic acid, 5,5'-[2,2,2-trifluoro-1 -[3-(Trifluoromethyl)phenyl]ethylidene]diphthalic acid, 5,5'-[2,2,3,3,3-pentafluoro-1-(trifluoromethyl) Propylene]diphthalic acid, 5,5'-oxybis[4,6,7-trifluoro-pyromellitic acid], 3,6-bis(trifluoromethyl)benzenetetracarboxylic acid, a fluorine-containing tetracarboxylic acid such as 4-(trifluoromethyl)benzenetetracarboxylic acid or 1,4-bis(3,4-dicarboxylic acid trifluorophenoxy)tetrafluorobenzene, or a second of the above tetracar
  • the other tetracarboxylic acid or its acid dianhydride includes a saturated linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, or a dianhydride compound of the above tetracarboxylic acid, or a combination thereof.
  • saturated linear hydrocarbon tetracarboxylic acid examples include butane tetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, or a combination of the above compounds.
  • the saturated linear hydrocarbon tetracarboxylic acid may also have a substituent.
  • alicyclic tetracarboxylic acid examples include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, norbornanetetracarboxylic acid, or a combination of the above compounds.
  • the alicyclic tetracarboxylic acid may also have a substituent.
  • aromatic tetracarboxylic acid examples include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, 1,2,3,6 - tetrahydrophthalic acid, or a compound of the above combination.
  • the aromatic tetracarboxylic acid may also have a substituent.
  • the dicarboxylic acid or its anhydride (a-1-3) includes a dicarboxylic acid containing a fluorine atom or an anhydride thereof, a dicarboxylic acid other than the fluorine atom-containing dicarboxylic acid or an anhydride thereof, or an anhydride thereof or the above A combination of two.
  • the dicarboxylic acid containing a fluorine atom or an anhydride thereof is selected from the group consisting of a fluorine atom-containing dicarboxylic acid compound represented by the formula (G-1) and a fluorine atom-containing dicarboxylic anhydride compound represented by the formula (G-2). .
  • the fluorine atom-containing dicarboxylic acid compound represented by the formula (G-1) and the fluorine atom-containing dicarboxylic acid anhydride compound represented by the formula (G-2) are as follows.
  • G 1 represents an organic group of a fluorine atom having 1 to 100 carbon atoms.
  • fluorine-containing dicarboxylic acid or its anhydride examples include 3-fluorophthalic acid, 4-fluorophthalic acid, tetrafluorophthalic acid, 3,6-difluorophthalic acid, and tetrafluoroethylene.
  • dicarboxylic acid or its anhydride examples include a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an unsaturated dicarboxylic acid, or an acid anhydride of the above dicarboxylic acid compound, or a combination of the above compounds.
  • saturated linear hydrocarbon dicarboxylic acid examples include succinic acid, acetyl succinic acid, adipic acid, sebacic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxopentane Acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, or a combination of the above compounds. Hydrocarbyl groups in saturated linear hydrocarbon dicarboxylic acids can also be substituted.
  • saturated cyclic hydrocarbon dicarboxylic acid examples include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, or the like combination.
  • the saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon substituted alicyclic dicarboxylic acid.
  • unsaturated dicarboxylic acid examples include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl bridgedmethylenetetrahydrophthalic acid, chlorinic acid, and trimellitic acid. , or a combination of the above compounds.
  • dicarboxylic acids or anhydrides thereof include trimethoxysilylpropyl succinic anhydride, triethyl ethoxide Oxysilylpropyl succinic anhydride, methyldimethoxysilyl propyl succinic anhydride, methyldiethoxysilyl propyl succinic anhydride, trimethoxysilylbutyl succinic anhydride, three Ethoxysilyl butyl succinic anhydride, methyl diethoxysilyl butyl succinic anhydride, p-(trimethoxysilyl) phenyl succinic anhydride, p-(triethoxysilyl) phenyl Succinic anhydride, p-(methyldimethoxysilyl)phenyl succinic anhydride, p-(methyldiethoxysilyl)phenyl succinic anhydride, m-(trimethoxysilyl)phenyl buty
  • the method for synthesizing the alkali-soluble resin (A-1) is not particularly limited as long as the diol compound (a-1-1) containing a polymerizable unsaturated group, tetracarboxylic dianhydride or its tetracarboxylic acid (a-1) -2) is obtained by reacting a dicarboxylic anhydride or a dicarboxylic acid thereof (a-1-3), and can be synthesized by referring to the patent of Taiwan Publication No. TW201508418.
  • the number average molecular weight of the alkali-soluble resin (A-1) is from 1,000 to 8,000.
  • the alkali-soluble resin (A-1) is used in an amount of 50 to 100 parts by weight, preferably 60 parts by weight to 100 parts by weight, and more preferably 70% by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts to 100 parts by weight.
  • the alkali-soluble resin (A-1) contains a fluorine atom, the reliability of the obtained photosensitive resin composition at high temperature and high humidity can be further improved.
  • the alkali-soluble resin (A-2) is synthesized by polycondensation of a silane monomer or by polycondensation using a silane monomer and another polymerizable compound.
  • the kind of the alkali-soluble resin (A-2) is not particularly limited as long as the object of the present invention can be attained.
  • Silane monomers include, but are not limited to, silane monomers (a-S1), silane monomers (a-S2); other polymerizable compounds comprise siloxane prepolymer (a-S3), silica particles (a -S4), or a combination thereof.
  • silane monomers a-S1
  • silane monomers a-S2
  • silica particles a -S4
  • the silane monomer (a-S1) is a compound represented by the formula (9-1).
  • each of U 1 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, and an acid anhydride group.
  • 2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 15 carbon atoms
  • w represents an integer of 1 to 3.
  • U 1 in the formula (9-1) represents an alkyl group having a carbon number of 1 to 10
  • U 1 is, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group. N-butyl, tert-butyl, n-hexyl or n-decyl.
  • U 1 may be an alkyl group having another substituent on the alkyl group, and specifically, U 1 is, for example, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-aminopropyl group, or a 3- Mercaptopropyl or 3-isocyanate propyl.
  • U 1 in the formula (9-1) represents an alkenyl group having 2 to 10 carbon atoms
  • U 1 is, for example, a vinyl group.
  • U 1 may be an alkenyl group having another substituent on the alkenyl group, and specifically, U 1 is, for example, a 3-acryloyloxypropyl group or a 3-methacryloxypropyl group.
  • U 1 in the formula (9-1) represents an aromatic group having a carbon number of 6 to 15, specifically, U 1 is, for example, a phenyl group, a tolyl group or a naphthyl group. Further, U 1 may also be an aromatic group having an alternative substituent on the aromatic group, and specifically, U 1 is, for example, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyl) Phenyl)ethyl or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl.
  • U 1 in the formula (9-1) represents an alkyl group having an acid anhydride group, wherein the alkyl group is preferably an alkyl group having a carbon number of 1 to 10.
  • the acid group-containing alkyl group is, for example, ethyl succinic anhydride represented by the formula (9-1-1), propyl succinic anhydride represented by the formula (9-1-2) or a formula ( The propyl glutaric anhydride shown in 9-1-3).
  • the acid anhydride group is a group formed by intramolecular dehydration of a dicarboxylic acid such as succinic acid or glutaric acid.
  • U 1 in the formula (9-1) represents an alkyl group having an epoxy group
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.
  • the epoxy group-containing alkyl group is, for example, propylene oxide pentyl group or 2-(3,4-epoxycyclohexyl)ethyl group.
  • the epoxy group is a group formed by intramolecular dehydration of a glycol, such as propylene glycol, butylene glycol or pentanediol.
  • U 1 in the formula (9-1) represents an alkoxy group having an epoxy group, and the alkoxy group is preferably an alkoxy group having a carbon number of 1 to 10.
  • the epoxy group-containing alkoxy group is, for example, a glycidoxypropyl group or a 2-epoxypropoxybutyloxy group.
  • U 2 of the formula (9-1) represents an alkyl group having a carbon number of 1 to 6, specifically, U 2 is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group.
  • U 2 in the formula (9-1) represents an acyl group having 1 to 6 carbon atoms, specifically, U 2 is, for example, an acetyl group.
  • U 2 in the formula (9-1) represents an aromatic group having a carbon number of 6 to 15, specifically, U 2 is, for example, a phenyl group.
  • w represents an integer of 1 to 3.
  • w represents 2 or 3
  • a plurality of U 1 may be the same or different;
  • w represents 1 or 2
  • a plurality of U 2 may be the same or different.
  • silane monomer (a-S1) examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-ring).
  • the silane monomers (a-S1) may be used singly or in combination of two or more.
  • the silane monomer (a-S2) is a compound represented by the formula (9-2).
  • U 3 each independently represent a hydrogen atom, alkyl having 1 to 10 carbon atoms or an alkenyl group of 2 to 10 carbon atoms, an aromatic group having 6 to 15;
  • U 4 are each independently It represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 15 carbon atoms; and
  • u represents an integer of 0 to 3.
  • U 3 in the formula (9-2) represents an alkyl group having a carbon number of 1 to 10
  • U 3 is, for example, a methyl group, an ethyl group, a n-propyl group or an isopropyl group. N-butyl, tert-butyl, n-hexyl or n-decyl.
  • U 3 may also be an alkyl group having another substituent on the alkyl group, and specifically, U 3 is, for example, a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-aminopropyl group, or a 3- Mercaptopropyl or 3-isocyanate propyl.
  • U 3 in the formula (9-2) represents an alkenyl group having 2 to 10 carbon atoms
  • U 3 is, for example, a vinyl group.
  • U 3 may be an alkenyl group having another substituent on the alkenyl group, and specifically, U 3 is, for example, a 3-acryloyloxypropyl group or a 3-methacryloxypropyl group.
  • U 3 in the formula (9-2) represents an aromatic group having a carbon number of 6 to 15, specifically, U 3 is, for example, a phenyl group, a tolyl group or a naphthyl group. Further, U 3 may also be an aromatic group having an alternative substituent on the aromatic group, and specifically, U 3 is, for example, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyl) Phenyl)ethyl or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl.
  • U 4 of the formula (9-2) represents an alkyl group having a carbon number of 1 to 6, specifically, U 4 is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group.
  • U 4 in the formula (9-2) represents an acyl group having 1 to 6 carbon atoms, specifically, U 4 is, for example, an acetyl group.
  • U 4 in the formula (9-2) represents an aromatic group having 6 to 15 carbon atoms, specifically, U 4 is, for example, a phenyl group.
  • u is an integer of 0 to 3.
  • a plurality of U 3 may be the same or different; when u represents 0, 1, or 2, a plurality of U 4 may be the same or different.
  • the hydrolyzable group refers to a group which can undergo a hydrolysis reaction and is bonded to silicon, and for example, the hydrolyzable group is, for example, an alkoxy group, an acyloxy group or a phenoxy group.
  • silane monomer represented by the formula (9-2) include, but are not limited to:
  • a tetrafunctional silane monomer tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane or tetraphenoxysilane;
  • Trifunctional silane monomer methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane , n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, mercaptotrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethyl Oxysilane, phenyltriethoxysilane, p-hydroxyphenyltrime
  • Difunctional silane monomer dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane or diphenyl Dimethoxysilane; or
  • the various silane monomers described may be used singly or in combination of two or more.
  • the siloxane prepolymer (a-S3) is a compound represented by the formula (9-3).
  • U 5 , U 6 , U 7 and U 8 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or a carbon number of 6 to An aromatic group of 15, wherein any one of the alkyl group, the alkenyl group and the aromatic group optionally has a substituent; and U 9 and U 10 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1 An acyl group to 6 or an aromatic group having 6 to 15 carbon atoms, wherein any one of the alkyl group, the acyl group and the aryl group optionally has a substituent; and v represents an integer of 1 to 1000.
  • U 5 , U 6 , U 7 and U 8 in the formula (9-3) each independently represent an alkyl group having a carbon number of 1 to 10, specifically, U 5 , U 6 , U 7 and U 8 are each independently, for example, methyl, ethyl or n-propyl.
  • U 5 , U 6 , U 7 and U 8 in the formula (9-3) each independently represent an alkenyl group having 2 to 10 carbon atoms, specifically, U 5 , U 6 , U 7 and U 8 are, for example, Each is independently a vinyl, acryloxypropyl or methacryloxypropyl group.
  • U 5 , U 6 , U 7 and U 8 in the formula (9-3) each independently represent an aromatic group having a carbon number of 6 to 15, specifically, U 5 , U 6 , U 7 and U 8 are, for example, Each is independently a phenyl group, a tolyl group or a naphthyl group. Further, any of the alkyl group, the alkenyl group and the aromatic group may have other substituents.
  • U 9 and U 10 of the formula (9-3) each independently represent an alkyl group having a carbon number of 1 to 6, specifically, U 9 and U 10 are each independently, for example, methyl, ethyl or n-propyl. Base, isopropyl or n-butyl.
  • U 9 and U 10 of the formula (9-3) each independently represent an acyl group having a carbon number of 1 to 6, specifically, U 9 and U 10 are, for example, an acetyl group.
  • U 9 and U 10 in the formula (9-3) each independently represent an aromatic group having a carbon number of 6 to 15, specifically, U 9 and U 10 are, for example, a phenyl group.
  • any one of the above alkyl group, acyl group and aryl group may optionally have a substituent.
  • v may be an integer of 1 to 1000, preferably an integer of 3 to 300, more preferably an integer of 5 to 200.
  • v is an integer of from 2 to 1000, each of U 5 is the same or different group, and each of U 6 is the same or different group.
  • siloxane prepolymer (a-S3) examples include, but are not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3, 3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane or by Gilles Commercially available silanol terminated polydimethylsiloxane (trade name such as DMS-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (trade name) Molecular weight 4200), DMS-S27 (molecular weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular weight 49000), DMS-S38 (molecular weight 58000) ), DMS-S42 (molecular
  • the siloxane prepolymer (a-S3) may be used singly or in combination of two or more.
  • the average particle diameter of the silica particles (a-S4) is not particularly limited.
  • the average particle diameter ranges from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more preferably from 10 nm to 100 nm.
  • silica particles include, but are not limited to, commercially available products manufactured by Catalyst Chemicals Co., Ltd. (trade names such as OSCAR 1132 (particle diameter: 12 nm; dispersant: methanol), OSCAR 1332 (particle size: 12 nm; dispersant is positive) Propanol), OSCAR 105 (particle size: 60 nm; dispersant: ⁇ -butyrolactone), OSCAR 106 (particle size: 120 nm; dispersant: diacetone alcohol), etc., and commercial products manufactured by Fuso Chemical Co., Ltd.
  • Quartron PL-1-IPA particle size 13nm; dispersant is isopropanone
  • Quartron PL-1-TOL particle size 13nm; dispersant is toluene
  • Quartron PL-2L-PGME particle size 18nm; dispersant
  • It is propylene glycol monomethyl ether) or Quartron PL-2L-MEK particle size 18 nm; dispersant is methyl ethyl ketone), etc. or a commercial product manufactured by Nissan Chemical Co., Ltd.
  • silica particles may be used singly or in combination of two or more.
  • the polymerization (ie, hydrolysis and partial condensation) of the silane monomer, the polysiloxane prepolymer, and/or the silica particles is carried out by adding a solvent, water, or The catalyst may be optionally added; and heated and stirred at 50 ° C to 150 ° C for 0.5 hours to 120 hours, and by-products (alcohols, water, etc.) may be further removed by distillation.
  • a solvent water
  • the catalyst may be optionally added; and heated and stirred at 50 ° C to 150 ° C for 0.5 hours to 120 hours, and by-products (alcohols, water, etc.) may be further removed by distillation.
  • the solvent used in the polycondensation reaction is not particularly limited, and the solvent can be used in the sense of the present invention.
  • the solvent (D) included in the photosensitive resin composition is the same or different.
  • the solvent is preferably used in an amount of from 15 parts by weight to 1200 parts by weight, more preferably from 20 parts by weight to 1100 parts by weight, still more preferably from 30 parts by weight to 1000 parts by weight, based on 100 parts by weight of the total of the silane monomers.
  • the hydrolyzable group based on the silane monomer is 1 mol, and the water used for the polycondensation reaction (i.e., water for hydrolysis) is preferably 0.5 mol to 2 mol.
  • the catalyst used in the polycondensation reaction is not particularly limited, and is preferably selected from an acid catalyst or a base catalyst.
  • the acid catalyst include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof, or an ion exchange resin.
  • the base catalyst include, but are not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, an alkoxy group-containing silane or an ion exchange resin containing an amine group.
  • the catalyst is preferably used in an amount of from 0.005 parts by weight to 15 parts by weight, based on the total amount of the silane monomer, of 100 parts by weight; more preferably from 0.01 part by weight to 12 parts by weight; still more preferably from 0.05 part by weight to 10 parts by weight.
  • the polysiloxane is preferably free of by-products (such as alcohols or water) and catalysts. Therefore, the reaction mixture after the polycondensation reaction can be selectively purified to obtain a polysiloxane.
  • the method of purification is not particularly limited, and it is preferred to dilute the reaction mixture with a hydrophobic solvent. Next, the hydrophobic solvent and the reaction mixture were transferred to a separatory funnel. Then, the organic layer was washed several times with water, and the organic layer was concentrated by a rotary evaporator to remove alcohol or water.
  • the catalyst can be removed using an ion exchange resin.
  • the alkali-soluble resin (A-2) is used in an amount of 0 to 50 parts by weight, preferably 0 parts by weight to 40 parts by weight, and more preferably 0, based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight to 30 parts by weight.
  • the alkali-soluble resin (A) contains the alkali-soluble resin (A-2), the reliability of the obtained photosensitive resin composition at high temperature and high humidity can be further improved.
  • the alkali-soluble resin (A) may also optionally include other alkali-soluble resins (A-3).
  • the other alkali-soluble resin (A-3) is a resin other than the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2).
  • the other alkali-soluble resin (A-3) is, for example, a resin having a carboxylic acid group or a hydroxyl group, but is not limited to a resin having a carboxylic acid group or a hydroxyl group.
  • Specific examples of the other alkali-soluble resin (A-3) include an acrylic resin and an urethane tree. Resin, resin such as novolak resin.
  • the compound (B) having an ethylenically unsaturated group includes the compound (B-1) having an acidic group and at least three (above) ethylenically unsaturated groups, and another compound (B-2) having an ethylenically unsaturated group.
  • the compound (B) having an ethylenically unsaturated group of the present invention may contain the compound (B-1) having an acidic group and at least three (above) ethylenically unsaturated groups.
  • the acidic group in the compound (B-1) having an acidic group and at least three (above) ethylenically unsaturated groups can act with an alkaline developer.
  • the acidic group include a carboxyl group, a sulfonic acid group or a phosphoric acid group.
  • the acidic group is preferably a carboxyl group which can exert a good effect with an alkali developer.
  • the compound (B-1) having an acidic group and at least three (above) ethylenically unsaturated groups may be (1) a polyfunctional (meth) acrylate having a hydroxyl group and a dicarboxylic acid anhydride or a dibasic acid. a modification reaction to synthesize a carboxyl group-containing polyfunctional (meth) acrylate, or (2) a modification reaction of an aromatic polyfunctional (meth) acrylate with concentrated sulfuric acid or fuming sulfuric acid to synthesize a A sulfonic acid based polyfunctional (meth) acrylate.
  • the compound (B-1) having an acidic group and at least three (above) ethylenically unsaturated groups has a structure represented by the following formula (IV) or (V):
  • T 1 represents -CH 2 -, -OCH 2 -, -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 - or -OCH 2 CH 2 CH 2 CH 2 -;
  • T 2 represents a structure represented by the following formula (IV-1) or formula (IV-2);
  • T 3 represents a structure represented by the following formula (IV-3), formula (IV-4) or formula (IV-5), wherein
  • the benzene ring in the structure shown in (IV-5) may also be tetrahydro or hexahydro, and e represents an integer of 1 to 8;
  • d represents an integer of 0 to 14:
  • T 1 , T 2 and T 3 are as defined above; T 4 represents -O- or the following formula (V-1)
  • T 1 and T 2 when the presence of a plurality of T 1 and T 2, T 1 and T 2, respectively, may be the same or different.
  • Specific examples of (B-1) may be monohydroxy oligoacrylate or monohydroxy oligomethyl group such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol penta methacrylate.
  • a carboxyl group-containing monoester compound formed from an acrylate and a diacid such as malonic acid, succinic acid, glutaric acid, isophthalic acid, terephthalic acid or phthalic acid.
  • the above compound having an acidic group and at least three (above) ethylenically unsaturated groups is preferably pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate and succinic acid, Carboxyl group formed by phthalic acid or glutaric acid Monoester compound.
  • the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups is used in an amount of 15 parts by weight to 150 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). It is preferably from 20 parts by weight to 120 parts by weight, more preferably from 25 parts by weight to 100 parts by weight.
  • the compound (B) having an ethylenically unsaturated group does not use the compound (B-1) having an acidic group and at least three ethylenically unsaturated groups, the resolution of the photosensitive resin composition produced is not good.
  • the compound (B) having an ethylenically unsaturated group may further contain another compound (B-2) having an ethylenically unsaturated group.
  • the other compound (B-2) having an ethylenically unsaturated group may be selected from a compound having one ethylenically unsaturated group or a compound having two or more (including two) ethylenically unsaturated groups.
  • the aforementioned compound having an ethylenically unsaturated group may include, but is not limited to, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylic acid-7-amino-3,7-dimethyloctyl Ester, isobutoxymethyl (meth) acrylamide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, B Diethylene glycol (meth) acrylate, third octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, (meth) acrylate Dodecyl ester, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, (meth
  • the above compound having two or more (including two) ethylenically unsaturated groups may include, but is not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, and triethylene glycol II.
  • the other ethylenically unsaturated group-containing compound (B-2) such as: trimethylolpropyl acrylate, trimethylol propyl triacrylate modified with ethylene oxide, epoxy Propane-modified trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol Acrylate, ditrimethylolpropyl methacrylate, propylene oxide modified glycerol triacrylate or any combination of the above.
  • trimethylolpropyl acrylate trimethylol propyl triacrylate modified with ethylene oxide
  • epoxy Propane-modified trimethylolpropyl triacrylate pentaerythritol triacrylate,
  • the compound (B) having an ethylenically unsaturated group is used in an amount of 15 parts by weight to 200 parts by weight, preferably 20 parts by weight to 170 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, it is 25 parts by weight to 150 parts by weight.
  • the photoinitiator (C) includes a photoinitiator (C-1) and other photoinitiators (C-2).
  • the photoinitiator (C) includes a photoinitiator (C-1) represented by the formula (1).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 20 alkyl, COR 16 , OR 17 , halogen, NO 2 ,
  • the group represented by the formula (2) is a group represented by the formula (3),
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (4). Substituted C 2 -C 10 alkenyl,
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently taken as —(CH 2 ) p —Y— (CH 2 ) q —;
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5) ;
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5).
  • R 9, R 10, R 11 and R 12 are independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups to one another: halo, Phenyl, CN, OH, SH, C 1 -C 4 -alkoxy, -(CO)OH or -(CO)O-(C 1 -C 4 alkyl);
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted by one or more of the following groups: C 1 -C 6 alkyl, halogen, CN, OR 17 , SR 18 or NR 19 R 20 ;
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, halogen, CN, OR 17 , SR 18 , SOR 18 , SO 2 R 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R 17 , R 18 , R 19 and/or R 20 ;
  • R 9 , R 10 , R 11 and R 12 are each independently a group represented by COR 16 , NO 2 or formula (2),
  • Y represents O, S, NR 26 or a direct bond
  • p represents an integer of 0, 1, 2 or 3;
  • q represents an integer of 1, 2 or 3;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 or a group represented by the formula (6);
  • R 13 represents a C 2 -C 20 alkyl group, interspersed with one or more of O, S, SO, SO 2 , NR 26 or CO, or a C 2 -C 12 alkenyl group which is unintercalated or heterozygous Or a plurality of O, CO or NR 26 , wherein the meta-hetero C 2 -C 20 alkyl group and the unmeta- or inter-hetero C 2 -C 12 alkenyl group are unsubstituted or substituted by one or more halogens ;
  • R 13 represents C 4 -C 8 cycloalkenyl, C 2 -C 12 alkynyl or C 3 -C 10 cycloalkyl having no or hetero or one or more O, S, CO or NR 26 ;
  • R 13 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , COR 16 , CN, NO 2 , halogen, C 1 a C 2 alkyl group, a C 1 -C 4 haloalkyl group, a C 2 -C 20 alkyl group having one or more O, S, CO or NR 26 or a group represented by the formula (7),
  • Each warp or C 3 -C 10 cycloalkyl, or interrupted by one or more O, S, CO or NR C 3 26 -C 10 cyclic group is unsubstituted;
  • k represents an integer from 1 to 10;
  • R 14 represents hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkoxy or C 1 -C 20 alkyl, which is unsubstituted or one or more Substituted by: halogen, phenyl, C 1 -C 20 alkylphenyl or CN;
  • R 14 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, halogen, CN, OR 17 , SR 18 and / or NR 19 R 20 ;
  • R 14 represents a C 3 -C 20 heteroaryl group, a C 1 -C 8 alkoxy group, a benzyloxy group or a phenoxy group, the benzyloxy group and the phenoxy group being unsubstituted or having one or more of the following groups Group substituted: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl and/or halogen;
  • R 15 is C 6 -C 20 aryl or C 3 -C 20 heteroaryl, each of which is unsubstituted or Substituted by one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, interrupted by one or more O, S or NR C
  • R 15 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 8 cycloalkyl having no or hetero or one or more O, CO or NR 26 ; or R 15 is C 1 -C 20 alkyl , which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxy a group represented by a carbonyl group, a C 3 -C 20 heteroaryloxycarbonyl group, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO(OC k H 2k+1 ) 2 , a phenyl group, and a formula (6) Or a group represented by the formula (8),
  • C 1 -C 20 alkyl group is substituted by a phenyl group which is substituted by halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents a C 2 -C 20 alkyl group in which one or more O, SO or SO 2 are heterogeneous, and the inter-hetero C 2 -C 20 alkyl group is unsubstituted or has one or more of the following groups Substituted: halogen, OR 17 , COOR 17 , CONR 19 R 20 , phenyl or phenyl substituted by OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents a C 2 -C 20 alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, phenyl, OR 17 , SR 18 Or NR 19 R 20 ; or R 15 is a naphthoyl group or a C 3 -C 14 heteroarylcarbonyl group which is unsubstituted or substituted by one or more OR 17 ;
  • R 15 represents a C 2 -C 12 alkoxycarbonyl group which is undoped or inter-hetero-doped with one or more O and the inter- or un-doped C 2 -C 12 alkoxycarbonyl group is unsubstituted or One or more hydroxyl substitutions;
  • R 15 represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents CN, CONR 19 R 20 , NO 2 , C 1 -C 4 haloalkyl, S(O) m -C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl or SO 2- C 1 -C 6 alkyl-substituted S(O) m -phenyl;
  • R 15 represents an SO 2 O-phenyl group which is unsubstituted or substituted by a C 1 -C 12 alkyl group; or a diphenylphosphono group or a di-(C 1 -C 4 alkoxy)-phosphono group ;
  • n 1 or 2;
  • R' 14 has one of the meanings given for R 14 ;
  • R' 15 has one of the meanings given for R 15 ;
  • X 1 represents O, S, SO or SO 2 ;
  • X 2 represents O, CO, S or a direct bond
  • R 16 represents a C 6 -C 20 aryl group or a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or a C 1 -C 20 alkyl group having one or more O, S or NR 26 ; or each of one or more C 1 -C 20 alkane Substituted, the C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19
  • R 16 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 )alkyl, O(CO)-(C 1 -C 4 alkyl), O(CO) -phenyl, (CO)OH or (CO)O(C 1 -C 4 alkyl);
  • R 16 represents a C 2 -C 12 alkyl group in which one or more O, S or NR 26 are heterogeneous; or R 16 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n ( CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl;
  • R 16 represents a phenyl substituted with SR 18 , wherein the group R 18 represents a direct bond to the phenyl or naphthyl ring of the oxazole moiety to which the COR 16 group is attached;
  • n 1 to 20;
  • R 17 represents hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl), O(CO) -(C 2 -C 4 )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl, SO 2 - (C 1 -C 4 haloalkyl), O(C 1 -C 4 haloalkyl) or a C 3 -C 20 cycloalkyl group having one or more O;
  • R 17 represents C 2 -C 20 alkyl, in which one or more O, S or NR 26 are heterogeneous;
  • R 17 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 1 -C 8 alkanoyl, C 2 -C a 12 -alkenyl, C 3 -C 6 enoyl group or a C 3 -C 20 cycloalkyl group having no or hetero or one or more O, S, CO or NR 26 ;
  • R 17 represents a C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl group which is undoped or hetero-has one or more O;
  • R 17 represents a benzoyl group which is unsubstituted or substituted by one or more C 1 -C 6 alkyl groups, halogen, OH or C 1 -C 3 alkoxy groups;
  • R 17 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 An alkyl) 2 , a diphenyl-amine group or a group represented by the formula (7);
  • R 17 forms a direct bond bonded to one of the carbon atoms of the phenyl or naphthyl ring in which the group represented by the formula (2) or the group represented by the formula (7) is bonded,
  • R 18 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl, wherein the C 2 -C 12 alkenyl, C 3 -C 20 naphthenic Or a phenyl-C 1 -C 3 alkyl group which has no or hetero or one or more O, S, CO, NR 26 or COOR 17 ; or R 18 is a C 1 -C 20 alkyl group which is not Substituted or substituted with one or more of the following groups: OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O (C 1 -C 4 alkyl) , O(CO)-(C 2 -C 4 )alkenyl, O(CO)-(C 1 -C 4 alkyl), O(CO)-phenyl or (CO)OR 17 ;
  • R 18 represents a C 2 -C 20 alkyl group with one or more O, S, CO, NR 26 or COOR 17 interspersed therebetween;
  • R 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 8 alkanoyl or C 3 -C 6 olefin Acyl group
  • R 18 represents a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy or C 1 -C 4 Alkylthio group;
  • R 18 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 12 alkyl, C 1 -C 4- haloalkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenylamino, (CO)O(C 1 -C 8 alkyl), (CO)-C 1 -C 8 alkyl, (CO)N (C 1 -C 8 alkyl) 2 or a group represented by the formula (7),
  • R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3 - C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkanoyl, C 1 -C 8 alkanoyloxy, C 3 -C 12 alkenoyl, SO 2 -(C 1 - C 4 haloalkyl) or benzoyl;
  • R 19 and R 20 represent phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 4 haloalkyl, C 1- C 20 alkoxy, C 1 -C 12 alkyl, benzoyl or C 1 -C 12 alkoxy;
  • R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 17 and which is either 5- or 6-membered saturated or unsaturated
  • R 21 and R 22 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl;
  • R 21 and R 22 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 26 and which is either 5- or 6-membered saturated or unsaturated The ring is unfused or the 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring;
  • R 23 represents hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, intervening one or more O, CO or NR 26 C 2 -C 20 alkyl, uninter or hetero-O a C 3 -C 20 cycloalkyl group of S, CO or NR 26 , or R 23 represents phenyl, naphthyl, phenyl-C 1 -C 4 alkyl, OR 17 , SR 18 or NR 21 R 22 ;
  • R 24 represents (CO)OR 17 , CONR 19 R 20 , (CO)R 17 ; or R 24 has one of the meanings given for R 19 and R 20 ;
  • R 25 represents COOR 17 , CONR 19 R 20 , (CO)R 17 ; or R 25 has one of the meanings given for R 17 ;
  • R 26 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl with one or more O or CO in between; or phenyl-C 1 -C 4 alkane a C 3 -C 8 cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R 19 ; or a phenyl group which is unsubstituted or one or more Substituted by: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or a group represented by formula (7);
  • a compound of formula (1) which contains one or more annelated unsaturated rings on the oxazole moiety.
  • at least one of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is represented by the formula (5).
  • C 1 -C 20 alkyl is straight or branched and is, for example, C 1 -C 18 -, C 1 -C 4 -, C 1 -C 12 -, C 1 -C 8 -, C 1 -C 8- or C 1 -C 4 alkyl or C 4 -C 12 - or C 4 -C 8 alkyl.
  • Examples are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Amyl, 2-ethylhexyl, octyl, decyl, decyl, dodecyl, tetradecyl, fifteen, hexadecyl, octadecyl and decyl.
  • the C 1 -C 6 alkyl group has the same meaning as given above for the C 1 -C 20 alkyl group and has the highest corresponding number of C atoms.
  • An unsubstituted or substituted C 1 -C 20 alkyl group containing one or more CC multiple bonds means an alkenyl group as explained below.
  • C 2 -C 4 hydroxyalkyl means a C 2 -C 4 alkyl group substituted with one or two O atoms. The alkyl group is straight or branched.
  • C 2 -C 10 alkoxyalkyl is interrupted by O atoms, a C 2 -C 10 alkyl.
  • the C 2 -C 10 alkyl group has the same meaning as given above for the C 1 -C 20 alkyl group and has the highest corresponding number of C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, Propoxypropyl.
  • the two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups).
  • the alkyl groups are straight or branched.
  • C 3 -C 10 cycloalkyl, C 3 -C 10 cycloalkyl and C 3 -C 8 cycloalkyl are understood in the context of the present application to mean an alkyl group containing at least one ring. It is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl.
  • C 3 -C 10 cycloalkyl is also intended to encompass the bicyclic ring in the context of the present invention, in other words, a bridging ring, for example
  • the C 3 -C 20 cycloalkyl group interspersed with O, S, CO, NR 26 has the meaning given above wherein at least one CH 2 - group in the alkyl group is replaced by O, S, CO or NR 26 .
  • An example is something like
  • C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl is C 3 -C 10 cycloalkyl as defined above substituted by one or more alkyl groups having up to 8 carbon atoms.
  • An example is:
  • a C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl group interspersed with one or more O is an O-interstitial C 3 - as defined above substituted with one or more alkyl groups having up to 8 carbon atoms C 10 cycloalkyl.
  • An example is:
  • C 1 -C 12 alkoxy is O-substituted by a C 1 -C 12 alkyl.
  • the C 1 -C 12 alkyl group has the same meaning as given above for the C 1 -C 20 alkyl group and has the highest corresponding number of C atoms.
  • C 1 -C 4 alkoxy is straight or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy or Tributoxy.
  • the C 1 -C 8 alkoxy group and the C 1 -C 4 -alkoxy group have the same meanings as described above and have the highest corresponding number of C atoms.
  • C 1 -C 12 alkylthio is S atom substituted by a C 1 -C 12 alkyl.
  • the C 1 -C 20 alkyl group has the same meaning as given above for the C 1 -C 20 alkyl group and has the highest corresponding number of C atoms.
  • C 1 -C 4 alkylthio is straight-chain or branched, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, second butylthio , isobutylthio group, tert-butylthio group.
  • Phenyl-C 1 -C 3 alkyl is, for example, benzyl, phenylethyl, ⁇ -methylbenzyl or ⁇ , ⁇ -dimethyl-benzyl, especially benzyl.
  • the phenyl-C 1 -C 3 alkoxy group is, for example, a benzyloxy group, a phenylethoxy group, an ⁇ -methylbenzyloxy group or an ⁇ , ⁇ -dimethylbenzyloxy group, especially a benzyloxy group.
  • C 2 -C 12 alkenyl is mono- or polyunsaturated and is, for example, C 2 -C 10 -, C 2 -C 8 -, C 2 -C 5 -alkenyl, such as vinyl, allyl, Methyl allyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-Octyl or dodecenyl, especially allyl.
  • the C 2 -C 5 alkenyl group has the same meaning as given above for the C 2 -C 12 alkenyl group and has the highest corresponding number of C atoms.
  • a C 2 -C 12 alkenyl group having one or more O, CO or NR 26 interspersed with O, S, NR 26 or CO, for example 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 time or 2 times. If more than one meta-group is present, it is the same species or different.
  • the two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups).
  • the C 4 -C 8 cycloalkenyl group has one or more double bonds and is, for example, a C 4 -C 6 -cycloalkenyl group or a C 6 -C 8 -cycloalkenyl group.
  • Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.
  • the C 3 -C 6 alkenyloxy group is mono- or polyunsaturated and has one of the meanings given above for an alkenyl group, and the attached oxy group has the highest corresponding number of C atoms. Examples are allyloxy, methylallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.
  • the C 2 -C 12 alkynyl group is a mono- or polyunsaturated straight or branched chain and is, for example, a C 2 -C 8 -, C 2 -C 6 - or C 2 -C 4 alkynyl group.
  • Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, Octyl group and the like.
  • the C 2 -C 20 alkanoyl group is straight or branched and is, for example, C 2 -C 18 -, C 2 -C 14 -, C 2 -C 12 -, C 2 -C 8 -, C 2 -C 6- or C 2 -C 4 alkanoyl or C 4 -C 12 - or C 4 -C 8 alkanoyl.
  • Examples are acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, heptanoyl, octanoyl, decanoyl, decanoyl, dodecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, ten
  • the octayl group, the icosyl group is preferably an acetyl group.
  • the C 1 -C 8 alkanoyl group has the same meaning as given above for the C 2 -C 20 alkanoyl group and has the highest corresponding number of C atoms.
  • C 2 -C 12 alkoxycarbonyl is straight-chain or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1,1 - dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methoxy A carbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a n-butoxycarbonyl group or an isobutoxycarbonyl group is preferably a methoxycarbonyl group.
  • the C 2 -C 12 alkoxycarbonyl group having one or more O interstitials is linear or branched.
  • the two O atoms are separated by at least two methylene groups (ie, ethylene groups).
  • the meta-heteroalkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups.
  • the C 5 -C 20 heteroaryloxycarbonyl group is a C 5 -C 20 heteroaryl-O-CO- group.
  • the C 3 -C 10 cycloalkylcarbonyl group is a C 3 -C 10 cycloalkyl-CO- group wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms.
  • the C 3 -C 10 cycloalkylcarbonyl group having one or more O, S, CO, NR 26 is inter-heterocycloalkyl-CO-, wherein the meta-heterocycloalkyl group is as defined above.
  • the C 3 -C 10 cycloalkoxycarbonyl group is C 3 -C 10 cycloalkyl-O-(CO)-, wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms.
  • the C 3 -C 10 cycloalkoxycarbonyl group having one or more O, S, CO, NR 26 inter-heterocycloalkyl-O-(CO)-, wherein the inter-heterocycloalkyl group is as described above Defined.
  • the C 1 -C 20 alkylphenyl group means a phenyl group substituted by one or more alkyl groups, wherein the sum of the C atoms is at most 20.
  • C 6 -C 20 aryl is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, tetracylphenyl, bistriphenyl, etc., especially phenyl or naphthyl, Good is phenyl.
  • the naphthyl group is 1-naphthyl or 2-naphthyl.
  • C 3 -C 20 heteroaryl is intended to include monocyclic or polycyclic systems, such as fused ring systems.
  • Examples are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thioxyl, furyl, dibenzofuranyl, xanthenyl, thioxanthyl, phenothiphenyl , pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, mesoindolyl, isodecyl, decyl, oxazolyl, fluorenyl, quinazolyl, isoquinoline , quinolyl, pyridazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, porphyrinyl, acridinyl, oxazoly
  • the C 3 -C 20 heteroaryl group is especially thienyl, benzo[b]thienyl, thioxyl, thioxanthyl, 1-methyl-2-indenyl or 1-methyl-3-indolyl Especially tienyl.
  • a C 4 -C 20 heteroarylcarbonyl group is a C 3 -C 20 heteroaryl group as defined above attached to the remainder of the molecule via a CO group.
  • a substituted aryl group (phenyl, naphthyl, C 6 -C 20 aryl or C 5 -C 20 heteroaryl) respectively with 1 to 7, 1 to 6 times or 1 to 4 times, in particular 1 , 2 or 3 substitutions. It will be apparent that the defined aryl group cannot have more substituents than the free position at the aryl ring.
  • the substituent on the phenyl ring is preferably in position 4 on the phenyl ring or in the 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration .
  • Intermixed with one or more interstitial hetero groups for example) 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times or 1 or 2 times (obviously, the number of heteroatoms depends on the number of C atoms to be inter-hetero).
  • the substituted group substituted by one or more times has, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.
  • a group substituted with one or more substituents as defined is intended to have one substituent or a plurality of substituents as defined or differently given.
  • Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently taken to be -(CH 2 ) P -Y- (CH 2 ) q -, forming, for example, such as:
  • R 17 forms a bond to have a group thereon
  • R 16 represents a phenyl group substituted by SR 18 , wherein the group R 19 represents a direct bond bonded to a phenyl or naphthyl ring to which a carbazole moiety of a COR 16 group is attached, for example, such as
  • R 16 is a phenyl group substituted by SR 18 , wherein the group R 18 represents a direct bond bonded to a phenyl or naphthyl ring to which a carbazole moiety of a COR 16 group is attached, the thioxanthyl group Part of it is formed together with a phenyl or naphthyl ring of the carbazole moiety.
  • R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is optionally interspersed with O, S or NR 17 , a saturated or unsaturated ring, such as aziridine, is formed.
  • a saturated or unsaturated ring such as aziridine.
  • R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring heterogeneously interspersed with O, S or NR 17 , an inter- or inter-molecular O is formed. Or a 5- or 6-membered saturated ring of NR 17 , especially O.
  • R 21 and R 22 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally mixed with O, S or NR 26 , and the benzene ring is optionally fused to the saturated or unsaturated ring.
  • a saturated or unsaturated ring such as aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine or corresponding ring
  • R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system the ring system is intended to contain more than one ring (eg 2 or 3 rings) and one or one from the same species or different species.
  • heteroatoms are, for example, N, S, O or P, especially N, S or O.
  • Examples are carbazole, anthracene, isoindole, carbazole, anthracene, isoquinoline, quinoline, porphyrin, phenothiazine and the like.
  • the term "at least" is intended to define one or more than one, for example one or two or three, preferably one or two.
  • interstitial means that the group to which it is referred is not miscellaneous or interstitial.
  • the oxime ester of formula (1) is prepared by the methods described in the literature, for example by reacting the corresponding hydrazine with an acid halide, especially a chloride or an acid anhydride, in an inert solvent (for example, tert-butyl methyl ether, tetrahydrofuran (THF) Or dimethylformamide) in the presence of a base such as triethylamine or pyridine or in a basic solvent such as pyridine.
  • an inert solvent for example, tert-butyl methyl ether, tetrahydrofuran (THF) Or dimethylformamide
  • THF tetrahydrofuran
  • dimethylformamide dimethylformamide
  • R 1 , R 2 , R 5 , R 6 , R 8 , R 13 , R 14 and R 15 are as defined above, and Hal means a halogen atom, especially Cl.
  • R 14 is preferably a methyl group.
  • Such reactions are well known to those skilled in the art and are typically carried out at a temperature of from -15 ° C to +50 ° C, preferably from 0 to 25 ° C.
  • the corresponding hydrazine is nitrosated by using an alkyl nitrite such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.
  • an alkyl nitrite such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.
  • the subject matter of the invention is also a process for the preparation of a compound of formula (1) as defined above by reacting the corresponding hydrazine compound with an acid halide of formula VI or an anhydride of formula VII in the presence of a mixture of bases or bases.
  • Hal is halogen, especially C1, and R 14 is as defined above.
  • the desired hydrazine as a starting material can be passed through standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg SRSandler & W. Karo, Organic functional group preparations, Vol. 3, Various methods are described in Academic Press).
  • One of the most convenient methods is to, for example, react an aldehyde or a ketone with hydroxylamine or a salt thereof in a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or an aqueous ethanol solution.
  • a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or an aqueous ethanol solution.
  • Tim A base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and the base can be added continuously at the beginning or during the reaction. Basic solvents such as pyridine can also be used as the base and/or solvent or cosolvent.
  • the reaction temperature is usually from room temperature to the reflux temperature of the mixture, and is usually from about 20 ° C to 120 ° C.
  • ketone intermediates are prepared, for example, by methods described in the literature (e.g., standard chemistry textbooks, e.g., J. March, Advanced Organic Chemistry, 4th Ed., Wiley Interscience, 1992).
  • the continuous Friedel-Crafts reaction can be effectively used to synthesize intermediates. Such reactions are well known to those skilled in the art.
  • hydrazine is the nitrosation of "active" methylene groups with nitrous acid or alkyl nitrite.
  • Basic conditions as described, for example, in Organic Syntheses coll., Volume VI (J. Wiley & Sons, New York, 1988), pages 199 and 840) and acidic conditions (eg, for example, Organic Synthesis coll. V, pages 32 and 373, coll. Volume III, pages 191 and 513, coll. Volume II, pages 202, 204 and 363)
  • a ruthenium used as a starting material in the present invention is prepared.
  • Nitrous acid is generally produced from sodium nitrite.
  • the alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.
  • Another embodiment of the invention is a free (1A) hydrazine compound
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, C 1 -C 20 alkyl, OR 17 , halogen, NO 2 or a group represented by the formula (3),
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently taken as —(CH 2 ) p —Y— (CH 2 ) q —;
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5) ,
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5). Represented group,
  • R 9, R 10, R 11 and R 12 are independently hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups to one another: halo, Phenyl, CN, OH, SH, C 1 -C 4 -alkoxy, -(CO)OH or -(CO)O-(C 1 -C 4 alkyl);
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, an unsubstituted phenyl group or a phenyl group substituted by one or more of the following groups: C 1 -C 6 alkyl, halogen, CN, OR 17 , SR 18 or NR 19 R 20 ;
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, halogen, CN, OR 17 , SR 18 , SOR 18 , SO 2 R 18 or NR 19 R 20 , wherein the substituents OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring via a carbon atom in the naphthyl ring via the groups R 17 , R 18 , R 19 and/or R 20 ;
  • R 9 , R 10 , R 11 and R 12 are independently of each other
  • Y represents O, S, NR 26 or a direct bond
  • p represents an integer of 0, 1, 2 or 3;
  • q represents an integer of 1, 2 or 3;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 or a group represented by the formula (6),
  • R 13 represents a C 2 -C 20 alkyl group, interspersed with one or more of O, S, SO, SO 2 , NR 26 or CO, or a C 2 -C 12 alkenyl group which is unintercalated or heterozygous Or a plurality of O, CO or NR 26 , wherein the meta-hetero C 2 -C 20 alkyl group and the unmeta- or inter-hetero C 2 -C 12 alkenyl group are unsubstituted or substituted by one or more halogens ;
  • R 13 represents C 4 -C 8 cycloalkenyl, C 2 -C 12 alkynyl or C 3 -C 10 cycloalkyl having no or hetero or one or more O, S, CO or NR 26 ;
  • R 13 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 ,
  • COR 16 CN, NO 2, halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, interrupted by one or more O, S, CO or NR C 26 of 2 -C 20 alkyl; or each warp C 3 -C 10 cycloalkyl, or interrupted by one or more O, S, CO or NR C 3 26 -C 10 cyclic group is unsubstituted;
  • k represents an integer from 1 to 10;
  • R 15 represents a C 6 -C 20 aryl group or a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 , SO-C 1 -C 10 alkyl, SO 2 -C 1 -C 10 alkyl, heterogeneous C 2 -C 20 alkyl group or a plurality of O, S or NR 26; or a C 1 -C 20 via respective substituted alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following Group substitution: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl
  • R 15 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 8 cycloalkyl, having no or hetero or one or more O, CO or NR 26 ;
  • R 15 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 Heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, NR 19 R 20 , COOR 17 , CONR 19 R 20 , PO(OC k H 2k+1 ) 2 , benzene base, Or a group represented by the formula (6)
  • C 1 -C 20 alkyl group is substituted by a phenyl group which is substituted by halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents a C 2 -C 20 alkyl group in which one or more O, SO or SO 2 are heterogeneous, and the inter-hetero C 2 -C 20 alkyl group is unsubstituted or has one or more of the following groups Substituted: halogen, OR 17 , COOR 17 , CONR 19 R 20 , phenyl or phenyl substituted by OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents a C 2 -C 20 alkanoyl or benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, phenyl, OR 17 , SR 18 Or NR 19 R 20 ;
  • R 15 represents a naphthoyl group or a C 3 -C 14 heteroarylcarbonyl group which is unsubstituted or substituted with one or more OR 17 ;
  • R 15 represents a C 2 -C 12 alkoxycarbonyl group which is undoped or inter-hetero-doped with one or more O and the inter- or un-doped C 2 -C 12 alkoxycarbonyl group is unsubstituted or One or more hydroxyl substitutions;
  • R 15 represents a phenoxycarbonyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, C 1 -C 4 haloalkyl, phenyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 15 represents CN, CONR 19 R 20 , NO 2 , C 1 -C 4 haloalkyl, S(O) m -C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl or SO 2- C 1 -C 6 alkyl-substituted S(O) m -phenyl;
  • R 15 represents an SO 2 O-phenyl group which is unsubstituted or substituted with a C 1 -C 12 alkyl group; or a diphenylphosphono group or a di-(C 1 -C 4 alkoxy)-phosphono group ;
  • n 1 or 2;
  • R' 15 has one of the meanings given for R 15 ;
  • X 1 represents O, S, SO or SO 2 ;
  • X 2 represents O, CO, S or a direct bond
  • R 16 represents a C 6 -C 20 aryl group or a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or a C 1 -C 20 alkyl group having one or more O, S or NR 26 ; or each of one or more C 1 -C 20 alkane Substituted, the C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 3 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19
  • R 16 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 )alkyl, O(CO)-(C 1 -C 4 alkyl), O(CO) -phenyl, (CO)OH or (CO)O(C 1 -C 4 alkyl);
  • R 16 represents a C 2 -C 12 alkyl group in which one or more O, S or NR 26 are heterogeneous; or R 16 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n ( CO)-(C 1 -C 8 alkyl), C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl;
  • R 16 represents a phenyl substituted with SR 18 , wherein the group R 18 represents a direct bond to the phenyl or naphthyl ring of the oxazole moiety to which the COR 16 group is attached;
  • n 1 to 20;
  • R 17 represents hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl), O(CO) -(C 2 -C 4 )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl, SO 2 - (C 1 -C 4 haloalkyl), O(C 1 -C 4 haloalkyl) or a C 3 -C 20 cycloalkyl group having one or more O;
  • R 17 represents C 2 -C 20 alkyl, in which one or more O, S or NR 26 are heterogeneous;
  • R 17 represents (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 1 -C 8 alkanoyl, C 2 -C a 12 -alkenyl, C 3 -C 6 enoyl group or a C 3 -C 20 cycloalkyl group having no or hetero or one or more O, S, CO or NR 26 ;
  • R 17 represents a C 1 -C 8 alkyl-C 3 -C 10 cycloalkyl group which is undoped or hetero-has one or more O;
  • R 17 represents a benzoyl group which is unsubstituted or substituted by one or more C 1 -C 6 alkyl groups, halogen, OH or C 1 -C 3 alkoxy groups;
  • R 17 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 Alkyl) 2 , diphenyl-amino group or
  • R 17 forms a bond to have a group thereon
  • R 18 represents hydrogen, C 2 -C 12 alkenyl, C 3 -C 20 cycloalkyl or phenyl-C 1 -C 3 alkyl, wherein the C 2 -C 12 alkenyl, C 3 -C 20 naphthenic Or a phenyl-C 1 -C 3 alkyl group which has no or hetero or one or more O, S, CO, NR 26 or COOR 17 ; or R 18 is a C 1 -C 20 alkyl group which is not Substituted or substituted with one or more of the following groups: OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 CN, OCH 2 CH 2 (CO)O (C 1 -C 4 alkyl) , O(CO)-(C 2 -C 4 )alkenyl, O(CO)-(C 1 -C 4 alkyl), O(CO)-phenyl or (CO)OR 17 ;
  • R 18 represents a C 2 -C 20 alkyl group with one or more O, S, CO, NR 26 or COOR 17 interspersed therebetween;
  • R 18 represents (CH 2 CH 2 O) n H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl), C 2 -C 8 alkanoyl or C 3 -C 6 olefin Acyl group
  • R 18 represents a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH, C 1 -C 4 alkoxy or C 1 -C 4 Alkylthio group;
  • R 18 represents phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 12 alkyl, C 1 -C 4- haloalkyl, C 1 -C 12 alkoxy, CN, NO 2 , phenyl-C 1 -C 3 alkoxy, phenoxy, C 1 -C 12 alkylthio, phenylthio, N (C 1 -C 12 alkyl) 2 , diphenylamino, (CO)O(C 1 -C 8 alkyl), (CO)-C 1 -C 8 alkyl, (CO)N (C 1 -C 8 alkyl) 2 or
  • R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3 - C 20 cycloalkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkanoyl, C 1 -C 8 alkanoyloxy, C 3 -C 12 alkenoyl, SO 2 -(C 1 - C 4 haloalkyl) or benzoyl;
  • R 19 and R 20 represent phenyl, naphthyl or C 3 -C 20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C 1 -C 4 haloalkyl, C 1- C 20 alkoxy, C 1 -C 12 alkyl, benzoyl or C 1 -C 12 alkoxy;
  • R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 17 and which is either 5- or 6-membered saturated or unsaturated
  • R 21 and R 22 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl;
  • R 21 and R 22 together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is unintermixed or interspersed with O, S or NR 26 and which is either 5- or 6-membered saturated or unsaturated The ring is unfused or the 5- or 6-membered saturated or unsaturated ring is fused to the benzene ring;
  • R 23 represents hydrogen, OH, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, intervening one or more O, CO or NR 26 C 2 -C 20 alkyl, uninter or hetero-O a C 3 -C 20 cycloalkyl group of S, CO or NR 26 ;
  • R 23 represents phenyl, naphthyl, phenyl-C 1 -C 4 alkyl, OR 17 , SR 18 or NR 21 R 22 ;
  • R 24 represents (CO)OR 17 , CONR 19 R 20 , (CO)R 17 ; or R 24 has one of the meanings given for R 19 and R 20 ;
  • R 25 represents COOR 17 , CONR 19 R 20 , (CO)R 17 ; or R 25 has one of the meanings given for R 17 ;
  • R 26 represents hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl with one or more O or CO in between; or phenyl-C 1 -C 4 alkane a C 3 -C 8 cycloalkyl group which is undoped or heterozygous with one or more O or CO; or (CO)R 19 ; or a phenyl group which is unsubstituted or one or more Substituted by the following groups: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 ,
  • Preferred for the groups defined for the compound of formula (1A) corresponds as given for the compound of formula (1) as given above, except for each of the defined oxime ester groups (eg Are replaced by corresponding free sulfonium groups
  • Each oxime ester group can exist in two configurations (Z) or (E). Isomers can be separated by existing methods, but mixtures of isomers can also be used as, for example, photoinitiators. Accordingly, the present invention is also directed to a mixture of configurational isomers of the compound of formula (1).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are, independently of one another, hydrogen, C 1 -C 20 Alkyl group, COR 16 , NO 2 or a group represented by formula (2)
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 are each independently a group represented by the formula (5)
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 or R 7 and R 8 is determined by the formula (5). Represented group
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 , NR 19 R 20 , PO(OC k H 2k+1 ) 2 ;
  • R 13 represents a C 2 -C 20 alkyl group with one or more O, S, SO, SO 2 , NR 26 or CO intermixed therebetween;
  • R 13 represents phenyl or naphthyl, both unsubstituted or via one or more COR 16 or Replaced
  • R 14 represents a C 1 -C 20 alkyl group, a phenyl group or a C 1 -C 8 alkoxy group
  • R 15 represents a phenyl group, a naphthyl group, a C 3 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 , a SR 18 or C 2 -C 20 alkyl group having one or more O or S hetero; or each substituted with one or more C 1 -C 20 alkyl groups, the C 1 -C 20 alkyl group being unsubstituted or Substituted by one or more of the following groups: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl , C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 , NR 19 R 20 or PO(OC k H 2k
  • R 15 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl , NR 19 R 20 , COOR 17 , CONR 19 R 20 or PO(OC k H 2k+1 ) 2 ;
  • R' 14 has one of the meanings given for R 14 ;
  • R' 15 has one of the meanings given for R 15 ;
  • R 16 represents a phenyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or a C 2 -C 20 alkane having one or more O, S or NR 26 base,
  • R 16 represents a phenyl group which -C 20 alkyl substituted by one or more C 1, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following radicals: halogen, COOR 17, CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 or NR 19 R 20 ;
  • R 16 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted by a halogen, phenyl, OH, SH, CN, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO) O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl) or (CO)O(C 1 -C 4 alkyl);
  • R 17 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O (C 1 -C 4 alkyl), (CO) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl interrupted by one or more O or a C 3 -C 20 cycloalkyl;
  • R 17 represents a C 2 -C 20 alkyl group, in which one or more O;
  • R 18 represents a methyl group substituted with (CO)OR 17 ;
  • R 19 and R 20 are each independently hydrogen, phenyl, C 1 -C 20 alkyl, C 1 -C 8 alkanoyl or C 1 -C 8 alkanoyloxy;
  • R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or Substituting; however, the condition is that at least one group represented by the formula (2) or a group represented by the formula (7) is present in the molecule,
  • R 1 , R 2 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, COR 16 NO 2 or a group represented by the formula (2) group,
  • R 3 and R 4 together are a group represented by the formula (5)
  • R 9 , R 10 , R 11 and R 12 represent hydrogen
  • X represents a direct key
  • R 13 represents a C 1 -C 20 alkyl group
  • R 14 represents a C 1 -C 20 alkyl group
  • R 15 represents a C 1 -C 20 alkyl group or a phenyl group which is substituted with one or more OR 17 or C 1 -C 20 alkyl groups;
  • R 16 represents a phenyl group which is substituted with one or more C 1 -C 20 alkyl groups or OR 17 ;
  • R 17 represents an unsubstituted or substituted by one or more halogen C 1 -C 20 alkyl interrupted by one or more O or a C 2 -C 20 alkyl group.
  • the subject matter of the invention is further a compound of formula (1) as defined above, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen,
  • R 1 and R 2 , R 3 and R 4 or R 5 and R 6 are each independently a group represented by the formula (5),
  • R 1 and R 2 , R 3 and R 4 or R 5 and R 6 is a group represented by the formula (5),
  • R 2 is a group represented by the formula (2), COR 16 , NO 2 or a group represented by the formula (3),
  • R 7 is a group represented by COR 16 or formula (2),
  • R 9 , R 11 and R 12 represent hydrogen
  • R 10 represents hydrogen, OR 17 or COR 16 ;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , OR 17 , SR 18 or PO(OC k H 2k+1 ) 2 ;
  • R 13 represents a C 2 -C 20 alkyl group, in which one or more O;
  • R 13 represents a phenyl group
  • k represents an integer of 2;
  • R 14 represents a C 1 -C 20 alkyl group or a thienyl group
  • R 15 represents phenyl or naphthyl, each of which is unsubstituted or substituted with one or more OR 17 or C 1 -C 20 alkyl groups;
  • R 15 represents a thiophene group, hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following groups: OR 17, SR 18, C 3 -C 8 Cycloalkyl, NR 19 R 20 or COOR 17 ;
  • R 15 represents a C 2 -C 20 alkyl group, interspersed with SO 2 ;
  • R 16 represents a phenyl or naphthyl group, each of which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl; or R 16 represents thienyl ;
  • R 17 represents hydrogen, C 1 -C 8 alkanoyl, C 1 -C 20 alkyl, which is unsubstituted or has one or more of the following groups: halogen, O(CO)-(C 1 -C 4 alkyl Or O(CO)-(C 2 -C 4 )alkenyl or a C 3 -C 20 cycloalkyl group having one or more O;
  • R 17 represents a C 2 -C 20 alkyl group, in which one or more O;
  • R 18 represents C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl, unsubstituted or via one or more OH, O(CO)-(C 2 -C 4 )alkenyl or (CO) Replaced by OR 17 ;
  • R 18 represents a phenyl group which is unsubstituted or substituted with one or more halogens
  • R 19 and R 20 are each independently a C 1 -C 8 alkanoyl group or a C 1 -C 8 alkanoyloxy group;
  • R 19 and R 20 together with the N atom to which they are attached form a 5- or 6-membered saturated ring interspersed with O;
  • condition is that at least one group represented by the formula (2) is present in the molecule.
  • An example of a compound of the invention is a compound of formula (Ia)-(Ig) as defined above.
  • Compounds of formula (Ia), (Ib), (Ic), especially formula (Ia) or (Ic), or formula (Ia), (Ic) or (Id), especially formula (Ia) are of interest.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, COR 16 , a group represented by formula (2), or R 1 And R 2 , R 2 and R 3 , R 3 and R 4 or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 are each independently a group represented by the formula (5),
  • R 3 and R 4 or R 1 and R 2 together are a group represented by the formula (5),
  • R 3 and R 4 and R 5 and R 6 together are a group represented by the formula (5),
  • R 3 and R 4 are in particular a group represented by the formula (5),
  • R 1 , R 5 , R 6 and R 8 represent hydrogen.
  • R 7 is especially a group represented by hydrogen COR 16 or formula (2),
  • R 7 is a group represented by COR 16 or formula (2), particularly a group represented by formula (2),
  • R 2 is especially a group represented by COR 16 , formula (2) or a group represented by formula (3),
  • R 2 together with R 1 is a group represented by formula (5)
  • X is preferably a direct bond.
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 ; or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , SR 18 or NR 19 R 20 wherein the substituent OR 17 SR 18 or NR 19 R 20 optionally via a group R 17, R 18, R 19 and / or R 20 and one carbon atom naphthyl ring form a 5-membered or 6-membered ring; or R 9, R 10, R 11 And R 12 are each independently a group represented by COR 16 or formula (2),
  • R 9 , R 10 , R 11 and R 12 are each independently hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 ; or R 9 , R 10 , R 11 and R 12 are, independently of each other, halogen, OR 17 , SR 18 or NR 19 R 20 ; or R 9 , R 10 And R 11 and R 12 are each independently a group represented by COR 16 or formula (2),
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl or substituted by one or more C 1 -C 6 alkyl groups.
  • Phenyl group; or R 9 , R 10 , R 11 and R 12 are each independently a group represented by COR 16 or formula (2),
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl or one or more of the following groups a substituted phenyl group: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 ; or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , SR 18 or NR 19 R 20 Wherein the substituent OR 17 , SR 18 or NR 19 R 20 optionally forms a 5- or 6-membered ring with one carbon atom of the naphthyl ring via the radicals R 17 , R 18 , R 19 and/or R 20 .
  • R 9 , R 10 , R 11 and R 12 are each independently hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups C 1 -C 6 alkyl, halogen, OR 17 or SR 18 , or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , SR 18 , NR 19 R 20 or COR 16 .
  • R 9 , R 10 , R 11 and R 12 are, independently of each other, hydrogen, C 1 -C 20 alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OR 17 or SR 18 , or R 9 , R 10 , R 11 and R 12 are each independently halogen, OR 17 , COR 16 or NR 19 R 20 .
  • R 9 , R 11 and R 12 represent hydrogen and R 10 represents hydrogen, OR 17 or COR 16 .
  • R 13 represents, for example, a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, COOR 17 or CONR 19 R 20 ; or R 13 represents C 2 -C 20 alkyl
  • one or more of O, S, SO, SO2, NR 26 or CO, or a C 2 -C 12 alkenyl group optionally having one or more O, CO or NR 26 or R 13 representing C 3 -C 10 cycloalkyl, which is optionally interrupted by one or more O, S, CO, NR 26 , or R 13 represents a phenyl or naphthyl group, these two unsubstituted or substituted with one or more of the following groups Substitution: OR 17 , SR 18 , NR 19 R 20 , COR 16 , NO 2 , halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl
  • a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 or PO (OC k H 2k +1 ) 2 ; or a C 2 -C 20 alkyl group in which one or more O are heterogeneous.
  • R 13 represents, for example, a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , COOR 17 , OR 17 , SR 18 , CONR 19 R 20 or PO(OC k H 2k+1 ) 2 ; or a C 2 -C 20 alkyl group in which one or more O is hetero; or a C 2 -C 12 alkenyl group, a C 3 -C 10 cycloalkyl group; or R 13 represents a phenyl or naphthyl group, which are unsubstituted or substituted by one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , COR 16 , NO 2 , halogen, C 1 -C 20 alkane a C 1 -C 4 haloalkyl group, a C 2 -C 20 alkyl group, having one or more O or a group represented by the formula
  • R 13 represents, for example, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following: halo, R 17 , OR 17 , SR 18 or PO (OC k H 2k+1 ) 2 ; or a C 2 -C 20 alkyl group in which one or more O is hetero; or a C 2 -C 12 alkenyl group, a C 3 -C 10 cycloalkyl group, a phenyl group or a naphthyl group; .
  • R 13 represents, for example, a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R 17 , OR 17 , SR 18 or PO(OC k H 2k+1 ) 2 ; or a C 2 -C 20 alkyl group having one or more O; or a phenyl group, a C 2 -C 12 alkenyl group or a C 3 -C 10 cycloalkyl group.
  • R 13 represents, for example, a C 1 -C 20 alkyl group, a phenyl group, a C 2 -C 12 alkenyl group or a C 3 -C 10 cycloalkyl group.
  • R 13 represents, for example, a C 1 -C 20 alkyl group, a C 2 -C 12 alkenyl group or a C 3 -C 10 cycloalkyl group.
  • R 13 represents a C 1 -C 20 alkyl group, especially a C 1 -C 8 alkyl group, such as 2-ethylhexyl.
  • R 14 represents, for example, hydrogen, C 3 -C 8 cycloalkyl, C 2 -C 5 alkenyl, C 1 -C 20 alkoxy or C 1 -C 20 alkyl, which is unsubstituted or subjected to one or Multiple halogen or phenyl substituted; or R 14 represents phenyl or naphthyl, both unsubstituted or substituted by one or more of the following groups: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl , halogen, OR 17 , SR 18 and/or NR 19 R 20 ; or R 14 represents a C 3 -C 5 heteroaryl group, for example a thienyl group, or a C 1 -C 8 alkoxy group, a benzyloxy group or a phenoxy group base.
  • R 14 represents, for example, a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more halogen or phenyl groups; or R 14 represents a C 3 -C 5 heteroaryl group (e.g., thienyl) or a phenyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, halogen, OR 17 , SR 18 and/or NR 19 R 20 ; R 14 represents a C 1 -C 8 alkoxy group, a benzyloxy group or a phenoxy group.
  • R 14 represents a C 1 -C 8 alkoxy group, a benzyloxy group or a phenoxy group.
  • R 14 represents C 1 -C 20 alkyl, which is unsubstituted or substituted with phenyl; or R 14 represents phenyl, which is unsubstituted or via one or more C 1 -C 6 Alkyl substitution.
  • R 14 represents C 1 -C 20 alkyl, C 3 -C 5 heteroaryl (such as thienyl), or phenyl, especially C 1 -C 20 alkyl or thienyl, especially C 1- C 8 alkyl.
  • R 15 represents, for example, a C 6 -C 20 aryl group or a C 5 -C 20 heteroaryl group, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkane a group, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 , C 1 -C 20 alkyl; or R 15 represents hydrogen, C 3 -C 8 cycloalkyl, the C 3 -C 8 cycloalkyl Depending on the case, one or more O, CO or NR 26 ; or R 15 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , C 3 -C 8 -cycloalkyl, C 5 -C 20 heteroaryl, C 8 -C 20 phenoxycarbonyl, C 5 -C 20 heteroaryloxy
  • R 15 represents a C 2 -C 20 alkyl group in which one or more O, S or SO 2 are heterogeneous, or R 15 represents a C 2 -C 20 alkanoyl group, a benzoyl group, a C 2 -C 12 alkoxycarbonyl group. , phenoxycarbonyl, CONR 19 R 20 , NO 2 or C 1 -C 4 haloalkyl.
  • R 15 represents, for example, hydrogen, C 6 -C 20 aryl, especially phenyl or naphthyl, each unsubstituted or substituted by C 1 -C 12 alkyl; or C 3 -C 5 hetero
  • An aryl group such as a thienyl group; or a C 3 -C 8 cycloalkyl group, a C 1 -C 20 alkyl group, which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 17 , C 3 - C 8 -cycloalkyl, NR 19 R 20 or COOR 17 ; or R 15 represents C 2 -C 20 alkyl with one or more O or SO 2 heteromixed therebetween.
  • R 15 represents, for example, hydrogen, phenyl, naphthyl, each unsubstituted or substituted by C 1 -C 8 alkyl; or R 15 represents thienyl, C 1 - a C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 17 , C 3 -C 8 -cycloalkyl, NR 19 R 20 or COOR 17 ; or R 15 represents C 2 a -C 20 alkyl group in which one or more O or SO 2 are heterogeneous.
  • R 15 is especially, for example, C 3 -C 8 cycloalkyl or C 1 -C 20 alkyl, especially C 1 -C 20 alkyl, especially C 1 -C 12 alkyl.
  • R' 14 and R' 15 are as given above for R 14 and R 15 respectively.
  • X 1 represents, for example, O, S or SO, such as O or S, especially O.
  • R 16 represents, for example, a C 6 -C 20 aryl group (especially phenyl or naphthyl, especially phenyl) or a C 5 -C 20 heteroaryl (especially thienyl), each unsubstituted or via one or more Substituted for: phenyl, halogen, C 1 -C 4 haloalkyl, CN, NO 2 , OR 17 , SR 18 , NR 19 R 20 or a C 1 -C 20 alkyl group having one or more O; or each with one or more C 1 -C 20 substituted alkyl, C 1 -C 20 alkyl which is unsubstituted or substituted with one or more of the following radicals: halogen, COOR 17, CONR 19 R 20 , benzyl , C 3 -C 8 cycloalkyl, C 5 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 5 -C 20 heteroaryloxy
  • R 16 represents, for example, phenyl or naphthyl, especially phenyl, thienyl or oxazole, each unsubstituted or substituted by one or more of the following groups: phenyl, halogen, C 1 -C a 4- haloalkyl group, OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl; or R 16 represents a C 1 -C 20 alkyl group which is unsubstituted or substituted with one or more of the following groups: Halogen, phenyl, OH, SH, C 3 -C 6 alkenyloxy, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl) , O(CO)-phenyl, (CO)OH or (CO)O(C 1 -C 4 alkyl); or R 16 represents a C 2 -C 12 alkyl group, wherein one
  • R 16 represents, for example, phenyl or naphthyl, especially phenyl, each unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl; or R 16 represents a C 3 -C 5 heteroaryl group, especially a thienyl group.
  • R 16 is especially, for example, phenyl which is unsubstituted or substituted by one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 or C 1 -C 20 alkyl, or R 16 represents thienyl .
  • R 16 represents, for example, phenyl or naphthyl, each of which is unsubstituted or substituted with one or more C 1 -C 20 alkyl groups.
  • R 16 is especially phenyl which is substituted by one or more C 1 -C 20 alkyl groups.
  • R 17 represents, for example, hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH 2 CH 2 (CO)O(C 1 -C 4 alkyl), O(CO)-(C 1 -C 4 alkyl), O(CO)-(C 2 -C 4 )alkenyl, O(CO)-benzene group, (CO) OH, (CO ) O (C 1 -C 4 alkyl), C 3 -C 20 cycloalkyl interrupted by one or more O or a C 3 -C 20 cycloalkyl; or R 17 represents a C 2 -C 20 alkyl group having one or more O in between; (CH 2 CH 2 O) n+1 H, (CH 2 CH 2 O) n (CO)-(C 1 -C 8 alkyl) a C 1 -C 8 alkanoy
  • R 17 represents, for example, hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following: halogen , O(CO)-(C 1 -C 4 alkyl), O(CO)-(C 2 -C 4 alkenyl) or a C 2 -C 20 alkyl group having one or more O; or C 1 a C 8 alkanoyl group, a C 2 -C 12 alkenyl group, a C 3 -C 6 alkenoyl group, a C 2 -C 20 alkyl group having one or more O interstitials, and optionally a C 3 -C having one or more O a 20 cycloalkyl group; or a benzoyl group which is unsubstituted or substituted with one or more of the following groups: C 1 -C 6 alkyl, halogen, OH or C 1 -C
  • R 17 is, for example, hydrogen, phenyl-C 1 -C 3 alkyl, C 1 -C 8 alkanoyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: Halogen, C 3 -C 20 cycloalkyl, O(CO)-(C 1 -C 4 alkyl), O(CO)-(C 2 -C 4 alkenyl) or C 2 having one or more O -C 20 alkyl, or R 17 represents C 2 -C 20 alkyl with one or more O intervening.
  • R 17 is especially hydrogen, C 1 -C 8 alkanoyl, C 1 -C 20 alkyl, which is unsubstituted or substituted by one or more of the following groups: O(CO)-(C 1 -C 4 alkyl , O(CO)-(C 2 -C 4 alkenyl) or a C 2 -C 20 alkyl group having one or more O, or R 17 representing a C 2 -C 20 alkyl group, one or more O.
  • R 18 represents, for example, a C 3 -C 20 cycloalkyl group which has no or a hetero or one or more O; or R 18 represents a C 1 -C 20 alkyl group which is unsubstituted or one or more of the following Group substitution: OH, O(CO)-(C 2 -C 4 ) alkenyl, O(CO)-(C 1 -C 4 alkyl) or (CO)OR 17 ; or R 18 represents C 2 -C a 20 alkyl group having one or more of O, S, CO, NR 26 or COOR 17 in between ; or R 18 represents a C 2 -C 8 alkanoyl group or a C 3 -C 6 alkenoyl group, a benzoyl group; or R 18 represents Phenyl, naphthyl or C 3 -C 20 heteroaryl, each unsubstituted or substituted by one or more of the following groups: halogen, C 1 -C 12 alkyl, C
  • R 18 represents, for example, C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more of the following groups: OH, O (CO )-(C 2 -C 4 )alkenyl, O(CO)-(C 1 -C 4 alkyl) or (CO)OR 17 ; or R 18 represents phenyl or naphthyl, each unsubstituted or via One or more halogen or C 1 -C 12 alkyl groups, especially halogen.
  • R 18 represents, for example, a C 1 -C 20 alkyl group, a C 2 -C 12 alkenyl group, a C 3 -C 20 cycloalkyl group, a phenyl-C 1 -C 3 alkyl group, a C 2 -C 8 alkanoyl group, Benzoyl, phenyl or naphthyl.
  • R 18 represents C 1 -C 20 alkyl substituted with one or more of the following groups: OH, O(CO)-(C 2 -C 4 )alkenyl, O(CO)-(C 1 -C 4 alkyl) or (CO)OR 17 , or R 18 represents a phenyl group which is substituted by one or more halogens.
  • R 18 represents C 1 -C 8 alkyl, which is substituted as defined above.
  • R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkane a phenyl or naphthyl group, a C 1 -C 8 alkanoyl group, a C 1 -C 8 alkanoyloxy group, a C 3 -C 12 alkenoyl group or a benzoyl group; or R 19 and R 20 attached thereto
  • the atoms together form a 5- or 6-membered saturated or unsaturated ring heterogeneously interspersed with O, S or NR 17 ; or R 19 and R 20 together with the N atom to which they are attached form a heteroaromatic ring system, the ring system is not Substituted or substituted with one or more of the following groups: a C 1 -C 20 alkyl group, a C 1 -C 4 haloalkyl
  • R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C a 3- alkyl group, a C 1 -C 8 alkanoyl group, a C 1 -C 8 alkanoyloxy group, a C 3 -C 12 alkenoyl group or a benzoyl group; or R 19 and R 20 together with the N atom to which they are attached In the case of a 5- or 6-membered saturated ring of O or NR 17 ; or R 19 and R 20 together with the N atom to which they are attached form an indazole ring.
  • R 19 and R 20 are each independently hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 3 -C 20 cycloalkyl, phenyl-C 1 -C 3 alkane a C 1 -C 8 alkanoyl group, a C 1 -C 8 alkanoyloxy group, a C 3 -C 12 alkenoyl group or a benzoyl group; or R 19 and R 20 together with the N atom to which they are attached form a heterogeneous There is a 5- or 6-membered saturated ring of O or NR 17 .
  • R 19 and R 20 are, independently of each other, a C 1 -C 8 alkanoyl group, a C 1 -C 8 alkanoyloxy group; or R 19 and R 20 together with the N atom to which they are attached form a morpholine ring.
  • R 21 and R 22 are each independently hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 3 -C 10 cycloalkyl or phenyl; or R 21 and R 22 The attached N atoms together form a morpholine ring.
  • R 21 and R 22 are, in particular, independently of one another hydrogen or C 1 -C 20 alkyl.
  • R 23 represents, for example, hydrogen, OH, phenyl or C 1 -C 20 alkyl. R 23 is especially hydrogen, OH or C 1 -C 4 alkyl.
  • R 24 is preferably as given for R 19 and R 20 .
  • R 25 is preferably as given for R 17 .
  • R 26 represents, for example, hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, C 2 -C 20 alkyl, heterogeneously having one or more O or CO; or phenyl-C 1 - a C 4 alkyl group, a C 3 -C 8 cycloalkyl group optionally having one or more O or CO; or (CO)R 19 or a phenyl group which is unsubstituted or has one or more of the following groups Substitution: C 1 -C 20 alkyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , NR 19 R 20 .
  • R 26 represents, for example, hydrogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl; phenyl-C 1 -C 4 alkyl, C 3 -C 8 cycloalkyl, (CO)R 19 or a phenyl group which is unsubstituted or substituted by one or more C 1 -C 20 alkyl groups.
  • R 26 represents, for example, hydrogen or a C 1 -C 20 alkyl group, especially a C 1 -C 4 alkyl group.
  • Examples of the compound of the formula (1) of the invention include the following compounds represented by the formula (1-1) to the formula (1-84):
  • the photoinitiator (C-1) represented by the formula (1) is used in an amount of 10 to 70 parts by weight, preferably 12 parts by weight to 60%, based on 100 parts by weight of the alkali-soluble resin (A).
  • the parts by weight are more preferably 15 parts by weight to 50 parts by weight.
  • the photosensitive resin composition does not use the photoinitiator (C-1), the photosensitive resin composition has poor reliability under high temperature and high humidity, and has poor resolution and poor heat resistance.
  • photoinitiator (C-2) examples include other oxy-acyl steroids (O-acyloxime) or non-oxy-acyl hydrazine-based photoinitiators.
  • oxy-acyl hydrazine compounds include 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-(O-benzoyl group). ⁇ ), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoylhydrazine), 1-[4-(phenylthio)phenyl ]-octane-1,2-dione-2-(O-benzoylhydrazine), or a combination of the above compounds.
  • oxy-acyl hydrazine compounds include 1-[4-(benzoyl)phenyl]-heptane-1,2-dione-2-(O-benzoyl hydrazine), 1-[9 -ethyl-6-(2-methylbenzoyl)-9H-indazole-3-substituted]-ethanone-1-(O-acetyl oxime), 1-[9-ethyl-6- (3-methylbenzoyl)-9H-indazole-3-substituted]-ethanone-1-(O-acetylindole), 1-[9-ethyl-6-benzoyl-9H-indole Zyrid-3-yl]-ethane ketone-1-(O-acetyl oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)- 9H-carbazole-3-substi
  • oxy-acyl hydrazine compounds may be used singly or in combination of two or more.
  • non-oxy-acyl hydrazine photoinitiator examples include a triazabenzene compound, an acetophenone compound, a diimidazole compound, a benzophenone compound, an ⁇ -diketone compound, and an alcohol ketone.
  • triazabenzene compound examples include a vinyl-halomethyl-s-triazabenzene compound, 2-(naphtho-1-substituted)-4,6-di(halomethyl)- An s-triazabenzene compound, a 4-(p-aminophenyl)-2,6-di(halomethyl)-s-triazabenzene compound, or a combination of the above compounds.
  • vinyl-halogenomethyl-s-triazabenzene compound examples include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, 2 ,4-di(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloromethyl- 3-Amino-6-p-methoxystyryl-s-triazabenzene, or a combination of the above compounds.
  • 2-(naphtho-1-substituted)-4,6-di(halomethyl)-s-triazabenzene compound examples include 2-(naphtho-1-substituted)-4,6 - bis(trichloromethyl)-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-di(trichloromethyl)-s-triazole Heterobenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-(4-butoxy-naphthalene And-1-substituted)-4,6-bis(trichloromethyl)-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-yl] -4,6-bis(trichloromethyl)-s-triazabenz
  • 4-(p-aminophenyl)-2,6-bis(halomethyl)-s-triazabenzene compound examples include 4-[p-N,N-di(ethoxycarbonyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(ethoxycarbonylmethyl) Aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6- Bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(chloroethyl)aminophenyl]-2,6-di(trichloromethane) -s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6--ch
  • the triazabenzene compound preferably includes 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)- S-triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, or a combination of the above compounds.
  • acetophenone compound examples include p-dimethylacetonone, ⁇ , ⁇ '-dimethoxy oxy acetophenone, and 2,2'-dimethyl-2-phenylbenzene.
  • the acetophenone compounds may be used singly or in combination of two or more.
  • 2-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone may be a product of the model IRGACURE 907 manufactured by Ciba Specialty Chemicals Co., Ltd.
  • 2-Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone is commercially available from Ciba Specialty Chemicals, Inc. under the model number IRGACURE 369.
  • the acetophenone-based compound preferably includes 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-di Methylamine-1-(4-morpholinophenyl)-1-butanone, or a combination of the above compounds.
  • diimidazole compound examples include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 , 2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4' , 5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (2,2',4,4'-tetrameth
  • the diimidazole compounds may be used singly or in combination of two or more.
  • the diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.
  • benzophenone compound examples include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamine) II. Benzophenone, 4,4'-bis(diethylamine)benzophenone, or a combination of the above compounds.
  • the benzophenone compounds can be used singly or in combination.
  • the benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone.
  • ⁇ -diketone compound examples include benzil, diacetyl, or a combination of the above compounds.
  • the ⁇ -diketone compounds may be used singly or in combination of two or more.
  • ketol compound examples include benzoin.
  • the ketol compounds may be used singly or in combination of two or more.
  • ketol ether compound examples include diphenylethanol ketone methyl ether, benzophenone ethyl ether, diphenylethanol ketone isopropyl ether, or a combination of the above compounds.
  • the ketol ether compounds may be used singly or in combination of two or more.
  • phosphinyl oxide-based compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl A phenylphosphine oxide, or a combination of the above compounds.
  • the acylphosphine oxide compounds may be used singly or in combination of two or more.
  • quinone compound examples include hydrazine, 1,4-naphthoquinone, or a combination of the above compounds.
  • the terpenoids may be used singly or in combination of two or more.
  • halogen-containing compound examples include benzoyl chloride, tribromomethylphenylsulfone, tris(trichloromethyl)-s-triazabenzene, or a combination of the above compounds.
  • the halogen-containing compound may be used singly or in combination of two or more.
  • peroxide examples include di-tert-butyl peroxide and the like.
  • the peroxides may be used singly or in combination of two or more.
  • the photoinitiator (C) is used in an amount of 10 to 80 parts by weight, preferably 12 parts by weight to 70 parts by weight, more preferably 15 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). 60 parts by weight.
  • the solvent (D) means an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, and a photoinitiator (C), and the following black pigment (E) and branched polymer (F).
  • the hot starter (G) and the compound (H) are dissolved, but do not react with the above components, and are preferably suitably volatile.
  • the solvent (D) include an alkyl glycol monoalkyl ether compound, an alkyl glycol monoalkyl ether acetate compound, a diethylene glycol alkyl ether, other ether compounds, a ketone compound, and lactic acid.
  • alkyl glycol monoalkyl ether compound examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol mono-n-butyl Ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether And tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether or an analogue thereof, or a combination of the above compounds.
  • alkyl glycol monoalkyl ether acetate compound examples include: ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate or propylene glycol diethyl ether acetate or the like, or the above compounds combination.
  • diethylene glycol alkyl ether examples include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or the like, or a combination of the above compounds.
  • ether compounds include tetrahydrofuran or the like.
  • ketone compound examples include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol or the like, or a combination of the above compounds.
  • lactate alkyl ester compound examples include methyl lactate, ethyl lactate or the like, or a combination of the above compounds.
  • ester compounds include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3 -methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Isobutyl ester, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n
  • aromatic hydrocarbon compound examples include toluene, xylene or the like, or a combination of the above compounds.
  • the above solvent (D) may be used singly or in combination of two or more.
  • the solvent (D) is preferably propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.
  • the solvent (D) is used in an amount of from 1000 parts by weight to 8,000 parts by weight, based on the above-mentioned alkali-soluble resin (A), in an amount of from 1,000 parts by weight to 8,000 parts by weight, preferably from 1200 parts by weight to 7,000 parts by weight, more preferably from 1,500 parts by weight to 6000 parts by weight.
  • the black pigment (E) is preferably a black pigment having heat resistance, light resistance, and solvent resistance.
  • the black pigment (E) include black organic pigments such as perylene black, cyanine black, or aniline black; red, blue, green, purple, and yellow.
  • the pigments such as cyanine or magenta
  • two or more pigments are selected.
  • a blackout material such as carbon black, chromium oxide, iron oxide, titanium black or graphite
  • specific examples of the above carbon black include CIpigment black 7 or a commercial product manufactured by Mitsubishi Chemical Corporation (trade name: MA100, MA230, MA8, #970, #1000, #2350 or #2650).
  • the above black pigments (E) may be used singly or in combination of two or more.
  • the black pigment (E) is preferably carbon black, and the carbon black is, for example, a commercially available product MA100 or MA230 manufactured by Mitsubishi Chemical Corporation.
  • the black pigment (E) is used in an amount of 150 parts by weight to 1200 parts by weight, preferably 200 parts by weight to 1000 parts by weight, more preferably 250 parts by weight, based on 100 parts by weight of the above-mentioned alkali-soluble resin (A). Up to 800 parts by weight.
  • the multi-branched polymer (F) may be formed by a Michael Addition Reaction of a polyfluorenyl compound represented by the formula (F2) and a polyfunctional (meth) acrylate represented by the formula (F1). polymer.
  • polyfunctional (meth) acrylate represented by the formula (F1) is as follows.
  • M 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • M 2 represents a residue obtained by esterification of g hydroxyl groups in a hydroxyl group-containing compound having h hydroxyl groups, wherein h ⁇ g, g represents an integer of 2 to 20.
  • the above hydroxyl group-containing compound is a compound in which M 3 (OH) h or M 3 (OH) h is modified with propylene oxide, epichlorohydrin, alkyl group, alkoxy group or hydroxypropyl acrylate.
  • M 3 (OH) h is a polyhydric alcohol having 2 to 18 carbon atoms, a polyhydric alcohol ether formed from the above polyhydric alcohol, an ester formed by reacting the above polyhydric alcohol with an acid, or silicone.
  • polyfluorenyl compound represented by the formula (F2) is as follows.
  • M 4 represents a single bond, a hydrocarbon group having a carbon number of 1, or a linear or branched hydrocarbon group having a carbon number of 2 to 22, and the skeleton of M 4 may further include a sulfur atom or constitute an ester group.
  • Oxygen atom (ie, M 4 is a single bond, a hydrocarbon group having a carbon number of 1, a linear or branched hydrocarbon group having a carbon number of 2 to 22 containing a sulfur atom or an oxygen atom, or a carbon having no sulfur atom or oxygen atom a linear or branched hydrocarbon group of 2 to 22; i represents an integer of 2 to 6, wherein when M 4 represents a single bond, i represents 2; when M 4 represents a hydrocarbon group of 1 carbon number, i represents An integer of 2 to 4; when M 4 represents a linear or branched hydrocarbon group having 2 to 22 carbon atoms, i represents an integer of 2 to 6.
  • the multi-branched polymer (F) of the present invention preferably has a polyhydrazino compound represented by the formula (F2) and a polyfunctional (meth) acrylate represented by the formula (F1), and remains (methyl group).
  • the mercapto compound having a carboxyl group represented by the formula (F3) is as follows.
  • M 5 represents an alkylene group having 1 to 12 carbon atoms
  • j represents an integer of 1 to 3.
  • the fluorenyl group contained in the polyfluorenyl compound represented by the formula (F2) and the fluorenyl compound having a carboxyl group represented by the formula (F3) is added to the polyfunctional group represented by the formula (F1) via photoreaction ( Methyl) acrylate on the carbon-carbon double bond.
  • the photoreactive carbon-carbon double bond is preferably 0.1% with respect to all carbon-carbon double bonds. Up to 50%.
  • the polyaddition (meth) acrylate represented by F1) may have an addition molar ratio of carbon-carbon double bond of from 1/200 to 1/2, preferably from 1/100 to 1/3, more preferably 1/. 50 to 1/5, more preferably 1/20 to 1/8.
  • the multi-branched polymer (F) preferably has a sufficient photopolymerizable functional group such as a carbon-carbon double bond. Specifically, the molecular weight of the multibranched polymer (F) per 1 mol of the carbon-carbon double bond is preferably from 100 to 100,000. The molecular weight of the multi-branched polymer (F) is preferably from 1,000 to 50,000, more preferably from 1,500 to 40,000, particularly preferably from 2,000 to 30,000.
  • the multi-branched polymer (F) preferably has a sufficient carboxyl group.
  • the molecular weight of the multibranched polymer (F) per one mole of the carboxyl group is preferably from 200 to 20,000, more preferably from 250 to 6,000.
  • the number (g) of the acrylate groups contained in the polyfunctional (meth) acrylate represented by the formula (F1) is preferably from 2 to 20, more preferably from 2 to 10, still more preferably from 2 to 6.
  • M 1 in the formula (F1) represents an alkyl group having 1 to 4 carbon atoms
  • M 1 may be a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group.
  • M 3 (OH) h preferably has a carbon number of 2 to 18, more preferably 2 to 14, particularly preferably 4 to 12.
  • polyfunctional (meth) acrylate represented by the formula (F1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, modified by ethylene oxide Trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol Di(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate
  • M 4 in the polyfluorenyl compound represented by the formula (F2) preferably has a carbon number of 0 to 22 (when the carbon number is 0, M 3 is a single bond, and the formula (F2) represents HS-CH 2 - CH 2 -SH) is more preferably from 1 to 16, particularly preferably from 2 to 12.
  • polyfluorenyl compound represented by the formula (F2) examples include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-didecylbutane, bisdidecylethanethiol (HS- CH 2 CH 2 -S-CH 2 CH 2 -SH), dimercaptotriethylene glycol, trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), pentaerythritol tetra ( Mercaptoacetate, pentaerythritol tris(mercaptoacetate), pentaerythritol tetrakis(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritopropionate), or a combination of the above compounds.
  • 1,2-dimercaptoethane 1,3-dimercaptopropane
  • the alkylene group having 1 to 12 carbon atoms of M 5 in the mercapto compound having a carboxyl group represented by the formula (F3) may be a linear or branched alkylene group.
  • the alkylene group is, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, an anthranylene group, an anthranylene group, and a decylene group.
  • a group such as a monoalkyl group or a dodecylene group.
  • the mercapto compound having a carboxyl group represented by the formula (F3) is exemplified by thioglycolic acid.
  • the above-mentioned addition reaction may first mix a polyfunctional (meth) acrylate (monomer) represented by the formula (F3) with a polyfluorenyl compound represented by the formula (F2) at room temperature to 100 ° C. And adding a basic catalyst to carry out.
  • the reaction time is usually from 30 minutes to about 6 hours. In this way, a multi-branched polymer can be obtained.
  • a mercapto compound having a carboxyl group represented by the formula (F3) may be added to the multi-branched polymer, and an addition reaction may be carried out once.
  • a multi-branched polymer having a carboxyl group can be obtained.
  • the synthesis of the multi-branched polymer (F) can be confirmed by a general analytical instrument such as liquid chromatography or gel filtration chromatography.
  • a polymerization inhibitor may be added as necessary.
  • a hydroquinone-based compound generally used for suppressing polymerization of a (meth) acrylate compound, a phenol compound, or a combination thereof can be used.
  • Specific examples of the polymerization inhibitor include, but are not limited to, hydroquinone, methoxy hydroquinone, catechol, p-tert-butyl catechol, cresol, dibutylhydroxytoluene, 2, 4, 6-Tri-tert-butylphenol (BHT), or a combination of the above compounds.
  • the multi-branched polymer (F) is used in an amount of 3 to 35 parts by weight, preferably 4 parts by weight to 30 parts by weight, and more preferably 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Up to 25 parts by weight.
  • the heat resistance resistance of the photosensitive resin composition can be further improved.
  • the thermal initiator (G) of the present invention is not particularly limited, and in one embodiment of the present invention, it may include, but is not limited to, an azo compound, an organic peroxide, a hydrogen peroxide compound, and the like.
  • azo compound examples include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis (cyclohexane) Alkan-2-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl)azo]carboxamide, 2,2-Azobis ⁇ 2-methyl-nitro-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide, 2,2'-azobis[nitro-(2- Propenyl)-2-methylpropionamide], 2,2'-azobis[nitro-(2-propenyl)-2-ethylpropanamide], 2,2'-azobis(nitrogen-butyl) 2-methylpropionamide), 2,2'-azobis(nitro-cyclohexyl-2-methylpropanamide), 2,2'-azobis(dimethyl-2-methylpropane) Amide), 2,2'-azobis(dimethyl)methylbut
  • organic peroxides include: benzoyl peroxide, dibutyl peroxide, diisobutyryl peroxide, cumene peroxy neodecanoate, dipropyl peroxydicarbonate, Diisopropyl peroxydicarbonate, dibutyl butyl dicarbonate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, bis(4-tert-butylcyclohexyl) peroxidation Dicarbonate, 1-cyclohexyl-1-methylethylperoxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate , Peroxidic neodecanoic acid trihexyl ester, dimethoxybutyl peroxydicarbonate, tert-butyl peroxy neodecanoate, third hexyl peroxypiva
  • hydrogen peroxide compound examples include: decane hydrogen peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, Tertiary butyl hydroperoxide, and the like.
  • the aforementioned thermal initiator (G) is 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis (2, 4-dimethylvaleronitrile), diisobutyryl peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, decane hydroperoxide, cumene hydroperoxide, neon peroxide Preferably, cumene acrylate or the like is preferred.
  • the above-mentioned hot starter (G) may be used singly or in combination of plural kinds, depending on actual needs.
  • the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the hot start agent (G) is 4 to 40 parts by weight; preferably 5 to 35 parts by weight. More preferably, it is 6 to 30 parts by weight.
  • the thermal initiator (G) is used, the resolution of the photosensitive resin composition can be further improved.
  • the photosensitive resin composition for a black matrix according to the present invention contains a compound represented by the formula (10) (H);
  • Z 1 , Z 2 and Z 3 each independently represent a trialkoxysilane group bonded via an alkylene group or an arylene group.
  • the alkylene group or the arylene group may have a substituent, and the substituent may be an amino group, a hydroxyl group, an alkoxy group or a halogen atom.
  • Specific examples of the alkylene group according to the present invention are a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, an anthranylene group, an anthranylene group, and the like.
  • a specific example of the arylene group according to the present invention is a phenylene group or a naphthylene group.
  • the structural compound represented by the formula (10-1) is 1,3,5-N-tris(trimethoxysilylpropyl)isocyanurate, which is commercially available from Nippon Unicar Company Limited.
  • the compound (H) represented by the formula (10) is preferably used in an amount of from 1 part by weight to 10 parts by weight, more preferably from 1.2 part by weight to 9 parts by weight, based on 100 parts by weight of the above-mentioned alkali-soluble resin (A). It is particularly preferably from 1.5 parts by weight to 8 parts by weight.
  • the compound (H) represented by the formula (10) is used, the reliability of the photosensitive resin composition at high temperature and high humidity can be further improved.
  • a method which can be used for preparing a photosensitive resin composition for example, an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment (E)
  • the mixture is placed in a stirrer and stirred to be uniformly mixed into a solution state.
  • a multi-branched polymer (F), a hot starter (G), and a compound (H) may be added, and uniformly mixed to obtain a solution state.
  • a photosensitive resin composition for example, an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment (E)
  • the mixture is placed in a stirrer and stirred to be uniformly mixed into a solution state.
  • the method for preparing the photosensitive resin composition is not particularly limited.
  • the photosensitive resin composition is prepared by, for example, dispersing a part of the alkali-soluble resin (A) and the compound (B) having an ethylenically unsaturated group in a part of the solvent (D) to form a dispersion solution; and then mixing The remaining The alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), the solvent (D), and the black pigment (E) are prepared.
  • the photosensitive resin composition may be formed by first dispersing a part of the black pigment (E) in a mixture of the partially alkali-soluble resin (A) and a part of the solvent (D) to form a black pigment dispersion; It is prepared by adding an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment (E). Further, the dispersion step of the above black pigment (E) can be carried out by mixing with a mixer such as a beads mill or a roll mill.
  • a mixer such as a beads mill or a roll mill.
  • the black matrix is produced by sequentially pre-baking, exposing, developing, and post-baking the photosensitive resin composition on the substrate. Further, when the film thickness of the obtained black matrix is 1 ⁇ m, the optical density may be 3.0 or more, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5. The preparation method of the black matrix will be described in detail below.
  • a photosensitive resin composition for a black matrix in a solution state is uniformly applied onto a substrate by a coating method such as spin coating or cast coating to form a coating film.
  • a coating method such as spin coating or cast coating to form a coating film.
  • the substrate include: alkali-free glass, soda lime glass, hard glass (Pyrus glass), quartz glass, and a transparent conductive film attached to the glass for a liquid crystal display device or the like; or A photoelectric conversion device substrate (for example, a silicon substrate) such as a photographing device.
  • drying under reduced pressure is carried out at a pressure of less than 200 mmHg for 1 second to 20 seconds, and the prebaking is performed by heating the coating film at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes.
  • the light used in the exposure process is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp and a metal halide lamp.
  • the exposed prebaked coating film is immersed in a developing solution at a temperature of 23 ⁇ 2° C. to remove the unexposed portion of the prebaked coating film, thereby forming a specific pattern on the substrate. .
  • the developing solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium silicate, sodium methyl silicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, Hydroxide
  • a basic compound such as tetramethylamine, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene.
  • the concentration of the developer is generally from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, and more preferably from 0.01% by weight to 1% by weight.
  • the substrate having the specific pattern is washed with water, and the above specific pattern is air-dried with compressed air or compressed nitrogen. Then, the post-baking treatment is performed by a heating device such as a hot plate or an oven.
  • the post-baking temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time using the oven is from 15 minutes to 150 minutes.
  • the manufacturing method of the pixel layer is similar to the manufacturing method of the black matrix. Specifically, the color filter is coated on the substrate on which the black matrix has been formed, and then pre-baked, exposed, developed, and post-baked. However, in the condition of drying under reduced pressure, drying under reduced pressure is carried out at a pressure of from 0 mmHg to 200 mmHg for from 1 second to 60 seconds. After the above processing steps, a specific pattern can be fixed, thereby forming a pixel layer. Then, by repeating the above steps, a red, green, and blue pixel layer is sequentially formed on the substrate, and a substrate on which the black matrix and the pixel layer are formed (that is, a color filter having a pixel layer) can be obtained.
  • a color filter formed by the above-described method of manufacturing a color filter and a substrate provided with a thin film transistor are disposed to face each other, and a gap (cell gap) is provided between the two.
  • the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left.
  • liquid crystal is injected from the injection hole in the gap between the surface of the substrate and the adhesive, and finally the injection hole is sealed to form a liquid crystal layer.
  • a liquid crystal display device was fabricated by providing a polarizing plate on the other side of the color filter that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer.
  • the liquid crystal used as described above, that is, a liquid crystal compound or a liquid crystal composition is not particularly limited herein. However, any liquid crystal compound and liquid crystal composition can be used.
  • liquid crystal alignment film used in the production of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any inorganic or organic substance may be used, and the present invention is not limited thereto.
  • the light yellow transparent mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound of Preparation Example 1 having a solid content of 99.9% by weight (a-1- 1-a).
  • the light yellow transparent mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound of Preparation Example 2 having a solid content of 99.9% by weight (a-1-1- b).
  • Feed speed is controlled at 25 Parts by weight/min, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C, and after 15 hours of reaction, a pale yellow transparent mixture having a solid content of 50% by weight was obtained.
  • the light yellow transparent mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound of Preparation Example 3 having a solid content of 99.9% by weight (a-1-1-c). ).
  • silictaneous addition means addition of a tetracarboxylic acid or its acid dianhydride (a-1-2) and a dicarboxylic acid or its anhydride (a-1-3) at the same reaction time.
  • a-1-2 tetracarboxylic acid or its acid dianhydride
  • a-1-3 dicarboxylic acid or its anhydride
  • “segmented addition” means adding tetracarboxylic acid or its acid dianhydride (a-1-2) and dicarboxylic acid or its anhydride (a-1-3) separately at different reaction times, that is, adding first The tetracarboxylic acid or its acid dianhydride (a-1-2) is then added with a dicarboxylic acid or its anhydride (a-1-3).
  • an alkali-soluble resin A-1-2 having an acid value of 92 mgKOH/g and a number average molecular weight of 5,130 was obtained.
  • the alkali-soluble resins of Synthesis Examples A-1-3, Synthesis Examples A-1-5 and Synthesis Examples A-1-6 are Synthesis Example A-1-2 was prepared in the same manner, and was different in that the composition of the first alkali-soluble resin and the amount thereof, the reaction time, the reaction temperature, and the reaction addition time (as shown in Table 1) were changed. .
  • the alkali-soluble resin of Synthesis Example A-1-4 was prepared in the same manner as in Synthesis Example A-1-1, and was distinguished by changing the kind of the component of the first alkali-soluble resin, the amount thereof, the reaction time, Reaction temperature and reactant addition time (as shown in Table 1).
  • DMDMS dimethyldimethoxysilane
  • PTES phenyltriethoxysilane
  • silanol silanol
  • the flask was immersed in an oil bath at 30 ° C and stirred for 30 minutes.
  • the oil bath was then warmed to 120 ° C in 30 minutes.
  • the temperature of the solution was lowered to 110 ° C (ie, the reaction temperature), heating and stirring were continued for 6 hours (that is, a polycondensation time).
  • the solvent is removed by distillation to obtain an alkali-soluble resin (A-2-1).
  • the component types of the alkali-soluble resin (A-2-1) and the amounts thereof used are shown in Table 2.
  • the alkali-soluble resin (A-2) of Synthesis Example A-2-2 to Synthesis Example A-2-4 was prepared in the same manner as in Synthesis Example A-2-1, and was distinguished by changing the alkali-soluble resin.
  • Example 1 100 parts by weight of an alkali-soluble resin A-1-1, 20 parts by weight of an esterified product of pentaerythritol triacrylate and phthalic acid (abbreviated as B-1-1), and 10 parts by weight of the formula (1-1)
  • the photoinitiator (abbreviated as C-1-1), 350 parts by weight of black pigment MA100 (abbreviated as E-1), and 4 parts by weight of 2,2'-azobis(2,4-dimethyl)
  • the sensitization of Example 1 can be obtained by adding 1000 parts by weight of propylene glycol monomethyl ether acetate (abbreviated as D-1) to propylene glycol monomethyl ether acetate (abbreviated as D-1) and stirring uniformly with a shaking stirrer. Resin composition.
  • the photosensitive resin composition of Example 1 was applied by spin coating to a plain glass substrate (having a size of 100 mm ⁇ 100 mm ⁇ 0.7 mm) to form a coating film having a thickness of about 6 ⁇ m.
  • the coating film was prebaked at 90 ° C for 2 to 3 minutes.
  • a photomask was placed between the exposure machine and the coating film, and the prebaked coating film was patterned and exposed with ultraviolet rays of 100 mJ/cm 2 (exposure machine model AG500-4N, by M&R Nanotechnology) )).
  • the exposed coating film was immersed in a 0.05% potassium hydroxide aqueous solution for 45 to 90 seconds to remove an unnecessary portion of the above-mentioned exposed coating film.
  • the photosensitive resin compositions and films of Examples 2 to 15 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof (Table 3) Shown).
  • the obtained film was evaluated in the following evaluation manners, and the results are shown in Table 3.
  • the photosensitive resin compositions and films of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof (Table 4) Shown).
  • the obtained film was evaluated in the following evaluation manners, and the results are shown in Table 4.
  • A-1-1 alkali-soluble resin of synthetic example A-1-1 (A-1) A-1-1 alkali-soluble resin of synthetic example A-1-1 (A-1)
  • A-1-2 Alkali-soluble resin of synthetic example A-1-2 (A-1) A-1-2 Alkali-soluble resin of synthetic example A-1-2 (A-1)
  • A-1-3 Alkali-soluble resin of synthetic example A-1-3 (A-1) A-1-3 Alkali-soluble resin of synthetic example A-1-3 (A-1)
  • A-1-4 alkali-soluble resin of synthetic example A-1-4 (A-1) A-1-4 alkali-soluble resin of synthetic example A-1-4 (A-1)
  • A-1-5 Alkali-soluble resin of synthetic example A-1-5 (A-1)
  • A-1-6 Alkali-soluble resin of synthetic example A-1-6 (A-1) A-1-6 Alkali-soluble resin of synthetic example A-1-6 (A-1)
  • the photosensitive resin compositions prepared in the above respective Examples and Comparative Examples were coated by a coater (Model: MS-A150, available from Shinko Trading), and coated by spin coating at a length and a width of 100 mm ( Mm) on the glass substrate. Then, it was dried under reduced pressure at a pressure of about 100 mmHg (mmHg) for about 5 seconds. Next, the above glass substrate was prebaked at 100 ° C for 2 minutes to form a prebaked film having a film thickness of 1.2 ⁇ m.
  • a coater Model: MS-A150, available from Shinko Trading
  • the above prebaked coating film was irradiated with ultraviolet light of 100 mJ/cm 2 (mJ/cm 2 ) using an exposure machine (manufactured by M&R Nano Technology Co., Ltd., model AG500-4N). After irradiation with ultraviolet light, the prebaked coating film was immersed in a developing solution (potassium hydroxide, concentration: 0.04%) at 23 °C. After 2 minutes, it was washed with pure water, and the prebaked coating film was placed at 230 ° C and baked for 60 minutes to form a light-shielding film having a film thickness of 1.0 ⁇ m on the glass substrate.
  • a developing solution potassium hydroxide, concentration: 0.04%
  • the above-mentioned light-shielding film was placed in an oven at a temperature of 121 ° C, a pressure of 2 atm (atm) and a relative humidity of 100%, and after 8 hours, according to JIS. 5400 (1900) 8.5 adhesion test method
  • the base plate method of 8.5.2 measures the reliability of the light-shielding film under high temperature and high humidity.
  • the above-mentioned light-shielding film was cut into 100 substrates by a knife. Then, it was peeled off with a tape, and the residue of the substrate was observed, and evaluated according to the following criteria:
  • the glass substrate having a specific pattern is washed with water.
  • the minimum value of the line width of the pattern formed on the glass substrate is defined as the resolution.
  • the line amplitude was evaluated in the following manner. It is to be noted that the smaller the minimum pattern line width, the better the resolution of the photosensitive resin composition.
  • the above pre-baked coating film having a film thickness of 1.2 ⁇ m was separately measured using a high-impedance meter (Model: MCP-HT450 type Hiresta-UP; manufactured by Mitsubishi Chemical Corporation). Three measurement points were taken on the pre-baked coating film, and the average value ( ⁇ 1 ) of the surface resistance values was measured.
  • the pre-baked coating films were irradiated with ultraviolet light at 100 mJ/cm 2 under a designated mask, and then immersed in a developer (0.04% potassium hydroxide) at 23 ° C for 2 minutes, and washed with pure water. Thereafter, after baking at 280 ° C for 60 minutes in an oven, a black matrix having a film thickness of 1.0 ⁇ m was formed on the glass substrate. Using a high-impedance meter at the same three measurement points, the average value of the surface resistance values ( ⁇ 2 ) was measured, and finally calculated by the following formula (IX), and evaluated according to the following criteria:
  • a film formed using a photosensitive resin composition containing a photoinitiator (C-1) (Example) 1 to Example 15)
  • the film formed by using the photosensitive resin composition containing no photoinitiator (C-1) had poor resolution and heat resistance. Poor impedance and poor reliability at high temperatures and high humidity.
  • the photosensitive resin composition of the present invention includes the compound (B) having an ethylenically unsaturated group and the photoinitiator (C-1) having a specific structure, the resolution and resistance of the black matrix can be improved.
  • the thermal resistance and the problem of poor reliability under high temperature and high humidity are further applicable to color filters and liquid crystal display devices.

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Abstract

一种感光性树脂组成物、彩色滤光片及其液晶显示元件，感光性树脂组成物包括碱可溶性树脂（A）、具有乙烯性不饱和基的化合物（B）、光起始剂（C）、溶剂（D）以及黑色颜料（E）。具有乙烯性不饱和基的化合物（B）包含具有酸性基及至少三个乙烯性不饱和基的化合物（B-1）。光起始剂（C）包括由式（1）表示的光起始剂（C-1）。

Description

感光性树脂组成物、彩色滤光片及其液晶显示元件 技术领域
本发明涉及一种感光性树脂组成物、彩色滤光片及其液晶显示元件。特别涉及一种在解析度、耐热阻抗性、高温及高湿条件下信赖性佳的黑色矩阵用感光性树脂组成物、彩色滤光片及其液晶显示元件。
背景技术
近年来，随着各式各样的液晶显示器技术蓬勃发展，而为了提高目前液晶显示器的对比度及显示品质，通常会在液晶显示器中的彩色滤光片的条纹(stripe)及点(dot)间隙中放置黑色矩阵(black matrix)。上述黑色矩阵可防止因画素间的漏光(light leakage)所引起的对比度(contrast ratio)下降及色纯度(color purity)下降等问题。
一般而言，黑色矩阵所使用的材料都以含有铬或氧化铬等的蒸镀膜为主。然而，以上述蒸镀膜作为黑色矩阵的材料时，存在制造程复杂且材料昂贵等缺点。为了解决此问题，先前提出有利用感光性树脂组成物透过光平版印刷(photo lithographic)的方式形成黑色矩阵的技术。
随着对于黑色矩阵的遮光性要求日益提高，其解决方法之一就是增加黑色颜料的使用量，藉此提高黑色矩阵的遮光性。举例而言，日本专利特开第2006-259716号公报揭示一种黑色矩阵用感光性树脂组成物，其包含高使用量的黑色颜料、碱可溶性树脂、光聚合起始剂、具有二官能基的反应性单体以及有机溶剂。值得注意的是，具有二官能基的反应性单体可改善化合物的间的反应，以形成精细的图案(fine pattern)。藉此，在感光性树脂组成物中，当以提升黑色颜料使用量的方式以增加遮光性的同时，尚可保持感光性树脂组成物的感度。
另外，日本专利特开第2008-268854号公报揭示一种黑色矩阵用的感光性树脂组成物。上述感光性树脂组成物包含具有羧酸基及具有不饱和基的碱可溶性树脂、具有乙烯性不饱和基的光聚合单体、光聚合起始剂及高使用量 的黑色颜料。上述黑色矩阵用感光性树脂组成物中，通过使用特定的碱可溶性树脂来改善高使用量黑色颜料的感光性树脂组成物的解析度。
虽然现有技术中提高了黑色颜料使用量的感光性树脂组成物能够增加遮光性，然而，上述现有的感光性树脂组成物仍有解析度不佳、耐热阻抗性不佳、高温及高湿下的信赖性不佳等问题。有鉴于此，仍需开发一种解析度、耐热阻抗性、高温及高湿下的信赖性均佳的黑色矩阵用感光性树脂组成物。
发明内容
有鉴于此，本发明提供一种感光性树脂组成物、彩色滤光片及其液晶显示元件，且此感光性树脂组成物解析度、耐热阻抗性、高温及高湿下的信赖性均佳。
本发明提供一种感光性树脂组成物，其包括碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)、光起始剂(C)、溶剂(D)以及黑色颜料(E)。其中，所述具有乙烯性不饱和基的化合物(B)包含具有酸性基及至少三个乙烯性不饱和基的化合物(B-1)。所述光起始剂(C)包括由式(1)表示的光起始剂(C-1)。
Figure PCTCN2015092009-appb-000001
其中R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、COR16、OR17、卤素、NO2、由式(2)所表示的基团或是由式(3)所表示的基团、
Figure PCTCN2015092009-appb-000002
Figure PCTCN2015092009-appb-000003
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地为经由式(4)所表示的基团取代的C2-C10烯基、
Figure PCTCN2015092009-appb-000004
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为—(CH2)p—Y—(CH2)q—；
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000005
但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团，
R9、R10、R11及R12彼此独立地为氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C1-C4-烷氧基、-(CO)OH或-(CO)O-(C1-C4烷基)；
或R9、R10、R11及R12彼此独立地为未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、CN、OR17、SR18或NR19R20；
或R9、R10、R11及R12彼此独立地为卤素、CN、OR17、SR18、SOR18、SO2R18或NR19R20，其中该等取代基OR17、SR18或NR19R20视情况经由该等基团R17、R18、R19和/或R20与萘基环中一个碳原子形成5元或6元环；
或R9、R10、R11及R12彼此独立地为COR16、NO2或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000006
Y表示O、S、NR26或直接键；
p表示0、1、2或3的整数；
q表示1、2或3的整数；
X表示CO或直接键；
R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20、NR19R20、PO(OCkH2k+1)2或是式(6)所表示的基团
Figure PCTCN2015092009-appb-000007
或R13表示C2-C20烷基，其间杂有一或多个O、S、SO、SO2、NR26或CO，或是C2-C12烯基，其是未经间杂或间杂有一或多个O、CO或NR26，其中该经间杂的C2-C20烷基及该未经间杂或经间杂的C2-C12烯基是未经取代或经一或多个卤素取代；
或R13表示C4-C8环烯基、C2-C12炔基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C10环烷基；
或R13表示苯基或萘基，其各为未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、COR16、CN、NO2、卤素、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、S、CO或NR26的C2-C20烷基或式(7)表示的基团、
Figure PCTCN2015092009-appb-000008
或其各经C3-C10环烷基或间杂有一或多个O、S、CO或NR26的C3-C10环烷基取代；
k表示1至10的整数；
R14表示氢、C3-C8环烷基、C2-C5烯基、C1-C20烷氧基或C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、苯基、C1-C20烷基苯基或 CN；
或R14表示苯基或萘基，其各未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基、卤素、CN、OR17、SR18和/或NR19R20；
或R14表示C3-C20杂芳基、C1-C8烷氧基、苄氧基或苯氧基，该苄氧基及苯氧基是未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基和/或卤素；R15表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20、PO(OCkH2k+1)2、SO-C1-C10烷基、SO2-C1-C10烷基、间杂有一或多个O、S或NR26的C2-C20烷基；或其各经C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R15表示氢、C2-C12烯基、未经间杂或间杂有一或多个O、CO或NR26的C3-C8环烷基；或R15表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OR17、SR18、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、NR19R20、COOR17、CONR19R20、PO(OCkH2k+1)2、苯基、式(6)所表示的基团或式(8)所表示的基团、
Figure PCTCN2015092009-appb-000009
或该C1-C20烷基是经苯基取代，该苯基是经卤素、C1-C20烷基、C1-C4卤代烷基、OR17、SR18或NR19R20取代；
或R15表示C2-C20烷基，其间杂有一或多个O、SO或SO2，且该经间杂的C2-C20烷基是未经取代或经一或多个以下基团取代：卤素、OR17、COOR17、CONR19R20、苯基或经OR17、SR18或NR19R20取代的苯基；
或R15表示C2-C20烷酰基或苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、苯基、OR17、SR18或NR19R20；或R15表示未经取代或经一或多个OR17取代的萘甲酰基或是C3-C14杂芳基羰基；
或R15表示C2-C12烷氧基羰基，其是未经间杂或间杂有一或多个O且该经间杂或未经间杂的C2-C12烷氧基羰基是未经取代或经一或多个羟基取代；
或R15表示苯氧基羰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、C1-C4卤代烷基、苯基、OR17、SR18或NR19R20；
或R15表示CN、CONR19R20、NO2、C1-C4卤代烷基、S(O)m-C1-C6烷基、未经取代或经C1-C12烷基或SO2-C1-C6烷基取代的S(O)m-苯基；
或R15表示SO2O-苯基，其是未经取代或经C1-C12烷基取代；或是二苯基膦酰基或二-(C1-C4烷氧基)-膦酰基；
m表示1或2；
R'14具有针对R14所给出含义中之一的；
R'15具有针对R15所给出含义中之一的；
X1表示O、S、SO或SO2；
X2表示O、CO、S或直接键；
R16表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C1-C20烷基；或其各经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R16表示氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4)烷基、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基)；
或R16表示C2-C12烷基，其间杂有一或多个O、S或NR26；或R16表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8环烷基；
或R16表示经SR18取代的苯基，其中该基团R18表示键结至该COR16基团所附接的该咔唑部分的该苯基或萘基环的直接键；
n表示1至20；
R17表示氢、苯基-C1-C3烷基、C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20环烷基、SO2-(C1-C4卤代烷基)、 O(C1-C4卤代烷基)或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O、S或NR26；
或R17表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷酰基、C2-C12烯基、C3-C6烯酰基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C20环烷基；
或R17表示C1-C8烷基-C3-C10环烷基，其是未经间杂或间杂有一或多个O；
或R17表示苯甲酰基，其是未经取代或经一或多个C1-C6烷基、卤素、OH或C1-C3烷氧基取代；
或R17表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或式(7)所表示的基团、
Figure PCTCN2015092009-appb-000010
或R17形成键结至该具有由式(2)所表示的基团、或是式(7)所表示的基团所处的苯基或萘基环的其中一个碳原子的直接键、
Figure PCTCN2015092009-appb-000011
R18表示氢、C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基，其中该C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基是未经间杂或间杂有一或多个O、S、CO、NR26或COOR17；或R18是C1-C20烷基，其是未经取代或经一或多个以下基团取代：OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)、O(CO)-苯基或(CO)OR17；
或R18表示C2-C20烷基，其间杂有一或多个O、S、CO、NR26或COOR17；
或R18表示(CH2CH2O)nH、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C8烷酰基或C3-C6烯酰基；
或R18表示苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6 烷基、卤素、OH、C1-C4烷氧基或C1-C4烷基硫基；
或R18表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C12烷基、C1-C4卤代烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基胺基、(CO)O(C1-C8烷基)、(CO)-C1-C8烷基、(CO)N(C1-C8烷基)2或式(7)所表示的基团、
Figure PCTCN2015092009-appb-000012
R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C2-C10烷氧基烷基、C2-C5烯基、C3-C20环烷基、苯基-C1-C3烷基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基、SO2-(C1-C4卤代烷基)或苯甲酰基；
或R19及R20表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C4卤代烷基、C1-C20烷氧基、C1-C12烷基、苯甲酰基或C1-C12烷氧基；
或R19及R20与其所附接的N原子一起形成未经间杂或间杂有O、S或NR17的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、NO2、卤素、C1-C4-卤代烷基、CN、苯基、未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000013
或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C4卤代烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、卤素、NO2、CN、苯基或未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000014
R21及R22彼此独立地为氢、C1-C20烷基、C1-C4卤代烷基、C3-C10环烷基或苯基；
或R21及R22与其所附接的N原子一起形成未经间杂或间杂有O、S或NR26的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未稠合或该5元或6元饱和或不饱和环与苯环稠合；
R23表示氢、OH、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、CO或NR26的C2-C20烷基、未经间杂或间杂有O、S、CO或NR26的C3-C20环烷基，或R23表示苯基、萘基、苯基-C1-C4烷基、OR17、SR18或NR21R22；
R24表示(CO)OR17、CONR19R20、(CO)R17；或R24具有针对R19及R20所给出含义中之一的；
R25表示COOR17、CONR19R20、(CO)R17；或R25具有针对R17所给出含义中之一的；
R26表示氢、C1-C20烷基、C1-C4卤代烷基、C2-C20烷基，其间杂有一或多个O或CO；或是苯基-C1-C4烷基、C3-C8环烷基，其是未经间杂或间杂有一或多个O或CO；或是(CO)R19；或是苯基，其是未经取代或经一或多个以下基团取代：C1-C20烷基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20或式(7)表示的基团；
Figure PCTCN2015092009-appb-000015
但条件为在该分子中存在至少一个式(2)或是式(7)所表示的基团
Figure PCTCN2015092009-appb-000016
在本发明的一实施例中，所述R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、COR16、NO2或由式(2)表示的基团；
Figure PCTCN2015092009-appb-000017
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团；
Figure PCTCN2015092009-appb-000018
但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团；
X表示CO或直接键；
R-13表示C-1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OR-17、SR18、COOR17、CONR19R20或PO(OCkH2k+1)2；
或R13表示C2-C20烷基，其间杂有一或多个O、S、NR26或CO；
或R13表示苯基或萘基，此两个是未经取代或经COR16取代或由一或多个式(7)表示的基团取代；
Figure PCTCN2015092009-appb-000019
R-14表示C1-C20烷基、苯基或C1-C8烷氧基；
R15表示苯基、萘基、C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、OR17、SR18或C2-C20烷基，其间杂有一或多个O或S；或其各经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C4-C20杂芳氧基羰基、OR17、SR18、NR19R20或PO(OCkH2k+1)2；
或R15表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：OR17、SR18、C3-C8环烷基、C3-C20杂芳基、NR19R20、COOR17、CONR19R20或PO(OCkH2k+1)2；
R'14具有针对R14所给出含义中之一的；
R'15具有针对R15所给出含义中之一的；
R16表示苯基，其是未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C2-C20烷基；
或R16表示苯基，其是经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8 环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C4-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R16表示C1-C20烷基，其是未经取代或经以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)或(CO)O(C1-C4烷基)；
R-17表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OCH2CH2(CO)O(C1-C4烷基)、O(C1-C4烷基)、(CO)O(C1-C4烷基)、C3-C20环烷基或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O；
R18表示经COOR17取代的甲基；
R19及R20彼此独立地为氢、苯基、C1-C20烷基、C1-C8烷酰基或C1-C8烷酰基氧基；
或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统是未经取代或经由式(7)表示的基团取代；
Figure PCTCN2015092009-appb-000020
但条件为在该分子中存在至少一个式(2)或是式(7)所表示的基团；
Figure PCTCN2015092009-appb-000021
在本发明的一实施例中，所述R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢，或R1及R2、R3及R4或R5及R6彼此独立地共同为式(5)所表示的基团；
Figure PCTCN2015092009-appb-000022
但条件为R1及R2、R3及R4或R5及R6中的至少一对是由式(5)所表示的基团；
或R2表示COR16、NO2或是由式(2)所表示的基团或是由式(3)所表示的基团；
Figure PCTCN2015092009-appb-000023
或R7表示COR16或是由式(2)所表示的基团；
R9、R11及R12表示氢；
R-10表示氢、OR17或COR16；
X表示CO或直接键；
R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、OR17、SR18或PO(OCkH2k+1)2；
或R13表示C2-C20烷基，其间杂有一或多个O；
或R13表示苯基；
k表示整数2；
R14表示C1-C20烷基或噻吩基；
R15表示苯基或萘基，其各是未经取代或经一或多个OR17或C1-C20烷基取代；
或R15表示噻吩基、氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：OR17、SR18、C3-C8环烷基、NR19R20或COOR17；
或R15表示C2-C20烷基，其间杂有SO2；
R16表示苯基或萘基，其各是未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或C1-C20烷基；
或R16表示噻吩基；
R17表示氢、C1-C8烷酰基、C1-C20烷基，该C1-C20烷基是未经取代或经 一或多个以下基团取代：卤素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O；
R18表示C3-C20环烷基、C1-C20烷基，其是未经取代或经一或多个OH、O(CO)-(C2-C4烯基)或(CO)OR17取代；
或R18表示苯基，其是未经取代或经一或多个卤素取代；
R19及R20彼此独立地为C1-C8烷酰基或C1-C8烷酰基氧基；
或R19及R20与其所附接的N原子一起形成间杂有O的5元或6元饱和环；
但条件为在该分子中存在至少一个由式(2)所表示的基团；
Figure PCTCN2015092009-appb-000024
在本发明的一实施例中，所述碱可溶性树脂(A)包括碱可溶性树脂(A-1)，其中所述碱可溶性树脂(A-1)是由混合物聚合而得，并且所述混合物包括:含有聚合性不饱和基的二醇化合物(a-1-1)；四羧酸或其酸二酐(a-1-2)；以及二羧酸或其酸酐(a-1-3)。所述含有聚合性不饱和基的二醇化合物(a-1-1)是由具有至少二个环氧基的环氧化合物及具有至少一个羧酸基及至少一个乙烯性不饱和基的化合物反应而得，且具有至少二个环氧基的环氧化合物包括式(a-1)所示的结构、式(a-2)所示的结构或上述两种结构。
Figure PCTCN2015092009-appb-000025
式(a-1)中，W1、W2、W3以及W4各自独立表示氢原子、卤素原子、碳数为1至5的烷基、碳数为1至5的烷氧基、碳数为6至12的芳基或碳数为6至12的芳烷基。
Figure PCTCN2015092009-appb-000026
式(a-2)中，W5至W18各自独立表示氢原子、卤素原子、碳数为1至8的烷基或碳数为6至15的芳香基，s表示0至10的整数。且该碱可溶性树脂(A-1)的数量平均分子量为1000～8000。
在本发明的一实施例中，所述四羧酸或其酸二酐(a-1-2)以及所述二羧酸或其酸酐(a-1-3)中，至少一个含有氟原子。
在本发明的一实施例中，所述碱可溶性树脂(A)包括碱可溶性树脂(A-2)，所述碱可溶性树脂(A-2)是由硅烷单体进行聚缩合来合成，或是使用硅烷单体及其他可聚合用的化合物进行聚缩合来形成。
在本发明的一实施例中，所述感光性树脂组成物还包括多分支聚合物(F)。所述多分支聚合物(F)是由式(F2)表示的多巯基化合物与由式(F1)表示的多官能基(甲基)丙烯酸酯反应而形成。
Figure PCTCN2015092009-appb-000027
式(F1)中，M1表示氢原子或碳数为1至4的烷基。M2表示具有h个羟基的含羟基的化合物中的g个羟基经酯化后的残基，其中h≥g，g表示2至20的整数。所述含羟基的化合物为M3(OH)h或所述M3(OH)h经环氧丙烷、环氧氯丙烷、烷基、烷氧基或丙烯酸羟丙酯改性的化合物。M3(OH)h为具有碳数为2至18的多元醇、由所述多元醇所形成的多元醇醚、由所述多元醇与酸反应而形成的酯类、或硅酮。
Figure PCTCN2015092009-appb-000028
式(F2)中，M4表示单键、碳数为1的烃基、或碳数为2至22的直链或支链的烃基。M4的骨架中可还包括硫原子或构成酯基中的氧原子。而i表示 2至6的整数，其中当M4表示单键时，i表示2；当M4表示碳数为1的烃基时，i表示2至4的整数；当M4表示碳数为2至22的直链或支链的烃基时，i表示2至6的整数。
在本发明的一实施例中，所述感光性树脂组成物还包括式(10)表示的化合物(H)。
Figure PCTCN2015092009-appb-000029
式(10)中，Z1、Z2及Z3各自独立代表经亚烷基或亚芳基结合的三烷氧基硅烷基。
在本发明的一实施例中，基于所述碱可溶性树脂(A)100重量份，所述具有乙烯性不饱和基的化合物(B)的使用量为15重量份至200重量份，所述具有酸性基及至少三个乙烯性不饱和基的化合物(B-1)的使用量为15重量份至150重量份，所述光起始剂(C)的使用量为10重量份至80重量份，所述由式(1)表示的光起始剂(C-1)的使用量为10重量份至70重量份，所述溶剂(D)的使用量为1000重量份至8000重量份，所述黑色颜料(E)的使用量为150重量份至1200重量份。
在本发明的一实施例中，基于所述碱可溶性树脂(A)100重量份，所述碱可溶性树脂(A-1)的使用量为50重量份至100重量份。
在本发明的一实施例中，基于所述碱可溶性树脂(A)100重量份，所述碱可溶性树脂(A-2)的使用量为0重量份至50重量份。
在本发明的一实施例中，基于所述碱可溶性树脂(A)100重量份，所述多分支聚合物(F)的使用量为3重量份至35重量份。
在本发明的一实施例中，基于所述碱可溶性树脂(A)100重量份，所述热起始剂(G)的使用量为4重量份至40重量份。
在本发明的一实施例中，基于所述碱可溶性树脂(A)100重量份，所述式(10)表示的化合物(H)的使用量为1重量份至10重量份。
本发明也提供一种黑色矩阵，其是使用上述的感光性树脂组成物而形成。
本发明还提供一种彩色滤光片，其包括上述的黑色矩阵。
本发明另提供一种一种液晶显示器，其包括上述的的彩色滤光片。
基于上述，本发明的感光性树脂组成物包括具有乙烯性不饱和基的化合物(B)以及特定结构的光起始剂(C)，因此可以改善黑色矩阵的解析度、耐热阻抗性以及高温及高湿下的信赖性不佳的问题，进而适用于彩色滤光片以及液晶显示装置。
为让本发明的上述特点和优点能更明显易懂，下文特举实施例，并作详细说明如下。
具体实施方式
<感光性树脂组成物>
本发明提供一种感光性树脂组成物，其包括碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)、光起始剂(C)、溶剂(D)以及黑色颜料(E)。此外，感光性树脂组成物可进一步包括多分支聚合物(F)、热起始剂(G)以及式(10)表示的化合物(H)。以下将详细说明用于本发明的感光性树脂组成物的各个成分：
在此说明的是，以下是以(甲基)丙烯酸表示丙烯酸和/或甲基丙烯酸，并以(甲基)丙烯酸酯表示丙烯酸酯和/或甲基丙烯酸酯；同样地，以(甲基)丙烯酰基表示丙烯酰基和/或甲基丙烯酰基。
碱可溶性树脂(A)：
碱可溶性树脂(A)包括碱可溶性树脂(A-1)、碱溶性树脂(A-2)以及其他碱可溶性树脂(A-3)。
碱可溶性树脂(A-1)
碱可溶性树脂(A-1)是由混合物聚合而得。混合物包括含有聚合性不饱和基的二醇化合物(a-1-1)、四羧酸或其酸二酐(a-1-2)以及二羧酸或其酸酐(a-1-3)。
含有聚合性不饱和基的二醇化合物(a-1-1)
含有聚合性不饱和基的二醇化合物(a-1-1)是由具有至少二个环氧基的环氧化合物及具有至少一个羧酸基及至少一个乙烯性不饱和基的化合物反应而得。
具有至少二个环氧基的环氧化合物包括式(a-1)所示的结构、式(a-2)所示的结构以及式(a-3)所示的结构，或上述三种结构。以下分别具体说明式(a-1)所示的结构、式(a-2)所示的结构、式(a-3)所示的结构。
具体而言，式(a-1)所表示的结构如下：
Figure PCTCN2015092009-appb-000030
式(a-1)中，W1、W2、W3以及W4各自独立表示氢原子、卤素原子、碳数为1至5的烷基、碳数为1至5的烷氧基、碳数为6至12的芳基或碳数为6至12的芳烷基。
含有式(a-1)所表示的结构的具有至少二个环氧基的环氧化合物可包括由双酚芴型化合物与卤化环氧丙烷反应而得的具有环氧基的双酚芴型化合物。
详言之，双酚芴型化合物的具体例包括：9,9-双(4-羟基苯基)芴、9,9-双(4-羟基-3-甲基苯基)芴、9,9-双(4-羟基-3-氯苯基)芴、9,9-双(4-羟基-3-溴苯基)芴、9,9-双(4-羟基-3-氟苯基)芴、9,9-双(4-羟基-3-甲氧基苯基)芴、9,9-双(4-羟基-3,5-二甲基苯基)芴、9,9-双(4-羟基-3,5-二氯苯基)芴、9,9-双(4-羟基-3,5-二溴苯基)芴或其类似物，或上述化合物的组合。
卤化环氧丙烷的具体例包括3-氯-1,2-环氧丙烷或3-溴-1,2-环氧丙烷或其类似物，或上述化合物的组合。
具有环氧基的双酚芴型化合物的具体例包括(1)新日铁化学制造的商品：例如ESF-300或其类似物；(2)大阪瓦斯制造的商品：例如PG-100、EG-210或其类似物；(3)S.M.S Technology Co.制造的商品：例如SMS-F9PhPG、 SMS-F9CrG、SMS-F914PG或其类似物。
另外，具体而言，式(a-2)所表示的结构如下：
Figure PCTCN2015092009-appb-000031
式(a-2)中，W5至W18各自独立表示氢原子、卤素原子、碳数为1至8的烷基或碳数为6至15的芳香基，s表示0至10的整数。
含有式(a-2)所表示的结构的具有至少二个环氧基的环氧化合物可包括在碱金属氢氧化物存在下，使具有下式(a-2-I)结构的化合物与卤化环氧丙烷进行反应而得。
Figure PCTCN2015092009-appb-000032
在上式(a-2-I)中，W5至W18以及s的定义是分别与式(a-2)中的W5至W18以及s的定义相同，在此不另赘述。
含有式(a-2)所表示的结构的具有至少二个环氧基的环氧化合物的合成方法可参考台湾公开号TW201508418的专利。
上述含有式(a-2)所表示的结构的具有至少二个环氧基的环氧化合物的具体例包括商品名为NC-3000、NC-3000H、NC-3000S以及NC-3000P等由日本化药制造的商品。
另外，具体而言，式(a-3)所表示的结构如下：
Figure PCTCN2015092009-appb-000033
式(a-3)中，Ar1表示萘环，Q1表示氰基、卤素或烃基，Q2表示烃基、烷氧基、环烷氧基、芳氧基、芳烷氧基、烷硫基、环烷硫基、芳硫基、芳烷硫基、酰基、卤素、硝基、氰基或是经取代的氨基，J表示伸烷基，xa表示0至4的整数，xb以及xc表示0以上的整数。
上述含有式(a-3)所表示的结构的具有至少二个环氧基的环氧化合物的具体例包括：9,9-双(缩水甘油氧基萘基)芴，且例如是9,9-双(6-缩水甘油氧基-2-萘基)芴或9,9-双(5-缩水甘油氧基-1-萘基)芴等类似之化合物。
具有至少一个羧酸基及至少一个乙烯性不饱和基的化合物选自于由以下(1)至(3)所组成的族群的其中一种：
(1)丙烯酸、甲基丙烯酸、2-甲基丙烯酰氧乙基丁二酸、2-甲基丙烯酰氧丁基丁二酸、2-甲基丙烯酰氧乙基己二酸、2-甲基丙烯酰氧丁基己二酸、2-甲基丙烯酰氧乙基六氢邻苯二甲酸、2-甲基丙烯酰氧乙基马来酸、2-甲基丙烯酰氧丙基马来酸、2-甲基丙烯酰氧丁基马来酸、2-甲基丙烯酰氧丙基丁二酸、2-甲基丙烯酰氧丙基己二酸、2-甲基丙烯酰氧丙基四氢邻苯二甲酸、2-甲基丙烯酰氧丙基邻苯二甲酸、2-甲基丙烯酰氧丁基邻苯二甲酸、2-甲基丙烯酰氧丁基氢邻苯二甲酸或其类似物；
(2)由具有羟基的(甲基)丙烯酸酯与二元羧酸化合物反应而得的化合物，其中二元羧酸化合物的具体例包括己二酸、丁二酸、马来酸、邻苯二甲酸或其类似物；以及
(3)由具有羟基的(甲基)丙烯酸酯与羧酸酐化合物反应而得的半酯化合物，其中具有羟基的(甲基)丙烯酸酯的具体例包括2-羟基乙基丙烯酸酯、2- 羟基乙基甲基丙烯酸酯、2-羟基丙基丙烯酸酯、2-羟基丙基甲基丙烯酸酯、4-羟基丁基丙烯酸酯、4-羟基丁基甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯或其类似物。
另外，此处所述的羧酸酐化合物与以下所述的四羧酸二酐或二羧酸酐相同，在此不另赘述。
四羧酸或其酸二酐(a-1-2)
四羧酸或其酸二酐(a-1-2)包括含有氟原子的四羧酸或其酸二酐、除了所述含有氟原子的四羧酸或其酸二酐之外的其他四羧酸或其酸二酐或上述两个的组合。
含有氟原子的四羧酸或其酸二酐选自由式(K-1)表示的含有氟原子的四羧酸化合物以及由式(K-2)表示的含有氟原子的四羧酸二酐化合物所组成的族群。具体而言，由式(K-1)表示的含有氟原子的四羧酸化合物以及由式(K-2)表示的含有氟原子的四羧酸二酐化合物如下。
Figure PCTCN2015092009-appb-000034
式(K-1)与式(K-2)中，L2为具有氟的四价芳香族基团，且较佳为具有苯环。具体而言，较佳为选自由式(L-1)至式(L-6)表示的基团中的其中一个。
Figure PCTCN2015092009-appb-000035
式(L-1)至式(L-6)中，E各自独立表示氟原子或三氟甲基，*表示与碳原子键结的位置。
详言之，含有氟原子的四羧酸或其酸二酐的具体例包括4,4'-六氟亚异丙基二邻苯二甲酸、1,4-二氟均苯四甲酸、1-单氟均苯四甲酸、1,4-二(三氟甲基)均苯四甲酸等含氟的芳香族四羧酸，或上述四羧酸的二酐化合物，或上述化合物的组合。
含有氟原子的四羧酸或其酸二酐的具体例还包括3,3'-六氟亚异丙基二邻苯二甲酸、5,5'-[2,2,2-三氟-1-[3-(三氟甲基)苯基]亚乙基]二邻苯二甲酸、5,5'-[2,2,3,3,3-五氟-1-(三氟甲基)亚丙基]二邻苯二甲酸、5,5'-氧基双[4,6,7-三氟-均苯四甲酸]、3,6-双(三氟甲基)均苯四甲酸、4-(三氟甲基)均苯四甲酸、1,4-双(3,4-二羧酸三氟苯氧基)四氟苯等含氟的四羧酸，或上述四羧酸的二酐化合物，或上述化合物的组合。
其他四羧酸或其酸二酐包括饱和直链烃四羧酸、脂环式四羧酸、芳香族四羧酸，或上述四羧酸的二酐化合物，或其组合。
饱和直链烃四羧酸的具体例包括丁烷四羧酸、戊烷四羧酸、己烷四羧酸，或上述化合物的组合。饱和直链烃四羧酸也可具有取代基。
脂环式四羧酸的具体例包括环丁烷四羧酸、环戊烷四羧酸、环已烷四羧酸，降冰片烷四羧酸，或上述化合物的组合。脂环式四羧酸也可具有取代基。
芳香族四羧酸的具体例包括均苯四甲酸、二苯甲酮四羧酸、联苯四羧酸、联苯醚四羧酸、二苯基砜四羧酸、1,2,3,6-四氢邻苯二甲酸，或上述化合物的 组合。芳香族四羧酸也可具有取代基。
二羧酸或其酸酐(a-1-3)
二羧酸或其酸酐(a-1-3)包括含有氟原子的二羧酸或其酸酐、除了所述含有氟原子的二羧酸或其酸酐之外的其他二羧酸或其酸酐或上述两个的组合。
含有氟原子的二羧酸或其酸酐选自由式(G-1)表示的含有氟原子的二羧酸化合物以及由式(G-2)表示的含有氟原子的二羧酸酐化合物所组成的族群。具体而言，由式(G-1)表示的含有氟原子的二羧酸化合物以及由式(G-2)表示的含有氟原子的二羧酸酐化合物如下。
Figure PCTCN2015092009-appb-000036
式(G-1)与式(G-2)中，G1表示碳数为1至100的含氟原子的有机基。
含有氟原子的二羧酸或其酸酐的具体例包括3-氟邻苯二甲酸、4-氟邻苯二甲酸、四氟邻苯二甲酸、3,6-二氟邻苯二甲酸、四氟琥珀酸，或上述二羧酸的酸酐化合物，或上述化合物的组合。
其他二羧酸或其酸酐的具体例包括饱和直链烃二羧酸、饱和环状烃二羧酸、不饱和二羧酸，或上述二羧酸化合物的酸酐，或上述化合物的组合。
饱和直链烃二羧酸的具体例包括丁二酸、乙酰基丁二酸、己二酸、壬二酸、柠苹酸、丙二酸、戊二酸、柠檬酸、酒石酸、氧代戊二酸、庚二酸、癸二酸、辛二酸、二甘醇酸，或上述化合物的组合。饱和直链烃二羧酸中的烃基也可被取代。
饱和环状烃二羧酸的具体例包括六氢邻苯二甲酸、环丁烷二羧酸、环戊烷二羧酸、降冰片烷二羧酸、六氢偏苯三酸，或上述化合物的组合。饱和环状烃二羧酸也可为饱和烃经取代的脂环式二羧酸。
不饱和二羧酸的具体例包括马来酸、衣康酸、邻苯二甲酸、四氢邻苯二甲酸、甲基桥亚甲基四氢邻苯二甲酸、氯茵酸、偏苯三酸，或上述化合物的组合。
其他二羧酸或其酸酐的具体例包括三甲氧基硅烷基丙基丁二酸酐、三乙 氧基硅烷基丙基丁二酸酐、甲基二甲氧基硅烷基丙基丁二酸酐、甲基二乙氧基硅烷基丙基丁二酸酐、三甲氧基硅烷基丁基丁二酸酐、三乙氧基硅烷基丁基丁二酸酐、甲基二乙氧基硅烷基丁基丁二酸酐、对(三甲氧基硅烷基)苯基丁二酸酐、对(三乙氧基硅烷基)苯基丁二酸酐、对(甲基二甲氧基硅烷基)苯基丁二酸酐、对(甲基二乙氧基硅烷基)苯基丁二酸酐、间(三甲氧基硅烷基)苯基丁二酸酐、间(三乙氧基硅烷基)苯基丁二酸酐、间(甲基二乙氧基硅烷基)苯基丁二酸酐等二羧酸酐，或上述二羧酸酐的二羧酸化合物，或上述化合物的组合。
碱可溶性树脂(A-1)的合成方法并无特别限制，只要将含有聚合性不饱和基的二醇化合物(a-1-1)、四羧酸二酐或其四羧酸(a-1-2)以及二羧酸酐或其二羧酸(a-1-3)反应即可获得，并且可参考台湾公开号TW201508418的专利进行合成。
碱可溶性树脂(A-1)的数量平均分子量为1000～8000。
基于所述碱可溶性树脂(A)100重量份，所述碱可溶性树脂(A-1)的使用量为50至100重量份，较佳为60重量份至100重量份，且更佳为70重量份至100重量份。当碱可溶性树脂(A-1)含有氟原子时，可进一步改善所制得的感光树脂组成物于高温及高湿下的信赖性。
碱可溶性树脂(A-2)
碱可溶性树脂(A-2)是由硅烷单体进行聚缩合来合成，或是使用硅烷单体及其他可聚合的化合物进行聚缩合来合成。碱可溶性树脂(A-2)的种类并没有特别限制，只要可达到本发明的目的即可。
硅烷单体包括但不限于除了硅烷单体(a-S1)、硅烷单体(a-S2)；其他可聚合的化合物包含硅氧烷预聚物(a-S3)、二氧化硅粒子(a-S4)，或其组合。以下，进一步说明各个成分以及聚缩合的反应步骤与条件。
硅烷单体(a-S1)
硅烷单体(a-S1)为由式(9-1)表示的化合物。
Si(U1)w(OU2)4-w  式(9-1)
式(9-1)中，U1各自独立表示氢原子、碳数为1至10的烷基、碳数为2至10的烯基、碳数为6至15的芳香基、含有酸酐基的烷基、含有环氧基的烷基或含有环氧基的烷氧基，至少一个U1为含有酸酐基的烷基、含有环氧基的烷基或含有环氧基的烷氧基；U2各自独立表示氢原子、碳数为1至6的烷基、碳数为1至6的酰基或碳数为6至15的芳香基；w表示1至3的整数。
更详细而言，当式(9-1)中的U1表示碳数为1至10的烷基时，具体而言，U1例如是甲基、乙基、正丙基、异丙基、正丁基、第三丁基、正己基或正癸基。又，U1也可以是烷基上具有其他取代基的烷基，具体而言，U1例如是三氟甲基、3,3,3-三氟丙基、3-胺丙基、3-巯丙基或3-异氰酸丙基。
当式(9-1)中的U1表示碳数为2至10的烯基时，具体而言，U1例如是乙烯基。又，U1也可以是烯基上具有其他取代基的烯基，具体而言，U1例如是3-丙烯酰氧基丙基或3-甲基丙烯酰氧基丙基。
当式(9-1)中的U1表示碳数为6至15的芳香基时，具体而言，U1例如是苯基、甲苯基或萘基。又，U1也可以是芳香基上具有其他取代基的芳香基，具体而言，U1例如是对-羟基苯基、1-(对-羟基苯基)乙基、2-(对-羟基苯基)乙基或4-羟基-5-(对-羟基苯基羰氧基)戊基。
此外，式(9-1)中的U1表示含有酸酐基的烷基，其中烷基较佳为碳数为1至10的烷基。具体而言，所述含有酸酐基的烷基例如是式(9-1-1)所示的乙基丁二酸酐、式(9-1-2)所示的丙基丁二酸酐或式(9-1-3)所示的丙基戊二酸酐。值得一提的是，酸酐基是由二羧酸经分子内脱水所形成的基团，其中二羧酸例如是丁二酸或戊二酸。
Figure PCTCN2015092009-appb-000037
Figure PCTCN2015092009-appb-000038
再者，式(9-1)中的U1表示含有环氧基的烷基，其中烷基较佳为碳数为1至10的烷基。具体而言，所述含有环氧基的烷基例如是环氧丙烷基戊基或2-(3,4-环氧环己基)乙基。值得一提的是，环氧基是由二元醇经分子内脱水所形成的基团，其中二元醇例如是丙二醇、丁二醇或戊二醇。
式(9-1)中的U1表示含有环氧基的烷氧基，其中烷氧基较佳为碳数为1至10的烷氧基。具体而言，所述含有环氧基的烷氧基例如是环氧丙氧基丙基或2-环氧丙烷基丁氧基。
另外，当式(9-1)的U2表示碳数为1至6的烷基时，具体而言，U2例如是甲基、乙基、正丙基、异丙基或正丁基。当式(9-1)中的U2表示碳数为1至6的酰基时，具体而言，U2例如是乙酰基。当式(9-1)中的U2表示碳数为6至15的芳香基时，具体而言，U2例如是苯基。
在式(9-1)中，w表示1至3的整数。当w表示2或3时，多个U1可为相同或不同；当w表示1或2时，多个U2可为相同或不同。
硅烷单体(a-S1)的具体例包括：3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基三乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、2-环氧丙烷基丁氧基丙基三苯氧基硅烷、由东亚合成所制造的市售品：2-环氧丙烷基丁氧基丙基三甲氧基硅烷、2-环氧丙烷基丁氧基丙基三乙氧基硅烷、3-(三苯氧基硅基)丙基丁二酸酐、由信越化学所制造的市售品：3-(三甲氧基硅基)丙基丁二酸酐(商品名X-12-967)、由WACKER公司所制造的市售品：3-(三乙氧基硅基)丙基丁二酸酐(商品名GF-20)、3-(三甲氧基硅基)丙基戊二酸酐(简称TMSG)、3-(三乙氧基硅基)丙基戊二酸酐、3-(三苯氧基硅基)丙基戊二酸酐、二异丙氧基-二(2-环氧丙烷基丁氧基丙基)硅烷、二(3-环氧丙烷基戊 基)二甲氧基硅烷、(二正丁氧基硅基)二(丙基丁二酸酐)、(二甲氧基硅基)二(乙基丁二酸酐)、3-环氧丙氧基丙基二甲基甲氧基硅烷、3-环氧丙氧基丙基二甲基乙氧基硅烷、二(2-环氧丙烷基丁氧基戊基)-2-环氧丙烷基戊基乙氧基硅烷、三(2-环氧丙烷基戊基)甲氧基硅烷、(苯氧基硅基)三(丙基丁二酸酐)、(甲基甲氧基硅基)二(乙基丁二酸酐)，或上述化合物的组合。
硅烷单体(a-S1)可单独使用或组合多种来使用。
硅烷单体(a-S2)
硅烷单体(a-S2)为由式(9-2)表示的化合物。
Si(U3)u(OU4)4-u  式(9-2)
式(9-2)中，U3各自独立表示氢原子、碳数为1至10的烷基、碳数为2至10的烯基或碳数为6至15的芳香基；U4各自独立表示氢原子、碳数为1至6的烷基、碳数为1至6的酰基或碳数为6至15的芳香基；u表示0至3的整数。
更详细而言，当式(9-2)中的U3表示碳数为1至10的烷基时，具体而言，U3例如是甲基、乙基、正丙基、异丙基、正丁基、第三丁基、正己基或正癸基。又，U3也可以是烷基上具有其他取代基的烷基，具体而言，U3例如是三氟甲基、3,3,3-三氟丙基、3-胺丙基、3-巯丙基或3-异氰酸丙基。
当式(9-2)中的U3表示碳数为2至10的烯基时，具体而言，U3例如是乙烯基。又，U3也可以是烯基上具有其他取代基的烯基，具体而言，U3例如是3-丙烯酰氧基丙基或3-甲基丙烯酰氧基丙基。
当式(9-2)中的U3表示碳数为6至15的芳香基时，具体而言，U3例如是苯基、甲苯基或萘基。又，U3也可以是芳香基上具有其他取代基的芳香基，具体而言，U3例如是对-羟基苯基、1-(对-羟基苯基)乙基、2-(对-羟基苯基)乙基或4-羟基-5-(对-羟基苯基羰氧基)戊基。
另外，当式(9-2)的U4表示碳数为1至6的烷基时，具体而言，U4例如是甲基、乙基、正丙基、异丙基或正丁基。当式(9-2)中的U4表示碳数为1至6的酰基时，具体而言，U4例如是乙酰基。当式(9-2)中的U4表示 碳数为6至15的芳香基时，具体而言，U4例如是苯基。
在式(9-2)中，u为0至3的整数。当u表示2或3时，多个U3可为相同或不同；当u表示0、1或2时，多个U4可为相同或不同。
在式(9-2)中，当u＝0时，表示硅烷单体为四官能性硅烷单体(即具有四个可水解基团的硅烷单体)；当u＝1时，表示硅烷单体为三官能性硅烷单体(即具有三个可水解基团的硅烷单体)；当u＝2时，表示硅烷单体为二官能性硅烷单体(即具有二个可水解基团的硅烷单体)；并且当u＝3时，则表示硅烷单体为单官能性硅烷单体(即具有一个可水解基团的硅烷单体)。值得一提的是，所述可水解基团是指可以进行水解反应并且与硅键结的基团，举例来说，可水解基团例如是烷氧基、酰氧基或苯氧基。
由式(9-2)表示的硅烷单体的具体例包括但不限于：
(1)四官能性硅烷单体：四甲氧基硅烷、四乙氧基硅烷、四乙酰氧基硅烷或四苯氧基硅烷等；
(2)三官能性硅烷单体：甲基三甲氧基硅烷、甲基三乙氧基硅烷、甲基三异丙氧基硅烷、甲基三正丁氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、乙基三异丙氧基硅烷、乙基三正丁氧基硅烷、正丙基三甲氧基硅烷、正丙基三乙氧基硅烷、正丁基三甲氧基硅烷、正丁基三乙氧基硅烷、正己基三甲氧基硅烷、正己基三乙氧基硅烷、癸基三甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、对-羟基苯基三甲氧基硅烷、1-(对-羟基苯基)乙基三甲氧基硅烷、2-(对-羟基苯基)乙基三甲氧基硅烷、4-羟基-5-(对-羟基苯基羰氧基)戊基三甲氧基硅烷、三氟甲基三甲氧基硅烷、三氟甲基三乙氧基硅烷、3,3,3-三氟丙基三甲氧基硅烷、3-胺丙基三甲氧基硅烷、3-胺丙基三乙氧基硅烷、3-巯丙基三甲氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷或3-甲基丙烯酰氧基丙基三乙氧基硅烷；
(3)二官能性硅烷单体：二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、二甲基二乙酰氧基硅烷、二正丁基二甲氧基硅烷或二苯基二甲氧基硅烷；或
(4)单官能性硅烷单体：三甲基甲氧基硅烷或三正丁基乙氧基硅烷等。
所述的各种硅烷单体可单独使用或组合多种来使用。
硅氧烷预聚物(a-S3)
硅氧烷预聚物(a-S3)是由式(9-3)表示的化合物。
Figure PCTCN2015092009-appb-000039
式(9-3)中，U5、U6、U7及U8各自独立表示氢原子、碳数为1至10的烷基、碳数为2至6的烯基或碳数为6至15的芳香基，其中该烷基、烯基及芳香基中任一个可选择地含有取代基；U9与U10各自独立表示氢原子、碳数为1至6的烷基、碳数为1至6的酰基或碳数为6至15的芳香基，其中该烷基、酰基及芳香基中任一个可选择地含有取代基；v表示1至1000的整数。
更详细而言，当式(9-3)中的U5、U6、U7及U8各自独立表示碳数为1至10的烷基时，具体而言，U5、U6、U7及U8例如各自独立为甲基、乙基或正丙基。当式(9-3)中的U5、U6、U7及U8各自独立表示碳数为2至10的烯基时，具体而言，U5、U6、U7及U8例如各自独立为乙烯基、丙烯酰氧基丙基或甲基丙烯酰氧基丙基。当式(9-3)中的U5、U6、U7及U8各自独立表示碳数为6至15的芳香基时，具体而言，U5、U6、U7及U8例如各自独立为苯基、甲苯基或萘基。又，所述烷基、烯基及芳香基中任一个可以具有其他取代基。
另外，当式(9-3)的U9与U10各自独立表示碳数为1至6的烷基时，具体而言，U9与U10例如各自独立为甲基、乙基、正丙基、异丙基或正丁基。当式(9-3)的U9与U10各自独立表示碳数为1至6的酰基时，具体而言，U9与U10例如是乙酰基。当式(9-3)中的U9与U10各自独立表示碳数为6至15的芳香基时，具体而言，U9与U10例如是苯基。其中，上述烷基、酰基及芳香基中任一个可选择地具有取代基。
式(9-3)中，v可为1至1000的整数，较佳为3至300的整数，更佳为5至200的整数。当v为2至1000的整数时，U5各自为相同或不同的基团，且U6各自为相同或不同的基团。
硅氧烷预聚物(a-S3)的具体例包括但不限于：1,1,3,3-四甲基-1,3-二甲氧基二硅氧烷、1,1,3,3-四甲基-1,3-二乙氧基二硅氧烷、1,1,3,3-四乙基-1,3-二乙氧基二硅氧烷或者由吉来斯特(Gelest)公司制造的末端为硅烷醇的聚硅氧烷(Silanol terminated polydimethylsiloxane)的市售品(商品名如DMS-S12(分子量400至700)、DMS-S15(分子量1500至2000)、DMS-S21(分子量4200)、DMS-S27(分子量18000)、DMS-S31(分子量26000)、DMS-S32(分子量36000)、DMS-S33(分子量43500)、DMS-S35(分子量49000)、DMS-S38(分子量58000)、DMS-S42(分子量77000)或PDS-9931(分子量1000至1400))。
硅氧烷预聚物(a-S3)可单独使用或组合多种来使用。
二氧化硅粒子(a-S4)
二氧化硅粒子(a-S4)的平均粒径并无特别的限制。平均粒径的范围为2nm至250nm，较佳为5nm至200nm，且更佳为10nm至100nm。
二氧化硅粒子的具体例包括但不限于：由触媒化成公司所制造的市售品(商品名如OSCAR 1132(粒径12nm；分散剂为甲醇)、OSCAR 1332(粒径12nm；分散剂为正丙醇)、OSCAR 105(粒径60nm；分散剂为γ-丁内酯)、OSCAR 106(粒径120nm；分散剂为二丙酮醇)等)、由扶桑化学公司所制造的市售品(商品名如Quartron PL-1-IPA(粒径13nm；分散剂为异丙酮)、Quartron PL-1-TOL(粒径13nm；分散剂为甲苯)、Quartron PL-2L-PGME(粒径18nm；分散剂为丙二醇单甲醚)或Quartron PL-2L-MEK(粒径18nm；分散剂为甲乙酮)等)或由日产化学公司所制造的市售品(商品名如IPA-ST(粒径12nm；分散剂为异丙醇)、EG-ST(粒径12nm；分散剂为乙二醇)、IPA-ST-L(粒径45nm；分散剂为异丙醇)或IPA-ST-ZL(粒径100nm；分散剂为异丙醇))。二氧化硅粒子可单独使用或组合多种来使用。
一般而言，硅烷单体、聚硅氧烷预聚物和/或二氧化硅粒子的聚合反应(即水解及部分缩合)是以下列步骤来进行：在硅烷单体中添加溶剂、水，或可选择性地添加催化剂；以及于50℃至150℃下加热搅拌0.5小时至120小时，且可进一步通过蒸馏除去副产物(醇类、水等)。
聚缩合反应所使用的溶剂并没有特别限制，且所述溶剂可与本发明的感 光性树脂组成物所包括的溶剂(D)相同或不同。基于硅烷单体的总量为100重量份，溶剂的使用量较佳为15重量份至1200重量份；更佳为20重量份至1100重量份；进而更佳为30重量份至1000重量份。
基于硅烷单体的可水解基团为1摩尔，聚缩合反应所使用的水(即用于水解的水)较佳为0.5摩尔至2摩尔。
聚缩合反应所使用的催化剂没有特别的限制，且较佳为选自酸催化剂或碱催化剂。酸催化剂的具体例包括但不限于盐酸、硝酸、硫酸、氢氟酸、草酸、磷酸、醋酸、三氟醋酸、蚁酸、多元羧酸或其酸酐或离子交换树脂等。碱催化剂的具体例包括但不限于二乙胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺、二乙醇胺、三乙醇胺、氢氧化钠、氢氧化钾、含有胺基的具有烷氧基的硅烷或离子交换树脂等。
基于硅烷单体的总量为100重量份，催化剂的使用量较佳为0.005重量份至15重量份；更佳为0.01重量份至12重量份；进而更佳为0.05重量份至10重量份。
基于安定性的观点，聚硅氧烷较佳为不含副产物(如醇类或水)及催化剂。因此，可选择性地将聚缩合反应后的反应混合物进行纯化来获得聚硅氧烷。纯化的方法无特别限制，较佳为可使用疏水性溶剂稀释反应混合物。接着，将疏水性溶剂与反应混合物转移至分液漏斗。然后，以水洗涤有机层数回，再以旋转蒸发器浓缩有机层，以除去醇类或水。另外，可使用离子交换树脂除去催化剂。
基于所述碱可溶性树脂(A)100重量份，所述具碱可溶性树脂(A-2)的使用量为0至50重量份，较佳为0重量份至40重量份，且更佳为0重量份至30重量份。当碱可溶性树脂(A)含有碱可溶性树脂(A-2)时，可进一步改善所制得的感光树脂组成物在高温及高湿下的信赖性。
其他碱可溶性树脂(A-3)
碱可溶性树脂(A)还可选择性包括其他碱可溶性树脂(A-3)。其他碱可溶性树脂(A-3)为碱可溶性树脂(A-1)与碱可溶性树脂(A-2)以外的树脂。其他碱可溶性树脂(A-3)例如为具有羧酸基或羟基的树脂，但不限于具有羧酸基或羟基的树脂。其他碱可溶性树脂(A-3)的具体例包括丙烯酸系树脂、胺基甲酸酯系树 脂、酚醛清漆树脂等树脂。
具有乙烯性不饱和基的化合物(B)：
具有乙烯性不饱和基的化合物(B)包括具有酸性基及至少三个(以上)乙烯性不饱和基的化合物(B-1)以及其它具有乙烯性不饱和基的化合物(B-2)。
具有酸性基及至少三个以上乙烯性不饱和基的化合物(B-1)
本发明的具有乙烯性不饱和基的化合物(B)可包含具有酸性基及至少三个(以上)乙烯性不饱和基的化合物(B-1)。
该具有酸性基与至少三个(以上)乙烯性不饱和基的化合物(B-1)中的酸性基可与碱性显影剂产生作用。该酸性基的具体例，如：羧基、磺酸基或磷酸基等。其中，该酸性基较佳是可与碱性显影剂产生良好作用的羧基。
该具有酸性基与至少三个(以上)乙烯性不饱和基的化合物(B-1)可为(1)将具有羟基的多官能(甲基)丙烯酸酯与二元羧酸酐或二元酸进行改性反应，以合成出含羧基的多官能(甲基)丙烯酸酯，或者(2)将芳香族多官能(甲基)丙烯酸酯与浓硫酸或发烟硫酸进行改性反应，以合成出含磺酸基的多官能(甲基)丙烯酸酯。
较佳地，该具有酸性基与至少三个(以上)乙烯性不饱和基的化合物(B-1)具有如下式(IV)或(V)所示的结构：
Figure PCTCN2015092009-appb-000040
于式(IV)中，T1代表-CH2-、-OCH2-、-OCH2CH2-、-OCH2CH2CH2-或-OCH2CH2CH2CH2-；T2代表下式(IV-1)或式(IV-2)所示的结构；T3代表下式(IV-3)、式(IV-4)或式(IV-5)所示的结构，其中式(IV-5)所示的结构中的苯环也可为四氢化或六氢化，且e代表1至8的整数；d代表0至14的整数：
Figure PCTCN2015092009-appb-000041
Figure PCTCN2015092009-appb-000042
于式(V)中，T1、T2与T3如前所述；T4代表-O-或下式(V-1)
所示的结构；e与d如前所述且c代表1至8的整数：
Figure PCTCN2015092009-appb-000043
于式(IV)或式(V)中，当T1与T2存在复数个时，T1与T2分别可为相同或不同。
于前述式(IV)或式(V)所示具有酸性基与至少三个(以上)乙烯性不饱和基的化合物(B-1)的具体例中，具有三个乙烯性不饱和基的化合物(B-1)的具体例可为季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、二季戊四醇五丙烯酸酯与二季戊四醇五甲基丙烯酸酯等的单羟基寡聚丙烯酸酯或单羟基寡聚甲基丙烯酸酯与丙二酸、琥珀酸、戊二酸、间苯二甲酸、对苯二甲酸、邻苯二甲酸等的二酸类所形成的含有羧基的单酯化合物。
上述具有酸性基与至少三个(以上)乙烯性不饱和基的化合物较佳为季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯与琥珀酸、邻苯二甲酸、戊二酸所形成的含有羧基的 单酯化合物。
基于前述的碱可溶性树脂(A)的总使用量为100重量份，具有酸性基与至少三个乙烯性不饱和基的化合物(B-1)的使用量为15重量份至150重量份，较佳为20重量份至120重量份，更佳为25重量份至100重量份。当具有乙烯性不饱和基的化合物(B)不使用具有酸性基与至少三个乙烯性不饱和基的化合物(B-1)时，所制作的感光性树脂组成物的解析度不佳。
其它具有乙烯性不饱和基的化合物(B-2)
具有乙烯性不饱和基的化合物(B)还可包含其他具有乙烯性不饱和基的化合物(B-2)。
其他具有乙烯性不饱和基的化合物(B-2)可选自于具有一个乙烯性不饱和基的化合物或具有二个以上(含二个)乙烯性不饱和基的化合物。
前述具有一个乙烯性不饱和基的化合物可包含但不限于(甲基)丙烯酰胺、(甲基)丙烯酰吗啉、(甲基)丙烯酸-7-胺基-3,7-二甲基辛酯、异丁氧基甲基(甲基)丙烯酰胺、(甲基)丙烯酸异冰片基氧乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸-2-乙基己酯、乙基二乙二醇(甲基)丙烯酸酯、第三辛基(甲基)丙烯酰胺、二丙酮(甲基)丙烯酰胺、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸二环戊烯氧基乙酯、(甲基)丙烯酸二环戊烯酯、N,N-二甲基(甲基)丙烯酰胺、(甲基)丙烯酸四氯苯酯、(甲基)丙烯酸-2-四氯苯氧基乙酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸四溴苯酯、(甲基)丙烯酸-2-四溴苯氧基乙酯、(甲基)丙烯酸-2-三氯苯氧基乙酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸-2-三溴苯氧基乙酯、2-羟基-(甲基)丙烯酸乙酯、2-羟基-(甲基)丙烯酸丙酯、乙烯基己内酰胺、N-乙烯基吡咯烷酮、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸五氯苯酯、(甲基)丙烯酸五溴苯酯、聚单(甲基)丙烯酸乙二酯、聚单(甲基)丙烯酸丙二酯或(甲基)丙烯酸冰片酯等的化合物。该具有一个乙烯性不饱和基的化合物可单独一种或混合复数种使用。
前述具有二个以上(含二个)乙烯性不饱和基的化合物可包含但不限于乙二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二环戊烯酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三(2-羟基乙基)异氰酸二(甲基)丙烯酸酯、三(2-羟基乙基)异氰酸三(甲基)丙烯酸酯、己内酯改性的三(2-羟基乙基)异氰酸 三(甲基)丙烯酸酯、三(甲基)丙烯酸三羟甲基丙酯、环氧乙烷(简称EO)改性的三(甲基)丙烯酸三羟甲基丙酯、环氧丙烷改性(简称PO)的三(甲基)丙烯酸三羟甲基丙酯、三丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、聚酯二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、己内酯改性的二季戊四醇六(甲基)丙烯酸酯、己内酯改性的二季戊四醇五(甲基)丙烯酸酯、四(甲基)丙烯酸二三羟甲基丙酯、经环氧乙烷改性的双酚A二(甲基)丙烯酸酯、经环氧丙烷改性的双酚A二(甲基)丙烯酸酯、经环氧乙烷改性的氢化双酚A二(甲基)丙烯酸酯、经环氧丙烷改性的氢化双酚A二(甲基)丙烯酸酯、经环氧乙烷改性的双酚F二(甲基)丙烯酸酯或酚醛清漆聚缩水甘油醚(甲基)丙烯酸酯等的化合物。该具有二个以上(含二个)乙烯性不饱和基的化合物可单独一种使用或混合复数种使用。
该其他具有乙烯性不饱和基的化合物(B-2)的具体例，如：三丙烯酸三羟甲基丙酯、经环氧乙烷改性的三丙烯酸三羟甲基丙酯、经环氧丙烷改性的三丙烯酸三羟甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己内酯改性的二季戊四醇六丙烯酸酯、四丙烯酸二三羟甲基丙酯、经环氧丙烷改性的甘油三丙烯酸酯或上述化合物的任意组合。
基于前述的碱可溶性树脂(A)的总使用量为100重量份，具有乙烯性不饱和基的化合物(B)的使用量为15重量份至200重量份，较佳为20重量份至170重量份，更佳为25重量份至150重量份。
光起始剂(C)
光起始剂(C)包括光起始剂(C-1)以及其它光起始剂(C-2)。
光起始剂(C-1)
光起始剂(C)包括由式(1)表示的光起始剂(C-1)。
Figure PCTCN2015092009-appb-000044
其中R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、COR16、OR17、卤素、NO2、由式(2)所表示的基团或是由式(3)所表示的基团、
Figure PCTCN2015092009-appb-000045
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地为经由式(4)所表示的基团取代的C2-C10烯基、
Figure PCTCN2015092009-appb-000046
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为—(CH2)p—Y—(CH2)q—；
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团；
Figure PCTCN2015092009-appb-000047
但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团，
R9、R10、R11及R12彼此独立地为氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C1-C4-烷氧基、-(CO)OH或-(CO)O-(C1-C4烷基)；
或R9、R10、R11及R12彼此独立地为未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、CN、OR17、SR18或NR19R20；
或R9、R10、R11及R12彼此独立地为卤素、CN、OR17、SR18、SOR18、SO2R18或NR19R20，其中该等取代基OR17、SR18或NR19R20视情况经由该等基团R17、R18、R19和/或R20与萘基环中一个碳原子形成5元或6元环；
或R9、R10、R11及R12彼此独立地为COR16、NO2或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000048
Y表示O、S、NR26或直接键；
p表示0、1、2或3的整数；
q表示1、2或3的整数；
X表示CO或直接键；
R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20、NR19R20、PO(OCkH2k+1)2或是式(6)所表示的基团；
Figure PCTCN2015092009-appb-000049
或R13表示C2-C20烷基，其间杂有一或多个O、S、SO、SO2、NR26或CO，或是C2-C12烯基，其是未经间杂或间杂有一或多个O、CO或NR26，其中该经间杂的C2-C20烷基及该未经间杂或经间杂的C2-C12烯基是未经取代或经一或多个卤素取代；
或R13表示C4-C8环烯基、C2-C12炔基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C10环烷基；
或R13表示苯基或萘基，其各为未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、COR16、CN、NO2、卤素、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、S、CO或NR26的C2-C20烷基、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000050
或其各经C3-C10环烷基或间杂有一或多个O、S、CO或NR26的C3-C10环烷基取代；
k表示1至10的整数；
R14表示氢、C3-C8环烷基、C2-C5烯基、C1-C20烷氧基或C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、苯基、C1-C20烷基苯基或CN；
或R14表示苯基或萘基，其各未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基、卤素、CN、OR17、SR18和/或NR19R20；
或R14表示C3-C20杂芳基、C1-C8烷氧基、苄氧基或苯氧基，该苄氧基及苯氧基是未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基和/或卤素；R15是C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20、PO(OCkH2k+1)2、SO-C1-C10烷基、SO2-C1-C10烷基、间杂有一或多个O、S或NR26的C2-C20烷基；或其各经C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R15表示氢、C2-C12烯基、未经间杂或间杂有一或多个O、CO或NR26的C3-C8环烷基；或R15是C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OR17、SR18、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、NR19R20、COOR17、CONR19R20、PO(OCkH2k+1)2、苯基、式(6)所表示的基团或式(8)所表示的基团、
Figure PCTCN2015092009-appb-000051
或该C1-C20烷基是经苯基取代，该苯基是经卤素、C1-C20烷基、C1-C4卤代烷基、OR17、SR18或NR19R20取代；
或R15表示C2-C20烷基，其间杂有一或多个O、SO或SO2，且该经间杂的C2-C20烷基是未经取代或经一或多个以下基团取代：卤素、OR17、COOR17、CONR19R20、苯基或经OR17、SR18或NR19R20取代的苯基；
或R15表示C2-C20烷酰基或苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、苯基、OR17、SR18或NR19R20；或R15是未经取代或经一或多个OR17取代的萘甲酰基或是C3-C14杂芳基羰基；
或R15表示C2-C12烷氧基羰基，其是未经间杂或间杂有一或多个O且该经间杂或未经间杂的C2-C12烷氧基羰基是未经取代或经一或多个羟基取代；
或R15表示苯氧基羰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、C1-C4卤代烷基、苯基、OR17、SR18或NR19R20；
或R15表示CN、CONR19R20、NO2、C1-C4卤代烷基、S(O)m-C1-C6烷基、未经取代或经C1-C12烷基或SO2-C1-C6烷基取代的S(O)m-苯基；
或R15表示SO2O-苯基，其是未经取代或经C1-C12烷基取代；或是二苯基膦酰基或二-(C1-C4烷氧基)-膦酰基；
m表示1或2；
R'14具有针对R14所给出含义中的一个；
R'15具有针对R15所给出含义中的一个；
X1表示O、S、SO或SO2；
X2表示O、CO、S或直接键；
R16表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C1-C20烷基；或其各经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R16表示氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4)烷基、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基)；
或R16表示C2-C12烷基，其间杂有一或多个O、S或NR26；或R16表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8环烷基；
或R16表示经SR18取代的苯基，其中该基团R18表示键结至该COR16基团所附接的该咔唑部分的该苯基或萘基环的直接键；
n表示1至20；
R17表示氢、苯基-C1-C3烷基、C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20环烷基、SO2-(C1-C4卤代烷基)、O(C1-C4卤代烷基)或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O、S或NR26；
或R17表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷酰基、C2-C12烯基、C3-C6烯酰基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C20环烷基；
或R17表示C1-C8烷基-C3-C10环烷基，其是未经间杂或间杂有一或多个O；
或R17表示苯甲酰基，其是未经取代或经一或多个C1-C6烷基、卤素、OH或C1-C3烷氧基取代；
或R17表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或式(7)所表示的基团；
Figure PCTCN2015092009-appb-000052
或R17形成键结至该具有由式(2)所表示的基团、或是式(7)所表示的基团所处的苯基或萘基环的其中一个碳原子的直接键、
Figure PCTCN2015092009-appb-000053
R18表示氢、C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基，其中该C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基是未经间杂或间杂有一或多个O、S、CO、NR26或COOR17；或R18是C1-C20烷基，其是未经取代或经一或多个以下基团取代：OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)、O(CO)-苯基或(CO)OR17；
或R18表示C2-C20烷基，其间杂有一或多个O、S、CO、NR26或COOR17；
或R18表示(CH2CH2O)nH、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C8烷酰基或C3-C6烯酰基；
或R18表示苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、OH、C1-C4烷氧基或C1-C4烷基硫基；
或R18表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C12烷基、C1-C4卤代烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基胺基、(CO)O(C1-C8烷基)、(CO)-C1-C8烷基、(CO)N(C1-C8烷基)2或式(7)所表示的基团、
Figure PCTCN2015092009-appb-000054
R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C2-C10烷氧基烷基、C2-C5烯基、C3-C20环烷基、苯基-C1-C3烷基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基、SO2-(C1-C4卤代烷基)或苯甲酰基；
或R19及R20表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C4卤代烷基、C1-C20烷氧基、C1-C12烷基、苯甲酰基或C1-C12烷氧基；
或R19及R20与其所附接的N原子一起形成未经间杂或间杂有O、S或NR17的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C20烷氧基、＝O、OR17、 SR18、NR21R22、(CO)R23、NO2、卤素、C1-C4-卤代烷基、CN、苯基、未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000055
或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C4卤代烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、卤素、NO2、CN、苯基或未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000056
R21及R22彼此独立地为氢、C1-C20烷基、C1-C4卤代烷基、C3-C10环烷基或苯基；
或R21及R22与其所附接的N原子一起形成未经间杂或间杂有O、S或NR26的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未稠合或该5元或6元饱和或不饱和环与苯环稠合；
R23表示氢、OH、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、CO或NR26的C2-C20烷基、未经间杂或间杂有O、S、CO或NR26的C3-C20环烷基，或R23表示苯基、萘基、苯基-C1-C4烷基、OR17、SR18或NR21R22；
R24表示(CO)OR17、CONR19R20、(CO)R17；或R24具有针对R19及R20所给出含义中的一个；
R25表示COOR17、CONR19R20、(CO)R17；或R25具有针对R17所给出含义中的一个；
R26表示氢、C1-C20烷基、C1-C4卤代烷基、C2-C20烷基，其间杂有一或多个O或CO；或是苯基-C1-C4烷基、C3-C8环烷基，其是未经间杂或间杂有一或多个O或CO；或是(CO)R19；或是苯基，其是未经取代或经一或多个以下基团取代：C1-C20烷基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20或式(7)表示的基团；
Figure PCTCN2015092009-appb-000057
但条件为在该分子中存在至少一个式(2)或是式(7)所表示的基团
Figure PCTCN2015092009-appb-000058
式(1)化合物，其在咔唑部分上包含一或多个成环(annelated)不饱和环。换言之，R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中至少一对是由式(5)所表示的基团、
Figure PCTCN2015092009-appb-000059
C1-C20烷基是直链或支链且是(例如)C1-C18-、C1-C4-、C1-C12-、C1-C8-、C1-C8-或C1-C4烷基或C4-C12-或C4-C8烷基。实例是甲基、乙基、丙基、异丙基、正丁基、第二丁基、异丁基、第三丁基、戊基、己基、庚基、2,4,4-三甲基戊基、2-乙基己基、辛基、壬基、癸基、十二基、十四基、十五基、十六基、十八基及二十基。C1-C6烷基具有与上文针对C1-C20烷基所给出相同的含义且具有最高相应C原子数。
含有一或多个C-C多重键的未经取代或经取代的C1-C20烷基是指如下文所解释的烯基。
C1-C4卤代烷基是如下文所定义经卤素取代的如上文所定义C1-C4烷基。烷基基团是(例如)单-或多卤化，直至所有H-原子替换为卤素。其是(例如)CzHxHaly，其中x+y＝2z+1且Hal是卤素，较佳为F。具体实例是氯甲基、三氯甲基、三氟甲基或2-溴丙基，尤其为三氟甲基或三氯甲基。C2-C4羟基烷基意指经一或两个O原子取代的C2-C4烷基。烷基基团是直链或支链。实例是2-羟基乙基、1-羟基乙基、1-羟基丙基、2-羟基丙基、3-羟基丙基、1-羟基丁基、4-羟基丁基、2-羟基丁基、3-羟基丁基、2,3-二羟基丙基或2,4-二羟基丁基。C2-C10烷氧基烷基是间杂有一个O原子的C2-C10烷基。C2-C10烷基具有与上文针对C1-C20烷基所给出相同的含义且具有最高相应C原子数。实例是甲氧基甲基、甲氧基乙基、甲氧基丙基、乙氧基甲基、乙氧基乙基、乙氧 基丙基、丙氧基甲基、丙氧基乙基、丙氧基丙基。
间杂有一或多个O、S、NR26或CO的C2-C20烷基经O、S、NR26或CO间杂(例如)1至9次、1至5次、1至3次或1次或2次。若存在一个以上间杂基团，则其为相同种类或不同。两个O原子由至少一个亚甲基、较佳至少两个亚甲基(即亚乙基)隔开。该等烷基是直链或支链。举例而言，将存在以下结构单元：-CH2-CH2-O-CH2CH3、-[CH2CH2O]y-CH3(其中y＝l至9)、-(CH2-CH2O)7-CH2CH3、-CH2-CH(CH3)-O-CH2-CH2CH3、-CH2-CH(CH3)-O-CH2-CH3、-CH2-CH2-S-CH2CH3、-CH2-CH(CH3)-NW26-CH2-CH3、-CH2-CH2-COO-CH2CH3或-CH2-CH(CH3)-OCO-CH2-CH2CH3。
C3-C10环烷基、C3-C10环烷基及C3-C8环烷基在本申请上下文中应理解为至少包含一个环的烷基。其是(例如)环丙基、环丁基、环戊基、环己基、环辛基、戊基环戊基及环己基。C3-C10环烷基在本发明上下文中也意欲涵盖二环，换言之，桥联环，例如
Figure PCTCN2015092009-appb-000060
以及相对应的环。其他实例是诸如
Figure PCTCN2015092009-appb-000061
Figure PCTCN2015092009-appb-000062
(例如
Figure PCTCN2015092009-appb-000063
)或是
Figure PCTCN2015092009-appb-000064
等结构、以及侨联或稠合环系统，举例而言，该术语也意欲涵盖:
Figure PCTCN2015092009-appb-000065
等结构。
间杂有O、S、CO、NR26的C3-C20环烷基具有上文给出的含义，其中烷基中至少一个CH2-基团替换为O、S、CO或NR26。实例是诸如
Figure PCTCN2015092009-appb-000066
(例如
Figure PCTCN2015092009-appb-000067
)、
Figure PCTCN2015092009-appb-000068
Figure PCTCN2015092009-appb-000069
Figure PCTCN2015092009-appb-000070
等结构。
C1-C8烷基-C3-C10环烷基是经一或多个具有最多8个碳原子的烷基取代的如上文所定义的C3-C10环烷基。实例是:
Figure PCTCN2015092009-appb-000071
等。
间杂有一或多个O的C1-C8烷基-C3-C10环烷基是经一或多个具有最多8个碳原子的烷基取代的如上文所定义的O间杂C3-C10环烷基。实例是:
Figure PCTCN2015092009-appb-000072
等。
C1-C12烷氧基是经一个O原子取代的C1-C12烷基。C1-C12烷基具有与上文针对C1-C20烷基所给出相同的含义且具有最高相应C原子数。C1-C4烷氧基是直链或支链，例如甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、第二 丁氧基、异丁氧基或第三丁氧基。C1-C8烷氧基及C1-C4-烷氧基具有与上文所述相同的含义且具有最高相应C原子数。
C1-C12烷基硫基是经一个S原子取代的C1-C12烷基。C1-C20烷基具有与上文针对C1-C20烷基所给出相同的含义且具有最高相应C原子数。C1-C4烷基硫基是直链或支链，例如甲基硫基、乙基硫基、丙基硫基、异丙基硫基、正丁基硫基、第二丁基硫基、异丁基硫基、第三丁基硫基。
苯基-C1-C3烷基是(例如)苄基、苯基乙基、α-甲基苄基或α,α-二甲基-苄基，尤其为苄基。
苯基-C1-C3烷氧基是(例如)苄氧基、苯基乙氧基、α-甲基苄氧基或α,α-二甲基苄氧基，尤其为苄氧基。
C2-C12烯基是单-或多不饱和且是(例如)C2-C10-、C2-C8-、C2-C5-烯基，例如乙烯基、烯丙基、甲基烯丙基、1,1-二甲基烯丙基、1-丁烯基、3-丁烯基、2-丁烯基、1,3-戊二烯基、5-己烯基、7-辛烯基或十二烯基，尤其为烯丙基。C2-C5烯基具有与上文针对C2-C12烯基所给出相同的含义且具有最高相应C原子数。
间杂有一或多个O、CO或NR26的C2-C12烯基经O、S、NR26或CO间杂(例如)1至9次、1至5次、1至3次或1次或2次。若存在一个以上间杂基团，则其为相同种类或不同。两个O原子由至少一个亚甲基、较佳至少两个亚甲基(即亚乙基)隔开。烯基是直链或支链且如上文所定义。举例而言，可形成以下结构单元:-CH＝CH-O-CH2CH3、-CH＝CH-O-CH＝CH2等。
C4-C8环烯基具有一或多个双键且是(例如)C4-C6-环烯基或C6-C8-环烯基。实例是环丁烯基、环戊烯基、环己烯基或环辛烯基，尤其为环戊烯基及环己烯基，较佳为环己烯基。
C3-C6烯氧基是单或多不饱和且具有上文针对烯基所给出含义中的一个，且附接氧基具有最高相应C原子数。实例是烯丙氧基、甲基烯丙氧基、丁烯氧基、戊烯氧基、1,3-戊二烯氧基、5-己烯氧基。
C2-C12炔基是单或多不饱和直链或支链且是(例如)C2-C8-、C2-C6-或C2-C4炔基。实例是乙炔基、丙炔基、丁炔基、1-丁炔基、3-丁炔基、2-丁炔基、戊炔基己炔基、2-己炔基、5-己炔基、辛炔基等。
C2-C20烷酰基是直链或支链且是(例如)C2-C18-、C2-C14-、C2-C12-、C2-C8-、 C2-C6-或C2-C4烷酰基或C4-C12-或C4-C8烷酰基。实例是乙酰基、丙酰基、丁酰基、异丁酰基、戊酰基、己酰基、庚酰基、辛酰基、壬酰基、癸酰基、十二酰基、十四酰基、十五酰基、十六酰基、十八酰基、二十酰基，较佳为乙酰基。C1-C8烷酰基具有与上文针对C2-C20烷酰基所给出相同的含义且具有最高相应C原子数。
C2-C12烷氧基羰基是直链或支链且是(例如)甲氧基羰基、乙氧基羰基、丙氧基羰基、正丁氧基羰基、异丁氧基羰基、1,1-二甲基丙氧基羰基、戊氧基羰基、己氧基羰基、庚氧基羰基、辛氧基羰基、壬氧基羰基、癸氧基羰基或十二氧基羰基，尤其为甲氧基羰基、乙氧基羰基、丙氧基羰基、正丁氧基羰基或异丁氧基羰基，较佳为甲氧基羰基。
间杂有一或多个O的C2-C12烷氧基羰基是直链或支链。两个O原子由至少两个亚甲基(即亚乙基)隔开。该经间杂的烷氧基羰基未经取代或经一或多个羟基取代。C6-C20芳氧基羰基是(例如)苯基氧基羰基[＝苯基-O-(CO)-]、萘氧基羰基、蒽氧基羰基等。C5-C20杂芳氧基羰基是C5-C20杂芳基-O-CO-。
C3-C10环烷基羰基是C3-C10环烷基-CO-，其中环烷基具有上文所示含义中的一个且具有最高相应C原子数。间杂有一或多个O、S、CO、NR26的C3-C10环烷基羰基是指经间杂环烷基-CO-，其中经间杂环烷基是如上文所述所定义。
C3-C10环烷氧基羰基是C3-C10环烷基-O-(CO)-，其中环烷基具有上文所示含义中的一个且具有最高相应C原子数。间杂有一或多个O、S、CO、NR26的C3-C10环烷氧基羰基是指经间杂环烷基-O-(CO)-，其中经间杂环烷基是如上文所述所定义。
C1-C20烷基苯基是指经一或多个烷基取代的苯基，其中C原子的总和最多为20。
C6-C20芳基是(例如)苯基、萘基、蒽基、菲基、芘基、屈基、并四苯基、联亚三苯基等，尤其为苯基或萘基，较佳为苯基。萘基是1-萘基或2-萘基。
在本发明上下文中，C3-C20杂芳基意欲包含单环或多环系统，例如稠合环系统。实例是噻吩基、苯并[b]噻吩基、萘并[2,3-b]噻吩基、噻蒽基、呋喃基、二苯并呋喃基、呫吨基、噻吨基、啡恶噻基、吡咯基、咪唑基、吡唑基、吡嗪基、嘧啶基、哒嗪基、中氮茚基、异吲哚基、吲哚基、吲唑基、嘌呤基、喹嗪基、异喹啉基、喹啉基、酞嗪基、萘啶基、喹恶啉基、喹唑啉基、噌啉 基、喋啶基、咔唑基、β-咔啉基、菲啶基、吖啶基、萘嵌间二氮苯基、菲咯啉基、吩噻基、异噻唑基、吩噻嗪基、异恶唑基、呋呫基、吩恶基、7-菲基、蒽醌-2-基(＝9,10-二侧氧基-9,10-二氢蒽-2-基)、3-苯并[b]噻吩基、5-苯并[b]噻吩基、2-苯并[b]噻吩基、4-二苯并呋喃基、4,7-二苯并呋喃基、4-甲基-7-二苯并呋喃基、2-呫吨基、8-甲基-2-呫吨基、3-呫吨基、2-啡恶噻基、2,7-啡恶噻基、2-吡咯基、3-吡咯基、5-甲基-3-吡咯基、2-咪唑基、4-咪唑基、5-咪唑基、2-甲基-4-咪唑基、2-乙基-4-咪唑基、2-乙基-5-咪唑基、1H-四唑-5-基、3-吡唑基、1-甲基-3-吡唑基、1-丙基-4-吡唑基、2-吡嗪基、5,6-二甲基-2-吡嗪基、2-中氮茚基、2-甲基-3-异吲哚基、2-甲基-1-异吲哚基、1-甲基-2-吲哚基、1-甲基-3-吲哚基、1,5-二甲基-2-吲哚基、1-甲基-3-吲唑基、2,7-二甲基-8-嘌呤基、2-甲氧基-7-甲基-8-嘌呤基、2-喹嗪基、3-异喹啉基、6-异喹啉基、7-异喹啉基、3-甲氧基-6-异喹啉基、2-喹啉基、6-喹啉基、7-喹啉基、2-甲氧基-3-喹啉基、2-甲氧基-6-喹啉基、6-酞嗪基、7-酞嗪基、1-甲氧基-6-酞嗪基、1,4-二甲氧基-6-酞嗪基、1,8-萘啶-2-基、2-喹恶啉基、6-喹恶啉基、2,3-二甲基-6-喹恶啉基、2,3-二甲氧基-6-喹恶啉基、2-喹唑啉基、7-喹唑啉基、2-二甲基胺基-6-喹唑啉基、3-噌啉基、6-噌啉基、7-噌啉基、3-甲氧基-7-噌啉基、2-喋啶基、6-喋啶基、7-喋啶基、6,7-二甲氧基-2-喋啶基、2-咔唑基、3-咔唑基、9-甲基-2-咔唑基、9-甲基-3-咔唑基、β-咔啉-3-基、1-甲基-β-咔啉-3-基、1-甲基-β-咔啉-6-基、3-菲啶基、2-吖啶基、3-吖啶基、2-萘嵌间二氮苯基、1-甲基-5-萘嵌间二氮苯基、5-菲咯啉基、6-菲咯啉基、1-吩嗪基、2-吩嗪基、3-异噻唑基、4-异噻唑基、5-异噻唑基、2-吩噻嗪基、3-吩噻嗪基、10-甲基-3-吩噻嗪基、3-异恶唑基、4-异恶唑基、5-异恶唑基、4-甲基-3-呋呫基、2-吩恶基、10-甲基-2-吩恶基等。
C3-C20杂芳基尤其为噻吩基、苯并[b]噻吩基、噻蒽基、噻吨基、1-甲基-2-吲哚基或1-甲基-3-吲哚基；尤其为噻吩基。
C4-C20杂芳基羰基是经由CO基团连接至分子其余部分的如上文所定义C3-C20杂芳基。
经取代的芳基(苯基、萘基、C6-C20芳基或C5-C20杂芳基)是分别经1至7次、1至6次或1至4次、尤其1次、2次或3次取代。显而易见，所定义芳基不能具有比芳基环处的自由位置为多的取代基。
苯基环上的取代基较佳在苯基环上的位置4中或呈3,4-、3,4,5-、2,6-、2,4-或2,4,6-组态。
间杂1次或多次的经间杂基团间杂(例如)1至19次、1至15次、1至12次、1至9次、1至7次、1至5次、1至4次、1至3次或1次或2次(显而易见，间杂原子数取决于拟间杂的C原子数)。经1次或多次取代的经取代基团具有(例如)1至7个、1至5个、1至4个、1至3个或1个或2个相同或不同取代基。
经一或多个所定义取代基取代的基团意欲具有一个取代基或多个如所给出相同或不同定义的取代基。卤素是氟、氯、溴及碘，尤其为氟、氯及溴，较佳为氟及氯。若R1及R2、R2及R3、R3及R4或R5及R6、R6及R7、R7及R8彼此独立地共同为由式(5)所表示的基团、
Figure PCTCN2015092009-appb-000073
则形成例如以下(Ia)-(Ii)结构:
Figure PCTCN2015092009-appb-000074
Figure PCTCN2015092009-appb-000075
较佳为结构(Ia)。
式(1)化合物，其至少一个苯基环与咔唑部分稠合以形成“萘基环”。即上述结构中的一个是以式(1)给出。
若R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为-(CH2)P-Y-(CH2)q-，则形成(例如)诸如:
Figure PCTCN2015092009-appb-000076
等结构。
若苯基或萘基环上的取代基OR17、SR18、SOR18、SO2R18或NR19R20经由基团R17、R18、R19和/或R20与萘基环的一个碳原子形成5元或6元环，则获得包含3个或更多个环(包括萘基环)的结构。实例是:
Figure PCTCN2015092009-appb-000077
Figure PCTCN2015092009-appb-000078
等结构。
若R17形成键结至其上具有基团
Figure PCTCN2015092009-appb-000079
的苯基或萘基环的一个碳原子的直接键，则形成例如诸如
Figure PCTCN2015092009-appb-000080
结构。
若R16表示经SR18取代的苯基，其中基团R19表示键结至其中附接有COR16基团的咔唑部分的苯基或萘基环的直接键，则形成(例如)诸如
Figure PCTCN2015092009-appb-000081
等结构。即，若R16是经SR18取代的苯基，其中基团R18表示键结至其中附接有COR16基团的咔唑部分的苯基或萘基环的直接键，则噻吨基部分与咔唑部分的一个苯基或萘基环一起形成。
若R19及R20与其所附接的N原子一起形成视情况间杂有O、S或NR17的5元或6元饱和或不饱和环，则形成饱和或不饱和环，例如氮丙啶、吡咯、噻唑、吡咯啶、恶唑、吡啶、1,3-二嗪、1,2-二嗪、六氢吡啶或吗啉。较佳地，若R19及R20与其所附接的N原子一起形成视情况间杂有O、S或NR17的5元或6元饱和或不饱和环，则形成未经间杂或间杂有O或NR17、尤其O的5元或6元饱和环。
若R21及R22与其所附接的N原子一起形成视情况间杂有O、S或NR26的5元或6元饱和或不饱和环，且苯环视情况与该饱和或不饱和环稠合，则形成饱和或不饱和环，例如氮丙啶、吡咯、噻唑、吡咯啶、恶唑、吡啶、1,3-二嗪、1,2-二嗪、六氢吡啶或吗啉或相应成环，例如
Figure PCTCN2015092009-appb-000082
等。
若R19及R20与其所附接的N原子一起形成杂芳香族环系统，则该环系统意欲包含一个以上环(例如2个或3个环)以及来自相同种类或不同种类的一个或一个以上杂原子。适宜杂原子是(例如)N、S、O或P、尤其N、S或O。实例是咔唑、吲哚、异吲哚、吲唑、嘌呤、异喹啉、喹啉、咔啉、吩噻嗪等。
术语“和/或”或“或/和”在本发明上下文中意欲表达不仅可存在所定义替代物(取代基)中的一个，而且可存在总共若干所定义替代物(取代基)，即不同替代物(取代基)的混合物。
术语“至少”意欲定义一个或一个以上，例如一个或两个或三个、较佳一个或两个。
术语“视情况经取代”意指其提及的基团未经取代或经取代。
术语“视情况经间杂”意指其提及的基团未经杂或经间杂。
在整个本说明书及下文的权利要求中，除非上下文另有要求，否则词语“包含(comprise)”或变体(例如，“comprises”或“comprising”)应理解为暗指包括所述整数或步骤或整数群组或步骤群组，但并不排除任一其他整数或步骤或整数群组或步骤群组。术语“(甲基)丙烯酸酯”在本申请上下文中意欲指丙烯酸酯以及相应甲基丙烯酸酯。
式(1)肟酯是通过文献中所述方法来制备，例如通过在以下条件下使相应肟与酰卤、尤其氯化物或酸酐反应：在惰性溶剂(例如第三丁基甲基醚、四氢呋喃(THF)或二甲基甲酰胺)中，在碱(例如三乙胺或吡啶)存在时，或在碱性溶剂(例如吡啶)中。在下文中作为实例，阐述式Ia化合物的制备，其中R7表示肟酯基团且X表示直接键[自适当肟开始实施化合物(Ib)-(Ih)的反应]：
Figure PCTCN2015092009-appb-000083
R1、R2、R5、R6、R8、R13、R14及R15是如上文所定义，Hal意指卤素原子、尤其为Cl。
R14较佳为甲基。
此等反应为彼等熟习此项技术者所熟知，且通常在-15℃至+50℃、较佳0至25℃的温度下实施。
当X表示CO时，相应肟是通过用亚硝酸烷基酯(例如亚硝酸甲酯、亚硝酸乙酯、亚硝酸丙酯、亚硝酸丁酯或亚硝酸异戊酯)将亚甲基亚硝化来合成。然后，酯化是在与上文所述相同的条件下实施：
Figure PCTCN2015092009-appb-000084
因此，本发明的标的也是通过在碱或碱的混合物存在下使相应肟化合物与式VI的酰卤或式VII的酸酐反应来制备如上文所定义式(1)化合物的方法。
Figure PCTCN2015092009-appb-000085
其中Hal是卤素、尤其C1，且R14是如上文所定义。
所需作为起始材料的肟可通过标准化学教材(例如J.March,Advanced Organic Chemistry，第4版，Wiley Interscience，1992)或专著(例如S.R.Sandler&W.Karo,Organic functional group preparations，第3卷，Academic Press)中所述多种方法来获得。
最便利的一种方法是(例如)在极性溶剂(例如二甲基乙酰胺(DMA)、DMA水溶液、乙醇或乙醇水溶液)中使醛或酮与羟胺或其盐反应。在此情形下，添 加诸如乙酸钠或吡啶等碱来控制反应混合物的pH。众所周知，反应速度具有pH依赖性，且可在开始时或在反应期间连续地添加碱。也可使用诸如吡啶等碱性溶剂作为碱和/或溶剂或共溶剂。反应温度通常为室温至混合物的回流温度，一般为约20℃至120℃。
相应酮中间体是(例如)通过文献(例如标准化学教材，例如J.March,Advanced Organic Chemistry，第4版，Wiley Interscience，1992)中所述方法来制备。另外，连续弗里德-克拉夫茨反应(Friedel-Crafts reaction)可有效用于合成中间体。此等反应为彼等熟习此项技术者所熟知。
肟的另一便利合成是用亚硝酸或亚硝酸烷基酯将“活性”亚甲基亚硝化。碱性条件(如(例如)Organic Syntheses coll.第VI卷(J.Wiley&Sons,New York,1988)，第199页及第840页中所述)与酸性条件(如(例如)Organic Synthesis coll.第V卷，第32页及第373页，coll.第III卷，第191页及第513页，coll.第II卷，第202页、第204页及第363页中所述)两种适于制备在本发明中用作起始材料的肟。一般自亚硝酸钠产生亚硝酸。亚硝酸烷基酯可为(例如)亚硝酸甲酯、亚硝酸乙酯、亚硝酸丙酯、亚硝酸丁酯或亚硝酸异戊酯。
本发明另一实施例是游离式(1A)肟化合物
Figure PCTCN2015092009-appb-000086
其中其中R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、
Figure PCTCN2015092009-appb-000087
OR17、卤素、NO2或是由式(3)所表示的基团、
Figure PCTCN2015092009-appb-000088
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地为经
Figure PCTCN2015092009-appb-000089
取代的C2-C10烯基；
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为—(CH2)p—Y—(CH2)q—；
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000090
但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团、
Figure PCTCN2015092009-appb-000091
R9、R10、R11及R12彼此独立地为氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C1-C4-烷氧基、-(CO)OH或-(CO)O-(C1-C4烷基)；
或R9、R10、R11及R12彼此独立地为未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、CN、OR17、SR18或NR19R20；
或R9、R10、R11及R12彼此独立地为卤素、CN、OR17、SR18、SOR18、SO2R18或NR19R20，其中该等取代基OR17、SR18或NR19R20视情况经由该等基团R17、R18、R19和/或R20与萘基环中一个碳原子形成5元或6元环；
或R9、R10、R11及R12彼此独立地为
Figure PCTCN2015092009-appb-000092
COR16或NO2；
Y表示O、S、NR26或直接键；
p表示0、1、2或3的整数；
q表示1、2或3的整数；
X表示CO或直接键；
R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20、NR19R20、PO(OCkH2k+1)2或是式(6)所表示的基团、
Figure PCTCN2015092009-appb-000093
或R13表示C2-C20烷基，其间杂有一或多个O、S、SO、SO2、NR26或CO，或是C2-C12烯基，其是未经间杂或间杂有一或多个O、CO或NR26，其中该经间杂的C2-C20烷基及该未经间杂或经间杂的C2-C12烯基是未经取代或经一或多个卤素取代；
或R13表示C4-C8环烯基、C2-C12炔基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C10环烷基；
或R13表示苯基或萘基，其各为未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、
Figure PCTCN2015092009-appb-000094
COR16、CN、NO2、卤素、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、S、CO或NR26的C2-C20烷基；或其各经C3-C10环烷基或间杂有一或多个O、S、CO或NR26的C3-C10环烷基取代；
k表示1至10的整数；
R15表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20、 PO(OCkH2k+1)2、SO-C1-C10烷基、SO2-C1-C10烷基、间杂有一或多个O、S或NR26的C2-C20烷基；或其各经C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R15表示氢、C2-C12烯基、C3-C8环烷基，基未经间杂或间杂有一或多个O、CO或NR26；
或R15表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OR17、SR18、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、NR19R20、COOR17、CONR19R20、PO(OCkH2k+1)2、苯基、
Figure PCTCN2015092009-appb-000095
或式(6)所表示的基团
Figure PCTCN2015092009-appb-000096
或该C1-C20烷基是经苯基取代，该苯基是经卤素、C1-C20烷基、C1-C4卤代烷基、OR17、SR18或NR19R20取代；
或R15表示C2-C20烷基，其间杂有一或多个O、SO或SO2，且该经间杂的C2-C20烷基是未经取代或经一或多个以下基团取代：卤素、OR17、COOR17、CONR19R20、苯基或经OR17、SR18或NR19R20取代的苯基；
或R15表示C2-C20烷酰基或苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、苯基、OR17、SR18或NR19R20；
或R15表示未经取代或经一或多个OR17取代的萘甲酰基或是C3-C14杂芳基羰基；
或R15表示C2-C12烷氧基羰基，其是未经间杂或间杂有一或多个O且该经间杂或未经间杂的C2-C12烷氧基羰基是未经取代或经一或多个羟基取代；
或R15表示苯氧基羰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、C1-C4卤代烷基、苯基、OR17、SR18或NR19R20；
或R15表示CN、CONR19R20、NO2、C1-C4卤代烷基、S(O)m-C1-C6烷基、未经取代或经C1-C12烷基或SO2-C1-C6烷基取代的S(O)m-苯基；
或R15表示SO2O-苯基，其是未经取代或经C1-C12烷基取代；或是二苯基 膦酰基或二-(C1-C4烷氧基)-膦酰基；
m表示1或2；
R'15具有针对R15所给出含义中的一个；
X1表示O、S、SO或SO2；
X2表示O、CO、S或直接键；
R16表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C1-C20烷基；或其各经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R16表示氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4)烷基、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基)；
或R16表示C2-C12烷基，其间杂有一或多个O、S或NR26；或R16表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8环烷基；
或R16表示经SR18取代的苯基，其中该基团R18表示键结至该COR16基团所附接的该咔唑部分的该苯基或萘基环的直接键；
n表示1至20；
R17表示氢、苯基-C1-C3烷基、C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20环烷基、SO2-(C1-C4卤代烷基)、O(C1-C4卤代烷基)或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O、S或NR26；
或R17表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷酰基、C2-C12烯基、C3-C6烯酰基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C20环烷基；
或R17表示C1-C8烷基-C3-C10环烷基，其是未经间杂或间杂有一或多个O；
或R17表示苯甲酰基，其是未经取代或经一或多个C1-C6烷基、卤素、OH或C1-C3烷氧基取代；
或R17表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或
Figure PCTCN2015092009-appb-000097
或R17形成键结至其上具有基团、
Figure PCTCN2015092009-appb-000098
的苯基或萘基环的其中一个碳原子的直接键；
R18表示氢、C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基，其中该C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基是未经间杂或间杂有一或多个O、S、CO、NR26或COOR17；或R18是C1-C20烷基，其是未经取代或经一或多个以下基团取代：OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)、O(CO)-苯基或(CO)OR17；
或R18表示C2-C20烷基，其间杂有一或多个O、S、CO、NR26或COOR17；
或R18表示(CH2CH2O)nH、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C8烷酰基或C3-C6烯酰基；
或R18表示苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、OH、C1-C4烷氧基或C1-C4烷基硫基；
或R18表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C12烷基、C1-C4卤代烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基胺基、(CO)O(C1-C8烷基)、(CO)-C1-C8烷基、(CO)N(C1-C8烷基)2或
Figure PCTCN2015092009-appb-000099
R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C2-C10烷氧基烷基、C2-C5烯基、C3-C20环烷基、苯基-C1-C3烷基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基、SO2-(C1-C4卤代烷基)或苯甲酰基；
或R19及R20表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C4卤代烷基、C1-C20烷氧基、C1-C12烷基、苯甲酰基或C1-C12烷氧基；
或R19及R20与其所附接的N原子一起形成未经间杂或间杂有O、S或NR17的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、NO2、卤素、C1-C4-卤代烷基、CN、苯基、
Figure PCTCN2015092009-appb-000100
或未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基；
或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C4卤代烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、
Figure PCTCN2015092009-appb-000101
卤素、NO2、CN、苯基或未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基；
R21及R22彼此独立地为氢、C1-C20烷基、C1-C4卤代烷基、C3-C10环烷基或苯基；
或R21及R22与其所附接的N原子一起形成未经间杂或间杂有O、S或NR26的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未稠合或该5元或6元饱和或不饱和环与苯环稠合；
R23表示氢、OH、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、CO或NR26的C2-C20烷基、未经间杂或间杂有O、S、CO或NR26的C3-C20环烷基；
或R23表示苯基、萘基、苯基-C1-C4烷基、OR17、SR18或NR21R22；
R24表示(CO)OR17、CONR19R20、(CO)R17；或R24具有针对R19及R20所给出含义中的一个；
R25表示COOR17、CONR19R20、(CO)R17；或R25具有针对R17所给出含义中的一个；
R26表示氢、C1-C20烷基、C1-C4卤代烷基、C2-C20烷基，其间杂有一或多个O或CO；或是苯基-C1-C4烷基、C3-C8环烷基，其是未经间杂或间杂有一或多个O或CO；或是(CO)R19；或是苯基，其是未经取代或经一或多个以下基团取代：C1-C20烷基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20、
Figure PCTCN2015092009-appb-000102
但条件为在该分子中存在至少一个基团
Figure PCTCN2015092009-appb-000103
针对式(1A)化合物所定义基团的较佳的对应于如针对如上文所给出式(1)化合物给出的，只是每一所定义肟酯基团(例如
Figure PCTCN2015092009-appb-000104
)皆替换为相应游离肟基团
Figure PCTCN2015092009-appb-000105
每一肟酯基团可以两种构型(Z)或(E)存在。可通过现有方法来分离异构体，但也可使用异构体混合物作为(例如)光起始物质。因此，本发明也是关于式(1)化合物的构型异构体的混合物。
较佳的是如上文所定义的式(1)化合物，其中R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、COR16、NO2或式(2)所表示的基团
Figure PCTCN2015092009-appb-000106
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团
Figure PCTCN2015092009-appb-000107
但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团
Figure PCTCN2015092009-appb-000108
X表示CO或直接键；
R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20、NR19R20、PO(OCkH2k+1)2；
或R13表示C2-C20烷基，其间杂有一或多个O、S、SO、SO2、NR26或CO；
或R13表示苯基或萘基，此两个未经取代或经一或多个COR16或
Figure PCTCN2015092009-appb-000109
所取代；
R14表示C1-C20烷基、苯基或C1-C8烷氧基；
R15表示苯基、萘基、C3-C20杂芳基，其各未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、OR17、SR18或C2-C20烷基，其间杂有一或多个O或S；或其各经一或多个C1-C20烷基取代，该C1-C20烷基未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C4-C20杂芳氧基羰基、OR17、SR18、NR19R20或PO(OCkH2k+1)2；
或R15表示C1-C20烷基，其未经取代或经一或多个以下基团取代：OR17、SR18、C3-C8环烷基、C3-C20杂芳基、NR19R20、COOR17、CONR19R20或PO(OCkH2k+1)2；
R'14具有针对R14所给出含义中的一个；
R'15具有针对R15所给出含义中的一个；
R16表示苯基，其未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C2-C20烷基，
或R16表示苯基，其经一或多个C1-C20烷基取代，该C1-C20烷基未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C4-C20杂芳氧基羰基、OR17、SR18或NR19R20；
或R16表示C1-C20烷基，其未经取代或经以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)或(CO)O(C1-C4烷基)；
R17表示C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、OCH2CH2(CO)O(C1-C4烷基)、O(C1-C4烷基)、(CO)O(C1-C4烷基)、C3-C20环烷基或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O；
R18表示经(CO)OR17取代的甲基；
R19及R20彼此独立地为氢、苯基、C1-C20烷基、C1-C8烷酰基或C1-C8烷酰基氧基；
或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统未经取代或经
Figure PCTCN2015092009-appb-000110
取代；但条件为在该分子中存在至少一个式(2)所表示的基团或是式(7)所表示的基团、
Figure PCTCN2015092009-appb-000111
必须重视如上文所定义的式(1)化合物，其中R1、R2、R5、R6、R7及R8彼此独立地为氢、COR16NO2或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000112
R3及R4一起为式(5)所表示的基团
Figure PCTCN2015092009-appb-000113
R9、R10、R11及R12表示氢
X表示直接键；
R13表示C1-C20烷基；
R14表示C1-C20烷基；
R15表示C1-C20烷基或苯基，其经一或多个OR17或C1-C20烷基取代；
R16表示苯基，其经一或多个C1-C20烷基或OR17取代；且
R17表示未经取代或经一或多个卤素取代的C1-C20烷基或是间杂有一或多个O的C2-C20烷基。
但条件为在该分子中存在至少一个由式(2)所表示的基团
Figure PCTCN2015092009-appb-000114
本发明的标的进一步是如上文所定义的式(1)化合物，其中R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢，
或R1及R2、R3及R4或R5及R6彼此独立地共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000115
但条件为R1及R2、R3及R4或R5及R6中至少一对为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000116
或R2为式(2)所表示的基团、COR16、NO2或是由式(3)所表示的基团、
Figure PCTCN2015092009-appb-000117
或R7为COR16或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000118
R9、R11及R12表示氢；
R10表示氢、OR17或COR16；
X表示CO或直接键；
R13表示C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、R17、OR17、SR18或PO(OCkH2k+1)2；
或R13表示C2-C20烷基，其间杂有一或多个O；
或R13表示苯基；
k表示2的整数；
R14表示C1-C20烷基或噻吩基；
R15表示苯基或萘基，其各未经取代或经一或多个OR17或C1-C20烷基取代；
或R15表示噻吩基、氢、C1-C20烷基，该C1-C20烷基未经取代或经一或多个以下基团取代：OR17、SR18、C3-C8环烷基、NR19R20或COOR17；
或R15表示C2-C20烷基，其间杂有SO2；
R16表示苯基或萘基，其各未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或C1-C20烷基；或R16表示噻吩基；
R17表示氢、C1-C8烷酰基、C1-C20烷基，其未经取代或经一或多个以下基团：卤素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基或间杂有一或多个O的C3-C20环烷基；
或R17表示C2-C20烷基，其间杂有一或多个O；
R18表示C3-C20环烷基、C1-C20烷基，其未经取代或经一或多个OH、O(CO)-(C2-C4)烯基或(CO)OR17取代；
或R18表示苯基，其未经取代或经一或多个卤素取代；
R19及R20彼此独立地为C1-C8烷酰基或C1-C8烷酰基氧基；
或R19及R20与其所附接的N原子一起形成间杂有O的5元或6元饱和环；
但条件为在该分子中存在至少一个式(2)所表示的基团
Figure PCTCN2015092009-appb-000119
本发明化合物的实例是如上文所定义的式(Ia)-(Ig)化合物。式(Ia)、(Ib)、(Ic)、尤其式(Ia)或(Ic)、或式(Ia)、(Ic)或(Id)、尤其式(Ia)的化合物令人关注。
举例而言，R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、COR16、由式(2)所表示的基团、或R1及R2、R2及R3、R3及R4或R5及R6、R6及R7、R7及R8彼此独立地共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000120
Figure PCTCN2015092009-appb-000121
举例而言，R3及R4或R1及R2共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000122
或R3及R4及R5及R6共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000123
R3及R4尤其共同为式(5)所表示的基团、
Figure PCTCN2015092009-appb-000124
Figure PCTCN2015092009-appb-000125
举例而言，R1、R5、R6及R8表示氢。
R7尤其为氢COR16或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000126
或R7为COR16或式(2)所表示的基团，尤其为式(2)所表示的基团、
Figure PCTCN2015092009-appb-000127
R2尤其为COR16、式(2)所表示的基团或是由式(3)所表示的基团、
Figure PCTCN2015092009-appb-000128
Figure PCTCN2015092009-appb-000129
或R2与R1一起为式(5)所表示的基团
Figure PCTCN2015092009-appb-000130
X较佳为直接键。
举例而言，R9、R10、R11及R12彼此独立地为氢、C1-C20烷基、未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、OR17或SR18；或R9、R10、R11及R12彼此独立地为卤素、OR17、SR18或NR19R20，其中取代基OR17、SR18或NR19R20视情况经由基团R17、R18、R19和/或R20与萘基环的一个碳原子形成5元或6元环；或R9、R10、R11及R12彼此独立地为COR16或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000131
具体而言，R9、R10、R11及R12彼此独立地为氢、C1-C20烷基、未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、OR17或SR18；或R9、R10、R11及R12彼此独立地为卤素、OR17、SR18或NR19R20；或R9、R10、R11及R12彼此独立地为COR16或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000132
举例而言，R9、R10、R11及R12彼此独立地为氢、C1-C20烷基、未经取代的苯基或经一或多个C1-C6烷基取代的苯基；或R9、R10、R11及R12彼此独立地为COR16或式(2)所表示的基团、
Figure PCTCN2015092009-appb-000133
在另一实施例中，举例而言，R9、R10、R11及R12彼此独立地为氢、C1-C20烷基、未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、OR17或SR18；或R9、R10、R11及R12彼此独立地为卤素、OR17、SR18或NR19R20，其中取代基OR17、SR18或NR19R20视情况经由基团R17、R18、R19和/或R20与萘基环的一个碳原子形成5元或6元环。
此外，举例而言，R9、R10、R11及R12彼此独立地为氢、C1-C20烷基、未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、OR17或SR18，或R9、R10、R11及R12彼此独立地为卤素、OR17、SR18、NR19R20或COR16。
或举例而言，R9、R10、R11及R12彼此独立地为氢、C1-C20烷基、未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、OR17或SR18，或R9、R10、R11及R12彼此独立地为卤素、OR17、COR16或NR19R20。
较佳地，R9、R11及R12表示氢且R10表示氢、OR17或COR16。
R13表示(例如)C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、COOR17或CONR19R20；或R13表示C2-C20烷基，其间杂有一或多个O、S、SO、SO2、NR26或CO，或是C2-C12烯基，其视情况间杂有一或多个O、CO或NR26，或R13表示C3-C10环烷基，其视情况间杂有一或多个O、S、CO、NR26，或R13表示苯基或萘基，此两种未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、COR16、NO2、卤素、C1-C20烷基、C1-C4卤代烷基、 C2-C20烷基，其间杂有一或多个O、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000134
或是C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20或PO(OCkH2k+1)2；或是C2-C20烷基，其间杂有一或多个O。
此外，R13表示(例如)C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20或PO(OCkH2k+1)2；或是C2-C20烷基，其间杂有一或多个O；或是C2-C12烯基、C3-C10环烷基；或R13表示苯基或萘基，此两种未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、COR16、NO2、卤素、C1-C20烷基、C1-C4卤代烷基、C2-C20烷基，其间杂有一或多个O、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000135
在另一实施例中，R13表示(例如)C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、R17、OR17、SR18或PO(OCkH2k+1)2；或是C2-C20烷基，其间杂有一或多个O；或是C2-C12烯基、C3-C10环烷基、苯基或萘基。
或R13表示(例如)C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、R17、OR17、SR18或PO(OCkH2k+1)2；或是C2-C20烷基，其间杂有一或多个O；或是苯基、C2-C12烯基或C3-C10环烷基。
或R13表示(例如)C1-C20烷基、苯基、C2-C12烯基或C3-C10环烷基。
或R13表示(例如)C1-C20烷基、C2-C12烯基或C3-C10环烷基。
较佳地，R13表示C1-C20烷基，尤其为C1-C8烷基，例如2-乙基己基。
R14表示(例如)氢、C3-C8环烷基、C2-C5烯基、C1-C20烷氧基或C1-C20烷基，其未经取代或经一或多个卤素或苯基取代；或R14表示苯基或萘基，此两种未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基、卤素、OR17、SR18和/或NR19R20；或R14表示C3-C5杂芳基，例如噻吩基，或是C1-C8烷氧基、苄氧基或苯氧基。
或R14表示(例如)C1-C20烷基，其未经取代或经一或多个卤素或苯基取代； 或R14表示C3-C5杂芳基(例如噻吩基)或是未经取代或经取代一或多个以下基团取代的苯基：C1-C6烷基、C1-C4卤代烷基、卤素、OR17、SR18和/或NR19R20；或R14表示C1-C8烷氧基、苄氧基或苯氧基。
在另一实施例中，R14表示C1-C20烷基，其未经取代或经苯基取代；或R14表示苯基，其未经取代或经一或多个C1-C6烷基取代。
较佳地，R14表示C1-C20烷基、C3-C5杂芳基(例如噻吩基)，或是苯基，尤其为C1-C20烷基或噻吩基，尤其为C1-C8烷基。
R15表示(例如)C6-C20芳基或C5-C20杂芳基，其各未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20、C1-C20烷基；或R15表示氢、C3-C8环烷基，该C3-C8环烷基视情况间杂有一或多个O、CO或NR26；或R15表示C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、OR17、C3-C8环烷基、C5-C20杂芳基、C8-C20苯氧基羰基、C5-C20杂芳氧基-羰基、NR19R20、COOR17、CONR19R20、PO(OCkH2k+1)2、式(6)所表示的基团、苯基、或经以下基团取代的苯基：卤素、C1-C20烷基、C1-C4卤代烷基、OR17或NR19R20；
Figure PCTCN2015092009-appb-000136
或R15表示C2-C20烷基，其间杂有一或多个O、S或SO2，或R15表示C2-C20烷酰基、苯甲酰基、C2-C12烷氧基羰基、苯氧基羰基、CONR19R20、NO2或C1-C4卤代烷基。
此外，R15表示(例如)氢、C6-C20芳基，尤其为苯基或萘基，其各未经取代或经C1-C12烷基取代；或是C3-C5杂芳基，例如噻吩基；或是C3-C8环烷基、C1-C20烷基，其未经取代或经一或多个以下基团取代：OR17、SR17、C3-C8-环烷基、NR19R20或COOR17；或R15表示C2-C20烷基，其间杂有一或多个O或SO2。
式(1)化合物令人关注，其中R15表示(例如)氢、苯基、萘基，其各未经取代或经C1-C8烷基取代；或R15表示噻吩基、C1-C20烷基，其未经取代或经一或多个以下基团取代：OR17、SR17、C3-C8-环烷基、NR19R20或COOR17；或R15表示C2-C20烷基，其间杂有一或多个O或SO2。
R15尤其为(例如)C3-C8环烷基或C1-C20烷基，尤其为C1-C20烷基，尤其为 C1-C12烷基。
R'14及R'15的较佳的分别是如上文针对R14及R15所给出的。
X1表示(例如)O、S或SO，例如O或S，尤其为O。
R16表示(例如)C6-C20芳基(尤其苯基或萘基、尤其苯基)或C5-C20杂芳基(尤其噻吩基)，其各未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20或间杂有一或多个O的C1-C20烷基；或其各经一或多个C1-C20烷基取代，该C1-C20烷基未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C5-C20杂芳基、C6-C20芳氧基羰基、C5-C20杂芳氧基羰基、OR17、SR18或NR19R20；或R16表示氢、C1-C20烷基，该C1-C20烷基未经取代或经一或多个以下基团取代：卤素、苯基、OH、SH、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基)；或R16表示C2-C12烷基，其间杂有一或多个O；或表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8环烷基，且n是1至20，例如1至12或1至8，尤其为1或2。
此外，R16表示(例如)苯基或萘基，尤其为苯基、噻吩基或咔唑，其各未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20或C1-C20烷基；或R16表示C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、苯基、OH、SH、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基)；或R16表示C2-C12烷基，其间杂有一或多个O；或是(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8环烷基，且n是1至20，例如1至12或1至8，尤其为1或2。
此外，R16表示(例如)苯基或萘基，尤其为苯基，其各未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20或C1-C20烷基；或R16表示C3-C5杂芳基，尤其为噻吩基。
R16尤其为(例如)苯基，其未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或C1-C20烷基，或R16表示噻吩基。
较佳地，R16表示(例如)苯基或萘基，其各未经取代或经一或多个C1-C20烷基取代。
R16尤其为苯基，其经一或多个C1-C20烷基取代。
R17表示(例如)氢、苯基-C1-C3烷基、C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、OH、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20环烷基或间杂有一或多个O的C3-C20环烷基；或R17表示C2-C20烷基，其间杂有一或多个O；是(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷酰基、C2-C12烯基、C3-C6烯酰基或C3-C20环烷基，其视情况间杂有一或多个O；或R17表示苯甲酰基，其未经取代或经一或多个C1-C6烷基、卤素、OH或C1-C3烷氧基取代；或R17表示苯基、萘基或C5-C20杂芳基，其各未经取代或经一或多个以下基团取代：卤素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或式(7)表示的基团
Figure PCTCN2015092009-appb-000137
在另一实施例中，R17表示(例如)氢、苯基-C1-C3烷基、C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或间杂有一或多个O的C2-C20烷基；或是C1-C8烷酰基、C2-C12烯基、C3-C6烯酰基、间杂有一或多个O的C2-C20烷基、视情况间杂有一或多个O的C3-C20环烷基；或是苯甲酰基，其未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、OH或C1-C3烷氧基；或是苯基或萘基，其各未经取代或经一或多个以下基团取代：卤素、C1-C12烷基或C1-C12烷氧基。
R17为(例如)氢、苯基-C1-C3烷基、C1-C8烷酰基、C1-C20烷基，其未经取代或经一或多个以下基团取代：卤素、C3-C20环烷基、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或间杂有一或多个O的C2-C20烷基，或R17表示C2-C20烷基，其间杂有一或多个O。
R17尤其为氢、C1-C8烷酰基、C1-C20烷基，其未经取代或经一或多个以下基团取代：O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或间杂有一或多个O的C2-C20烷基，或R17表示C2-C20烷基，其间杂有一或多个O。
R18表示(例如)C3-C20环烷基，其未经间杂或间杂有一或多个O；或R18表示C1-C20烷基，其未经取代或经一或多个以下基团取代：OH、O(CO)-(C2-C4) 烯基、O(CO)-(C1-C4烷基)或(CO)OR17；或R18表示C2-C20烷基，其间杂有一或多个O、S、CO、NR26或COOR17；或R18表示C2-C8烷酰基或C3-C6烯酰基、苯甲酰基；或R18表示苯基、萘基或C3-C20杂芳基，其各未经取代或经一或多个以下基团取代：卤素、C1-C12烷基、C1-C4卤代烷基、C1-C12烷氧基或NO2。
在另一实施例中，R18表示(例如)C3-C20环烷基、C1-C20烷基，其未经取代或经一或多个以下基团取代：OH、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)或(CO)OR17；或R18表示苯基或萘基，其各未经取代或经一或多个卤素或C1-C12烷基、尤其卤素取代。
R18表示(例如)C1-C20烷基、C2-C12烯基、C3-C20环烷基、苯基-C1-C3烷基、C2-C8烷酰基、苯甲酰基、苯基或萘基。
举例而言，R18表示C1-C20烷基，其经一或多个以下基团取代：OH、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)或(CO)OR17，或R18表示苯基，其经一或多个卤素取代。
较佳地，R18表示C1-C8烷基，其如上文所定义经取代。
举例而言，R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C3-C20环烷基、苯基-C1-C3烷基、苯基或萘基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基或苯甲酰基；或R19及R20与其所附接的N原子一起形成视情况间杂有O、S或NR17的5元或6元饱和或不饱和环；或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C4卤代烷基、或式(7)表示的基团、
Figure PCTCN2015092009-appb-000138
此外，举例而言，R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C3-C20环烷基、苯基-C1-C3烷基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基或苯甲酰基；或R19及R20与其所附接的N原子一起形成视情况间杂有O或NR17的5元或6元饱和环；或R19及R20与其所附接的N原子一起形成咔唑环。
举例而言，R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C3-C20环烷基、苯基-C1-C3烷基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基或 苯甲酰基；或R19及R20与其所附接的N原子一起形成视情况间杂有O或NR17的5元或6元饱和环。
较佳地，R19及R20彼此独立地为C1-C8烷酰基、C1-C8烷酰基氧基；或R19及R20与其所附接的N原子一起形成吗啉环。
举例而言，R21及R22彼此独立地为氢、C1-C20烷基、C1-C4卤代烷基、C3-C10环烷基或苯基；或R21及R22与其所附接的N原子一起形成吗啉环。R21及R22尤其彼此独立地为氢或C1-C20烷基。
R23表示(例如)氢、OH、苯基或C1-C20烷基。R23尤其为氢、OH或C1-C4烷基。
R24的较佳的是如针对R19及R20所给出。R25的较佳的是如针对R17所给出。
R26表示(例如)氢、C1-C20烷基、C1-C4卤代烷基、C2-C20烷基，其间杂有一或多个O或CO；或是苯基-C1-C4烷基、C3-C8环烷基，其视情况间杂有一或多个O或CO；或是(CO)R19或苯基，其未经取代或经一或多个以下基团取代：C1-C20烷基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20。
或R26表示(例如)氢、C1-C20烷基、C1-C4卤代烷基；是苯基-C1-C4烷基、C3-C8环烷基、(CO)R19或苯基，其未经取代或经一或多个C1-C20烷基取代。此外，R26表示(例如)氢或C1-C20烷基、尤其为C1-C4烷基。
发明式(1)化合物的实例包括下列由式(1-1)至式(1-84)所表示的化合物:
Figure PCTCN2015092009-appb-000139
Figure PCTCN2015092009-appb-000140
Figure PCTCN2015092009-appb-000141
Figure PCTCN2015092009-appb-000142
Figure PCTCN2015092009-appb-000143
Figure PCTCN2015092009-appb-000144
Figure PCTCN2015092009-appb-000145
Figure PCTCN2015092009-appb-000146
Figure PCTCN2015092009-appb-000147
Figure PCTCN2015092009-appb-000148
Figure PCTCN2015092009-appb-000149
Figure PCTCN2015092009-appb-000150
Figure PCTCN2015092009-appb-000151
Figure PCTCN2015092009-appb-000152
Figure PCTCN2015092009-appb-000153
基于所述碱可溶性树脂(A)为100重量份，所述由式(1)表示的光起始剂(C-1)的使用量为10至70重量份，较佳为12重量份至60重量份，更佳为15重量份至50重量份。
当感光性树脂组成物不使用光起始剂(C-1)时，则感光性树脂组成物在高温及高湿下的信赖性不佳，解析度不佳以及耐热阻抗性不佳。
光起始剂(C-2)
光起始剂(C-2)的具体例包括其他氧-酰基肟类化合物(O-acyloxime)或非氧-酰基肟类光起始剂。
其他氧-酰基肟类化合物
其它氧-酰基肟类化合物的具体例包括具体例包括1-[4-(苯基硫代)苯基]-丙烷-3-环戊烷-1,2-二酮2-(O-苯酰基肟)、1-[4-(苯基硫代)苯基]-庚烷-1,2-二酮2-(O-苯酰基肟)、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮-2-(O-苯酰基肟)，或上述化合物的组合。1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮-2-(O-苯酰基肟)可为由汽巴精化(Ciba Specialty Chemicals)有限公司制造，型号为IRGACURE OXE-01的商品。
此外，其他氧-酰基肟类化合物的具体例包括1-[4-(苯酰基)苯基]-庚烷-1,2-二酮-2-(O-苯酰基肟)、1-[9-乙基-6-(2-甲基苯酰基)-9H-咔唑-3-取代基]-乙烷酮-1-(O-乙酰基肟)、1-[9-乙基-6-(3-甲基苯酰基)-9H-咔唑-3-取代基]-乙烷酮-1-(O-乙酰基肟)、1-[9-乙基-6-苯酰基-9H-咔唑-3-取代基]-乙烷酮-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢呋喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢吡喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢呋喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢吡喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢呋喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢吡喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢呋喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢吡喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧杂戊环基)苯酰基}-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧杂戊环基)甲氧基苯酰基}-9H-咔唑-3-取代基]-1-(O-乙酰基肟)，或上述化合物的组合。1-[9-乙基-6-(2-甲基苯酰基)-9H-咔唑-3-取代基]-乙烷酮-1-(O-乙酰基肟)可为由汽巴精化有限公司制造，型号为IRGACURE OXE-02的商品。
其他氧-酰基肟类化合物可单独使用或组合多种来使用。
非氧-酰基肟类光起始剂
非氧-酰基肟类光起始剂的具体例包括三氮杂苯类化合物、苯乙烷酮类化合物、二咪唑类化合物、二苯甲酮类化合物、α-二酮类化合物、醇酮类化合 物、醇酮醚类化合物、酰膦氧化物类化合物、醌类化合物、含卤素类化合物、过氧化物，或上述化合物的组合。
三氮杂苯类化合物的具体例包括乙烯基-卤代甲基-s-三氮杂苯化合物、2-(萘并-1-取代基)-4,6-二(卤代甲基)-s-三氮杂苯化合物、4-(对-胺基苯基)-2,6-二(卤代甲基)-s-三氮杂苯化合物，或上述化合物的组合。
乙烯基-卤代甲基-s-三氮杂苯化合物的具体例包括2,4-二(三氯甲基)-6-对-甲氧基苯乙烯基-s-三氮杂苯、2,4-二(三氯甲基)-3-(1-对-二甲基胺基苯基-1,3-丁二烯基)-s-三氮杂苯、2-三氯甲基-3-胺基-6-对-甲氧基苯乙烯基-s-三氮杂苯，或上述化合物的组合。
2-(萘并-1-取代基)-4,6-二(卤代甲基)-s-三氮杂苯化合物的具体例包括2-(萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(4-甲氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(4-乙氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(4-丁氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-[4-(2-甲氧基乙基)-萘并-1-取代基]-4,6-二(三氯甲基)-s-三氮杂苯、2-[4-(2-乙氧基乙基)-萘并-1-取代基]-4,6-二(三氯甲基)-s-三氮杂苯、2-[4-(2-丁氧基乙基)-萘并-1-取代基]-4,6-二(三氯甲基)-s-三氮杂苯、2-(2-甲氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(6-甲氧基-5-甲基-萘并-2-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(6-甲氧基-萘并-2-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(5-甲氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(4,7-二甲氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(6-乙氧基-萘并-2-取代基)-4,6-二(三氯甲基)-s-三氮杂苯、2-(4,5-二甲氧基-萘并-1-取代基)-4,6-二(三氯甲基)-s-三氮杂苯，或上述化合物的组合。
4-(对-胺基苯基)-2,6-二(卤代甲基)-s-三氮杂苯化合物的具体例包括4-[对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-甲基-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-甲基-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-(对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-[对-N,N-二(苯基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-(对-N-氯乙基羰基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-[对 -N-(对-甲氧基苯基)羰基胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-溴-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-氯-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-氟-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-溴-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-氯-对-N,N-二(乙氧基羰基甲基)胺基苯基-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-氟-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-溴-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-氯-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[邻-氟-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-溴-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-氯-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-[间-氟-对-N,N-二(氯乙基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、4-(间-溴-对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(间-氯-对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(间-氟-对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(邻-溴-对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(邻-氯-对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(邻-氟-对-N-乙氧基羰基甲基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(间-溴-对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(间-氯-对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(间-氟-对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(邻-溴-对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(邻-氯-对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、4-(邻-氟-对-N-氯乙基胺基苯基)-2,6-二(三氯甲基)-s-三氮杂苯、2,4-二(三氯甲基)-6-[3-溴-4-[N,N-双(乙氧基羰基甲基)胺基]苯基]-1,3,5-三氮杂苯，或上述化合物的组合。三氮杂苯类化合物可单独使用或组合多种来使用。
三氮杂苯类化合物较佳为包括4-[间-溴-对-N,N-二(乙氧基羰基甲基)胺基苯基]-2,6-二(三氯甲基)-s-三氮杂苯、2,4-二(三氯甲基)-6-对-甲氧基苯乙烯基-s-三氮杂苯，或上述化合物的组合。
苯乙烷酮类化合物的具体例包括对二甲胺苯乙烷酮、α,α’-二甲氧基氧化偶氮苯乙烷酮、2,2’-二甲基-2-苯基苯乙烷酮、对-甲氧基苯乙烷酮、2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮、2-苄基-2-N,N-二甲胺-1-(4-吗啉代苯基)-1-丁酮，或上述化合物的组合。
苯乙烷酮类化合物可单独使用或组合多种来使用。
2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮可为由汽巴精化有限公司制造，型号为IRGACURE 907的商品。2-苄基-2-N,N-二甲胺-1-(4-吗啉代苯基)-1-丁酮可为由汽巴精化有限公司制造，型号为IRGACURE 369的商品。
苯乙烷酮类化合物较佳为包括2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮、2-苄基-2-N,N-二甲胺-1-(4-吗啉代苯基)-1-丁酮，或上述化合物的组合。
二咪唑类化合物的具体例包括2,2’-双(邻-氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(邻-氟苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(邻-甲基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(邻-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(邻-乙基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(对-甲氧基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(2,2’,4,4’-四甲氧基苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(2-氯苯基)-4,4’,5,5’-四苯基二咪唑、2,2’-双(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑，或上述化合物的组合。
二咪唑类化合物可单独使用或组合多种来使用。
二咪唑类化合物较佳为2,2’-双(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑。
二苯甲酮类化合物的具体例包括噻吨酮、2,4-二乙基噻吨酮、噻吨酮-4-砜、二苯甲酮、4,4’-双(二甲胺)二苯甲酮、4,4’-双(二乙胺)二苯甲酮，或上述化合物的组合。二苯甲酮类化合物可单独或混合使用。二苯甲酮类化合物较佳为4,4’-双(二乙胺)二苯甲酮。
α-二酮类化合物的具体例包括苯偶酰、双乙酰，或上述化合物的组合。α-二酮类化合物可单独使用或组合多种来使用。
酮醇类化合物的具体例包括二苯乙醇酮。酮醇类化合物可单独使用或组合多种来使用。
酮醇醚类化合物的具体例包括二苯乙醇酮甲醚、二苯乙醇酮乙醚、二苯乙醇酮异丙醚，或上述化合物的组合。酮醇醚类化合物可单独使用或组合多种来使用。
酰膦氧化物类化合物的具体例包括2,4,6-三甲基苯酰基二苯基膦氧化物、双(2,6-二甲氧基苯酰)-2,4,4-三甲基苯基膦氧化物，或上述化合物的组合。酰膦氧化物类化合物可单独使用或组合多种来使用。
醌类化合物的具体例包括蒽醌、1,4-萘醌，或上述化合物的组合。醌类化合物可单独使用或组合多种来使用。
含卤素类化合物的具体例包括苯酰甲基氯、三溴甲基苯砜、三(三氯甲基)-s-三氮杂苯，或上述化合物的组合。含卤素类化合物可单独使用或组合多种来使用。
过氧化物的具体例包括二-第三丁基过氧化物等。过氧化物可单独使用或组合多种来使用。
基于所述碱可溶性树脂(A)100重量份，所述光起始剂(C)的使用量为10至80重量份，较佳为12重量份至70重量份，更佳为15重量份至60重量份。
溶剂(D)
溶剂(D)是指可以将碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)以及光起始剂(C)以及下述的黑色颜料(E)、分支聚合物(F)、热起始剂(G)以及化合物(H)溶解，但又不与上述成分反应的溶剂，并且较佳为具有适当挥发性的。
上述溶剂(D)的具体例包括：烷基二醇单烷醚类化合物、烷基二醇单烷醚醋酸酯类化合物、二乙二醇烷基醚、其他醚类化合物、酮类化合物、乳酸烷酯类化合物、其他酯类化合物、芳香族烃类化合物、羧酸胺类化合物或上述化合物的组合
烷基二醇单烷醚类化合物的具体例包括：乙二醇单甲醚、乙二醇单乙醚、二乙二醇单乙醚、二乙二醇单正丙醚、二乙二醇单正丁醚、三乙二醇单甲醚、三乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙醚、二丙二醇单正丁醚、三丙二醇单甲醚或三丙二醇单乙醚或其类似物，或上述化合物的组合。
烷基二醇单烷醚醋酸酯类化合物的具体例包括：乙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯或丙二醇甲醚醋酸酯或丙二醇乙醚醋酸酯或其类似物，或上述化合物的组合。
二乙二醇烷基醚的具体例包括二乙二醇二甲醚、二乙二醇甲乙醚、二乙二醇二乙醚或其类似物，或上述化合物的组合。
其他醚类化合物的具体例包括四氢呋喃或其类似物。
酮类化合物的具体例包括甲乙酮、环己酮、2-庚酮、3-庚酮、二丙酮醇或其类似物，或上述化合物的组合。
乳酸烷酯类化合物的具体例包括乳酸甲酯、乳酸乙酯或其类似物，或上述化合物的组合。
其他酯类化合物的具体例包括2-羟基-2-甲基丙酸甲酯、2-羟基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基醋酸乙酯、羟基醋酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基丙酸酯、醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸正丁酯、醋酸异丁酯、醋酸正戊酯、醋酸异戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸异丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙酰醋酸甲酯、乙酰醋酸乙酯、2-氧基丁酸乙酯或其类似物，或上述化合物的组合。
芳香族烃类化合物的具体例包括甲苯、二甲苯或其类似物，或上述化合物的组合。
羧酸胺类化合物N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或其类似物，或上述化合物的组合。上述溶剂(D)可单独使用或组合多种来使用。
溶剂(D)较佳为丙二醇甲醚醋酸酯、环己酮或3-乙氧基丙酸乙酯。
基于上述碱可溶性树脂(A)的使用量为100重量份，溶剂(D)的使用量为1000重量份至8000重量份，较佳为1200重量份至7000重量份，更佳为1500重量份至6000重量份。
黑色颜料(E)
黑色颜料(E)较佳为具有耐热性、耐光性以及耐溶剂性的黑色颜料。
黑色颜料(E)的具体例包括：二萘嵌苯黑(perylene black)、花青黑(cyanine black)或苯胺黑(aniline black)等的黑色有机颜料；由红、蓝、绿、紫、黄色、花青(cyanine)或洋红(magenta)等的颜料中，选择两种或两种以上的颜料进行 混合，使其形成接近黑色化的混色有机颜料；碳黑(carbon black)、氧化铬、氧化铁、钛黑(titanium black)或石墨等的遮光材，其中上述碳黑的具体例包括C.I.pigment black 7或三菱化学所制造的市售品(商品名MA100、MA230、MA8、#970、#1000、#2350或#2650)。上述黑色颜料(E)可单独使用或组合多种来使用。
黑色颜料(E)较佳为碳黑，且碳黑例如是三菱化学所制造的市售品MA100或MA230。
基于上述碱可溶性树脂(A)的使用量为100重量份，黑色颜料(E)的使用量为150重量份至1200重量份，较佳为200重量份至1000重量份，更佳为250重量份至800重量份。
多分支聚合物(F)
多分支聚合物(F)可以是由式(F2)表示的多巯基化合物与由式(F1)表示的多官能基(甲基)丙烯酸酯经麦克尔加成反应(Michael Addition Reaction)而形成的聚合物。
具体而言，由式(F1)表示的多官能基(甲基)丙烯酸酯如下所示。
Figure PCTCN2015092009-appb-000154
式(F1)中，M1表示氢原子或碳数为1至4的烷基；M2表示具有h个羟基的含羟基的化合物中的g个羟基经酯化后的残基，其中h≥g，g表示2至20的整数。
上述含羟基的化合物为M3(OH)h或M3(OH)h经环氧丙烷、环氧氯丙烷、烷基、烷氧基或丙烯酸羟丙酯改性的化合物。
M3(OH)h为具有碳数为2至18的多元醇、由上述多元醇所形成的多元醇醚、由上述多元醇与酸反应而形成的酯类、或硅酮。
另外，由式(F2)表示的多巯基化合物如下所示。
Figure PCTCN2015092009-appb-000155
式(F2)中，M4表示单键、碳数为1的烃基、或碳数为2至22的直链或支链的烃基，M4的骨架中可还包括硫原子或构成酯基中的氧原子(即M4为单键、碳数为1的烃基、含硫原子或氧原子的碳数为2至22的直链或支链的烃基、或不含硫原子或氧原子的碳数为2至22的直链或支链的烃基)；i表示2至6的整数，其中当M4表示单键时，i表示2；当M4表示碳数为1的烃基时，i表示2至4的整数；当M4表示碳数为2至22的直链或支链的烃基时，i表示2至6的整数。
又，本发明的多分支聚合物(F)较佳为由式(F2)表示的多巯基化合物及由式(F1)表示的多官能基(甲基)丙烯酸酯反应后而残存的(甲基)丙烯酸酯基，进一步与由式(F3)表示的具有羧基的巯基化合物反应而形成的聚合物。
由式(F3)表示的具有羧基的巯基化合物如下所示。
Figure PCTCN2015092009-appb-000156
式(F3)中，M5表示碳数为1至12的亚烷基，j表示1至3的整数。
详言之，由式(F2)表示的多巯基化合物与由式(F3)表示的具有羧基的巯基化合物所含有的巯基是经由光反应而加成至由式(F1)表示的多官能基(甲基)丙烯酸酯的碳-碳双键上。一般而言，由式(F1)表示的多官能基(甲基)丙烯酸酯的碳-碳双键中，进行光反应的碳-碳双键相对于所有碳-碳双键较佳为0.1％至50％。
进一步而言，由式(F2)表示的多巯基化合物的巯基，或是由式(F2)表示的多巯基化合物与由式(F3)表示的具有羧基的巯基化合物的巯基，相对于由式(F1)表示的多官能基(甲基)丙烯酸酯的碳-碳双键的加成摩尔比率可为1/200至1/2，较佳为1/100至1/3，更佳为1/50至1/5，再更佳为1/20至1/8。
多分支聚合物(F)较佳为具有充分的光聚合官能基，例如碳-碳双键。具体而言，每1摩尔的碳-碳双键所对应的多分支聚合物(F)的分子量较佳为100至100,000。多分支聚合物(F)的分子量较佳为1,000至50,000，更佳为1,500至40,000，特佳为2,000至30,000。
此外，为制造可碱显影的感光性树脂组成物，多分支聚合物(F)较佳为具有充分的羧基。具体而言，每1摩尔的羧基所对应的多分支聚合物(F)的分子量较佳为200至20,000，更佳为250至6,000。
由式(F1)表示的多官能基(甲基)丙烯酸酯所含有的丙烯酸酯基的个数(g)较佳为2至20，更佳为2至10，再更佳为2至6。当式(F1)中的M1表示碳数为1至4的烷基时，M1可为甲基、乙基、丙基或丁基，较佳为甲基。又，M3(OH)h所具有的碳数较佳为2至18，更佳为2至14，特别佳为4至12。
由式(F1)表示的多官能基(甲基)丙烯酸酯的具体例包括乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、四亚甲基二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、经环氧乙烷改性的三羟甲基丙烷三(甲基)丙烯酸酯、经环氧丙烷改性的三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基乙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、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、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、经己内酯改性的季戊四醇三(甲基)丙烯酸酯、经己内酯改性的季戊四醇四(甲基)丙烯酸酯、经己内酯改性的二季戊四醇六(甲基)丙烯酸酯、经环氧氯丙烷改性的六氢化邻苯二甲酸二(甲基)丙烯酸酯、羟基特戊酸新戊二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、经环氧乙烷改性的新戊二醇二(甲基)丙烯酸酯、经环氧丙烷改性的新戊二醇二(甲基)丙烯酸酯、经己内酯改性的羟基特戊酸酯新戊二醇二(甲基)丙烯酸酯、经硬脂酸改性的季戊四醇二(甲基)丙烯酸酯、经环氧氯丙烷改性的邻苯二甲酸二(甲基)丙烯酸酯、聚(乙二醇四亚甲基二醇)二(甲基)丙烯酸酯、聚(丙二醇四亚甲基二醇)二(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚乙二醇聚丙二醇聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、经环氧氯丙烷改性的丙二醇二(甲基)丙烯酸酯、经环氧丙烷改性的双酚A二缩水甘油醚二(甲基)丙烯酸酯、硅酮二(甲基)丙烯酸 酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三环癸烷二甲醇二(甲基)丙烯酸酯、经新戊二醇改性的三羟甲基丙烷二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、经环氧乙烷改性的三丙二醇二(甲基)丙烯酸酯、三甘油二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、经环氧氯丙烷改性的甘油三(甲基)丙烯酸酯、经环氧乙烷改性的甘油三(甲基)丙烯酸酯、经环氧丙烷改性的甘油三(甲基)丙烯酸酯、经环氧乙烷改性的磷酸三(甲基)丙烯酸酯、经己内酯改性的三羟甲基丙烷三(甲基)丙烯酸酯、经丙烯酸羟丙酯改性的三羟甲基丙烷三(甲基)丙烯酸酯、经环氧乙烷改性的三羟甲基丙烷三(甲基)丙烯酸酯、经环氧丙烷改性的三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷苯甲酸酯(甲基)丙烯酸酯、三((甲基)丙烯酰基乙基)异氰尿酸酯、经烷氧基改性的三羟甲基丙烷三(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、经烷基改性的二季戊四醇三(甲基)丙烯酸酯、二三羟甲基丙烷四(甲基)丙烯酸酯等的(甲基)丙烯酸酯，或上述化合物的组合。
由式(F2)表示的多巯基化合物中的M4所具有的碳数较佳为0至22(当碳数为0时，M3为单键，且式(F2)表示HS-CH2-CH2-SH)，更佳为1至16，特别佳为2至12。由式(F2)表示的多巯基化合物的具体例包括1,2-二巯基乙烷、1,3-二巯基丙烷、1,4-二巯基丁烷、双二巯基乙烷硫醇(HS-CH2CH2-S-CH2CH2-SH)、二巯基三乙二醇、三羟甲基丙烷三(巯基醋酸酯)、三羟甲基丙烷三(巯基丙酸酯)、季戊四醇四(巯基醋酸酯)、季戊四醇三(巯基醋酸酯)、季戊四醇四(巯基丙酸酯)、二季戊四醇六(巯基醋酸酯)、二季戊四醇六(巯基丙酸酯)，或上述化合物的组合。
由式(F3)表示的具有羧基的巯基化合物中的M5所具有的碳数为1至12的亚烷基可为直链或支链的亚烷基。具体而言，该亚烷基例如是亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基或亚十二烷基等基。由式(F3)表示的具有羧基的巯基化合物可列举如巯基乙酸。
在本发明中，上述加成反应可先将由式(F3)表示的多官能基(甲基)丙烯酸酯(单体)与由式(F2)表示的多巯基化合物混合，于室温至100℃下，并且添加碱性催化剂来进行。反应时间通常为30分钟至约6小时。如此，即可获得多分支聚合物。
接着，可于该多分支聚合物中添加由式(F3)表示的具有羧基的巯基化合物，再进行一次加成反应。如此，即可获得具有羧基的多分支聚合物。
另外，可利用液相层析法(liquid chromatography)、凝胶过滤层析法(gel filtration chromatography)等的一般分析仪器来确认多分支聚合物(F)的合成结束。
又，在合成多分支聚合物(F)时，根据需要，必要时可添加阻聚剂。阻聚剂可使用一般用来抑制(甲基)丙烯酸酯化合物聚合的苯二酚(hydroquinone)类化合物、苯酚类化合物，或其组合。阻聚剂的具体例包括但不限于对苯二酚、甲氧基对苯二酚、邻苯二酚、对-第三丁基邻苯二酚、甲酚、二丁基羟基甲苯、2,4,6-三-第三丁基苯酚(BHT)，或上述化合物的组合。
基于碱可溶性树脂(A)的使用量为100重量份，多分支聚合物(F)的使用量为3至35重量份，较佳为4重量份至30重量份，且更佳为5重量份至25重量份。当使用了多分支聚合物(F)，则可进一步改善感光性树脂组成物的耐热阻抗性。
热起始剂(G)
本发明的热起始剂(G)并无特别限制，在本发明的一实施例中，其可包含但不限于偶氮化合物、有机过氧化物及过氧化氢化合物等。
上述的偶氮化合物的具体例为：2,2'-偶氮二异丁腈、2,2'-偶氮二(2-甲基丁腈)、1,1'-偶氮二(环己烷-2-甲腈)、2,2'-偶氮二(2,4-二甲基戊腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲酰胺、2,2-偶氮二{2-甲基-氮-[1,1-二(羟基甲基)-2-羟基乙基]丙酰胺、2,2'-偶氮二[氮-(2-丙烯基)-2-甲基丙酰胺]、2,2'-偶氮二[氮-(2-丙烯基)-2-乙基丙酰胺]、2,2'-偶氮二(氮-丁基-2-甲基丙酰胺)、2,2'-偶氮二(氮-环己基-2-甲基丙酰胺)、2,2'-偶氮二(二甲基-2-甲基丙酰胺)、2,2'-偶氮二(二甲基-2-甲基丙酸酯)或2,2'-偶氮二(2,4,4-三甲基戊烯)等。
上述的有机过氧化物的具体例为：过氧化苯甲酰、过氧化二第三丁基、过氧化二异丁酰、过氧化新癸酸异丙苯酯、过氧化二碳酸二丙酯、过氧化二碳酸二异丙酯、过氧化二碳酸二第二丁酯、1,1,3,3-四甲基丁基过氧化新癸酸酯、二(4-第三丁基环己基)过氧化二碳酸酯、1-环己基-1-甲基乙基过氧化二碳酸酯、双(2-乙氧基乙基)过氧化二碳酸酯、双(2-乙基己基)过氧化二碳酸酯、 过氧化新癸酸第三己酯、二甲氧基丁基过氧化二碳酸酯、第三丁基过氧化新癸酸酯、第三己基过氧化新戊酸酯、第三丁基过氧化新戊酸酯、过氧化二(3,5,5-三甲基己酰)、过氧化二辛酰、过氧化二月桂酰、过氧化二硬脂酸、2-乙基过氧化己酸-1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-二(2-乙基己酸过氧化)己烷、2-乙基过氧化己酸第三己酯、过氧化二(4-甲基苯甲酰)、2-乙基过氧化己酸第三丁酯、过氧化二苯甲酰、过氧化异丁酸第三丁酯、1,1-二(第三丁基过氧化)-2-甲基环己烷、1,1-二(第三丁基过氧化)-3,3,5-三甲基环己烷、1,1-二(第三己基过氧化)环己烷、1,1-二(第三丁基过氧化)环己烷、2,2-二[4,4-二(第三丁基过氧化)环己基]丙烷、第三己基过氧化异丙基碳酸酯、第三丁基过氧化马来酸酯、第三丁基过氧化-3,5,5-三甲基己酸酯、第三丁基过氧化月桂酸酯、2,5-二甲基-2,5-二(3-甲基苯甲酰过氧化)己烷、第三丁基过氧化异丙基碳酸酯、第三丁基过氧化-2-乙基己基碳酸酯、第三己基过氧化苯甲酸酯、2,5-二甲基-2,5-二(苯甲酰过氧化)己烷、第三丁基过氧化醋酸酯、2,2-二(第三丁基过氧化)丁烷、第三丁基过氧化苯甲酸酯、丁基-4,4-二(第三丁基过氧化戊酸酯、二(2-第三丁基过氧化异丙基)苯、过氧化异丙苯、二第三己基过氧化物、2,5-二甲基-2,5-二(第三丁基过氧化)己烷、二第三丁基过氧化物、2,5-二甲基-2,5-二(第三丁基过氧化)己炔、第三丁基三甲基过氧化硅烷、二(3-甲基苯甲酰基)过氧化物与苯甲酰基(3-甲基丙甲酰基)过氧化物与二苯甲酰基过氧化物的混合物等。
上述的过氧化氢化合物的具体例为：萜烷过氧化氢、二异丙基苯过氧化氢、1,1,3,3-四甲基丁基过氧化氢、异丙苯过氧化氢、第三丁基过氧化氢等。
前述的热起始剂(G)以2,2'-偶氮二异丁腈、2,2'-偶氮二(2-甲基丁腈)、2,2'-偶氮二(2,4-二甲基戊腈)、过氧化二异丁酰、过氧化二苯甲酰、过氧化异丁酸第三丁酯、萜烷过氧化氢、异丙苯过氧化氢、过氧化新癸酸异丙苯酯等为较佳。上述的热起始剂(G)可单独一种或混合复数种使用，视实际需要而定。
在本发明的一具体例中，基于碱可溶性树脂(A)的使用量为100重量份，该热起始剂(G)的使用量为4至40重量份；较佳为5至35重量份；更佳为6至30重量份。若使用热起始剂(G)时，则可进一步改善感光树脂组成物的解析度。
式(10)表示的化合物(H)
根据本发明的黑色矩阵用感光性树脂组成物包含式(10)表示的化合物 (H)；
Figure PCTCN2015092009-appb-000157
其中式(10)中：Z1、Z2及Z3各自独立代表经亚烷基或亚芳基结合的三烷氧基硅烷基。其中该亚烷基或亚芳基可具有取代基，该取代基可为氨基、羟基、烷氧基或卤素原子。根据本发明的亚烷基的具体例为亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基等碳原子数为1至10的亚烷基。根据本发明的亚芳基的具体例为亚苯基或亚萘基。
根据本发明的该式(10)所示的化合物(H)的具体例为下式(10-1)至(10-9)所示的化合物：
Figure PCTCN2015092009-appb-000158
Figure PCTCN2015092009-appb-000159
Figure PCTCN2015092009-appb-000160
其中式(10-1)所示结构化合物为1,3,5-N-三(三甲氧基硅烷基丙基)异氰脲酸酯，可购自Nippon Unicar Company Limited。
基于上述碱可溶性树脂(A)的使用量为100重量份，该式(10)表示的化合物(H)的使用量较佳为1重量份至10重量份，更佳为1.2重量份至9重量份，尤佳为1.5重量份至8重量份。若使用式(10)表示的化合物(H)时，则可进一步改善感光树脂组成物在高温及高湿下的信赖性。
感光性树脂组成物的制备方法
可用来制备感光性树脂组成物的方法例如：将碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)、光起始剂(C)、溶剂(D)以及黑色颜料(E)放置于搅拌器中搅拌，使其均匀混合成溶液状态，必要时可添加多分支聚合物(F)、热起始剂(G)以及化合物(H)，予以均匀混合后，便可获得溶液状态的感光性树脂组成物。
又，感光性树脂组成物的制备方法没有特别的限制。感光性树脂组成物的制备方法例如是先将一部分的碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)分散于一部分的溶剂(D)中，以形成分散溶液；并且接着混合其余的 碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)、光起始剂(C)、溶剂(D)以及黑色颜料(E)来制备。
或者，感光性树脂组成物也可以是由先将一部分的黑色颜料(E)分散于由部分碱可溶性树脂(A)以及一部分的溶剂(D)所组成的混合物来形成黑色颜料分散液后；并且加入碱可溶性树脂(A)、具有乙烯性不饱和基的化合物(B)、光起始剂(C)、溶剂(D)以及黑色颜料(E)来制备。又，上述黑色颜料(E)的分散步骤可通过例如珠磨机(beads mill)或辊磨机(roll mill)等混合器混合来进行。
黑色矩阵的制造方法
黑色矩阵是由上述的感光树脂组成物依序在基板上施予预烤、曝光、显影及曝后烤处理而制造得。又，所得的黑色矩阵的膜厚为1μm时，光学密度范围可为3.0以上，较佳为3.2至5.5，且更佳为3.5至5.5。以下详述黑色矩阵的制备方法。
首先，通过旋转涂布或流延涂布等涂布方式，在基板上均匀地涂布溶液状态的黑色矩阵用感光性树脂组成物，以形成涂膜。上述基材的具体例包括：用于液晶显示装置等的无碱玻璃、钠钙玻璃、硬质玻璃(派勒斯玻璃)、石英玻璃及于该玻璃上附着透明导电膜者；或用于固体摄影装置等的光电变换装置基板(如：硅基板)等。
形成涂膜之后，以减压干燥去除大部分溶剂，然后以预烤(pre-bake)方式将残余的溶剂完全去除，以形成预烤涂膜。值得注意的是，减压干燥及预烤的条件，依各成分的种类、比率而改变。一般而言，减压干燥是在小于200mmHg的压力下进行1秒至20秒，并且预烤乃在70℃至110℃温度下对涂膜进行1分钟至15分钟的加热处理。
接着，以具有特定图案的光罩对上述预烤涂膜进行曝光。在曝光过程中所使用的光线例如是g线、h线或i线等的紫外线为佳，而紫外线照射装置可为(超)高压水银灯及金属卤素灯。
然后，在23±2℃的温度下，将上述经曝光的预烤涂膜浸渍于显影液中，以去除上述未经曝光的部分的预烤涂膜，藉此可在基板上形成特定的图案。
显影液例如是氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、硅酸钠、甲基硅酸钠、氨水、乙胺、二乙胺、二甲基乙醇胺、氢氧化 四甲胺、氢氧化四乙胺、胆碱、吡咯、哌啶或1,8-二氮杂二环-[5,4,0]-7-十一烯等的碱性化合物等。显影液的浓度一般为0.001wt％至10wt％，较佳为0.005wt％至5wt％，且更佳为0.01wt％至1wt％。
在预烤涂膜经显影之后，将具有特定的图案的基板以水洗净，再以压缩空气或压缩氮气将上述特定的图案风干。然后，以热板或烘箱等加热装置进行后烤处理。后烤温度通常为150至250℃，其中使用热板的加热时间为5分钟至60分钟，并且使用烘箱的加热时间为15分钟至150分钟。经过上述的处理步骤后，即可于基板上形成黑色矩阵。
画素层与彩色滤光片的制备方法
画素层的制造方法与黑色矩阵的制造方法类似。具体而言，将彩色滤光片用感光性组成物涂布在上面已形成黑色矩阵的基板上，接着依序施予预烤、曝光、显影及后烤处理而制得。惟，在减压干燥的条件中，减压干燥是在0mmHg至200mmHg的压力下进行1秒至60秒。经过上述的处理步骤后，即可固定特定的图案，藉此形成画素层。并且，重复上述步骤，依序在基板上形成红、绿、蓝等画素层，即可获得上面形成了黑色矩阵及画素层的基板(即具有画素层的彩色滤光片)。
液晶显示元件的制备方法
首先，将通过上述彩色滤光片的制造方法所形成的彩色滤光片以及设置有薄膜电晶体的基板作对向配置，并且在上述两个之间设置间隙(晶胞间隔，cell gap)。接着，以粘着剂贴合彩色滤光片与上述基板的周围部分并且留下注入孔。然后，在基板表面以及粘着剂所分隔出的间隙内由注入孔注入液晶，最后封住注入孔来形成液晶层。随后，通过在彩色滤光片中接触液晶层的另一侧与基板中接触液晶层的另一侧提供偏光板来制作液晶显示装置。上述所使用的液晶，即液晶化合物或液晶组成物，此处并未特别限定。惟，可使用任何一种液晶化合物及液晶组成物。
此外，于制作彩色滤光片中所使用的液晶配向膜是用来限制液晶分子的配向，并且没有特别的限制，举凡无机物或有机物任一个均可，并且本发明并不限于此。
含有聚合性不饱和基的二醇化合物(a-1-1)的制备例
以下说明含有聚合性不饱和基的二醇化合物(a-1-1)的制备例1至制备例3：
制备例1
首先，将100重量份的芴环氧化合物(型号ESF-300，新日铁化学制造；环氧当量231)、30重量份的丙烯酸、0.3重量份的氯化苄基三乙基铵、0.1重量份的2,6-二第三丁基对甲酚以及130重量份的丙二醇单甲醚醋酸酯以连续式添加方式加入至500毫升的四颈烧瓶中。入料速度控制在25重量份/分钟，并且反应过程的温度维持在100℃至110℃，反应15小时后，即可获得固成分浓度为50重量％的淡黄色透明混合液。接着，使上述淡黄色透明混合液经受萃取、过滤及加热烘干的步骤，即可得固体成分含量为99.9重量％的制备例1的含有聚合性不饱和基的二醇化合物(a-1-1-a)。
制备例2
首先，将100重量份的芴环氧化合物(型号PG-100，大阪瓦斯制造；环氧当量259)、35重量份的甲基丙烯酸、0.3重量份的氯化苄基三乙基铵、0.1重量份的2,6-二第三丁基对甲酚以及135重量份的丙二醇单甲醚醋酸酯以连续添加方式加入至500毫升的四颈烧瓶中。入料速度控制在25重量份/分钟，并且反应过程的温度维持在100℃至110℃下，反应15小时后，即可获得固体成分含量为50重量％的淡黄色透明混合液。使上述淡黄色透明混合液经受萃取、过滤及加热烘干的步骤，即可得固体成分含量为99.9重量％的制备例2的含有聚合性不饱和基的二醇化合物(a-1-1-b)。
制备例3
将100重量份的芴环氧化合物(型号ESF-300，新日铁化学制造；环氧当量231)、100重量份的2-甲基丙烯酰乙氧基丁二酸酯、0.3重量份的氯化苄基三乙基铵、0.1重量份的2,6-二第三丁基对甲酚以及200重量份的丙二醇单甲醚醋酸酯以连续添加方式加入至500毫升的四颈烧瓶中。入料速度控制在25 重量份/分钟，且反应过程的温度维持在100℃至110℃下，反应15小时后，即可获得固体成分含量为50重量％的淡黄色透明混合液。使上述淡黄色透明混合液经受萃取、过滤及加热烘干的步骤，可得固体成分含量为99.9重量％的制备例3的含有聚合性不饱和基的二醇化合物(a-1-1-c)。
碱可溶性树脂(A-1)的合成例
以下说明碱可溶性树脂(A-1)的合成例A-1-1至合成例A-1-6：
合成例A-1-1
首先，将1.0摩尔制备例1的具有聚合性不饱和基的二醇化合物(a-1-1-a)、0.3摩尔的联苯四羧酸(a-1-2-d)、1.4摩尔的马来酸(a-1-3-d)、1.9克的氯化苄基三乙基铵、0.6克的2,6-二第三丁基对甲酚、700克的丙二醇单甲醚醋酸酯以及100克的3-乙氧基丙酸乙酯以同时添加方式加入至500毫升的四颈烧瓶中，以形成反应溶液。在此，“同时添加”是指于相同反应时间添加四羧酸或其酸二酐(a-1-2)与二羧酸或其酸酐(a-1-3)。接着，将上述反应溶液加热至110℃，并且反应2小时，即可得酸价为125毫克KOH/克且数量平均分子量为2455的碱可溶性树脂A-1-1。
合成例A-1-2
将1.0摩尔制备例2的具有聚合性不饱和基的二醇化合物(a-1-1-b)、2.9克的氯化苄基三乙基铵以及950克的丙二醇甲醚醋酸酯加入至500毫升的四颈烧瓶中，以形成反应溶液。接着，添加0.6摩尔的二苯甲酮四羧酸二酐(a-1-2-e)并在90℃下反应2小时。然后，添加0.8摩尔的四氢邻苯二甲酸酐(a-1-3-e)，并在90℃下反应4小时。在此，“分段添加”是指于不同的反应时间分别添加四羧酸或其酸二酐(a-1-2)与二羧酸或其酸酐(a-1-3)，即先添加四羧酸或其酸二酐(a-1-2)，之后再添加二羧酸或其酸酐(a-1-3)。经上述合成步骤，可得酸价为92毫克KOH/克且数量平均分子量为5130的碱可溶性树脂A-1-2。
合成例A-1-3、合成例A-1-5以及合成例A-1-6
合成例A-1-3、合成例A-1-5以及合成例A-1-6合的碱可溶性树脂是以与 合成例A-1-2相同的步骤来制备，并且其不同处在于：改变第一碱可溶性树脂的成分种类及其使用量、反应时间、反应温度以及反应物添加时间(如表1所示)。
合成例A-1-4
合成例A-1-4的碱可溶性树脂是以与合成例A-1-1相同的步骤来制备，并且其不同处在于：改变第一碱可溶性树脂的成分种类及其使用量、反应时间、反应温度以及反应物添加时间(如表1所示)。
表1中的简称所对应的化合物如下所示。
简称        成分
a-1-1-a     制备例1的含有聚合性不饱和基的二醇化合物(a-1-1-a)
a-1-1-b     制备例2的含有聚合性不饱和基的二醇化合物(a-1-1-b)
a-1-1-c     制备例3的含有聚合性不饱和基的二醇化合物(a-1-1-c)
a-1-2-a     4,4'-六氟亚异丙基二邻苯二甲酸二酐(4,4'-hexafluoro
            isopropylidene diphthalic dianhydride；6FDA)
a-1-2-b     1,4-二氟均苯四甲酸二酐(1,4-difluoropyromellitic 
            dianhydride)
a-1-2-c     1,4-二(三氟甲基)均苯四甲酸二酐(1,4-difluoropyromellitic 
            dianhydride)
a-1-2-d     联苯四羧酸(Biphenyl tetracarboxylic acid)
a-1-2-e     二苯甲酮四羧酸二酐(Benzophenone tetracarboxylic 
            dianhydride)
a-1-2-f     均苯四甲酸二酐(Pyromellitic dianhydride)
a-1-3-a     3-氟邻苯二甲酸酐(3-fluorophthalic anhydride)
a-1-3-b     3,6-二氟邻苯二甲酸酐(3,6-difluorophthalic anhydride)
a-1-3-c     4-氟邻苯二甲酸酐(4-fluorophthalic anhydride)
a-1-3-d     马来酸(Maleic acid)
a-1-3-e     四氢邻苯二甲酸酐(Tetrahydrophthalic anhydride)
PGMEA       丙二醇单甲醚醋酸酯(propylene glycol monomethyl ether
            acetate,PGMEA)
EEP         3-乙氧基丙酸乙酯(Ethyl 3-ethoxypropionate，EEP)
-           氯化苄基三乙基铵(Benzyltriethylammonium chloride)
-           2,6-二第三丁基对甲酚(2,6-di-tert-butyl-p-cresol)
表1
Figure PCTCN2015092009-appb-000161
表1(续)
Figure PCTCN2015092009-appb-000162
碱可溶性树脂(A-2)的合成例
以下说明碱可溶性树脂(A-2)的合成例A-2-1至合成例A-2-4：
合成例A-2-1
在容积为500毫升的三颈烧瓶中，加入0.40摩尔的二甲基二甲氧基硅烷(以下简称DMDMS)、0.55摩尔的苯基三乙氧基硅烷(以下简称PTES)、0.05摩尔的硅烷醇末端聚硅氧烷(以下简称DMS-S27)以及180克的4-羟基-4-甲基-2-戊酮(以下简称DAA)，并于室温下一边搅拌一边于30分钟内添加草酸水溶液(0.40克草酸/75克水)。接着，将烧瓶浸渍于30℃的油浴中并搅拌30分钟。然后，于30分钟内将油浴升温至120℃。待溶液的温度降到110℃(即反应温度)时，持续加热搅拌进行聚合6小时(即聚缩合时间)。再接着，利用蒸馏方式将溶剂移除，即可获得碱可溶性树脂(A-2-1)。碱可溶性树脂(A-2-1)的成分种类及其使用量如表2所示。
合成例A-2-2至合成例A-2-4
合成例A-2-2至合成例A-2-4的碱可溶性树脂(A-2)是以与合成例A-2-1相同的步骤来制备，并且其不同处在于：改变碱可溶性树脂(A-2)的成分种类及其使用量、反应温度及聚缩合时间(如表2所示)，其中表2中标号所对应的化合物如下所示。
简称        化合物
GF-20       3-(三乙氧基硅基)丙基丁二酸酐
            (3-(triethoxysilyl)propylsuccinic anhydride)
TMSG        3-(三甲氧基硅基)丙基戊二酸酐
            (3-(trimethoxysilyl)propylglutaric anhydride)
TMSOX       3-乙基-3-{[3-(三甲氧基硅基)丙氧基]甲基}环氧丙烷
            3-ethyl-3-((3-(trimethoxysilyl)propoxy)methyl)
            epoxypropane
TMS-GAA     3-环氧丙氧基丙基三甲氧基硅烷3-(glycidoxypropyl 
            trimethoxysilane)
MTMS        甲基三甲氧基硅烷(Methyltrimethoxysilane)
DMDMS       二甲基二甲氧基硅烷(Dimethyldimethoxysilane)
PTMS        苯基三甲氧基硅烷(Phenyltrimethoxysilane)
PTES        苯基三乙氧基硅烷(Phenyltriethoxysilane)
DMS-S27     硅烷醇末端聚硅氧烷，商品名为DMS-S27，由吉来斯特
            (Gelest)公司制造。
OSCAR       二氧化硅粒子、触媒化成公司制
1132
PGEE        丙二醇单乙醚(Propylene glycol monoethyl ether)
DAA         二丙酮醇(即4-羟基-4-甲基-2-戊酮)(Diacetone alcohol)
-           水(DI water)
-           草酸(Oxalic acid)
表2
Figure PCTCN2015092009-appb-000163
多分支聚合物(F)的合成例
以下说明多分支聚合物(F)的合成例F-1至合成例F-3：
合成例F-1
在容量为1L的四颈烧瓶中，加入25克的三羟甲基丙烷三(巯基醋酸酯)(巯基0.28摩尔)、177克的季戊四醇四丙烯酸酯(碳-碳双键2.01摩尔)、0.1克的对苯二酚及0.01克的苯甲基二甲胺(作为光起始剂，benzyl dimethyl amine)， 并在60℃下反应12小时。对每一个反应生成物，通过碘滴定法确认巯基消失，即可获得多分支聚合物F-1。多分支聚合物F-1经凝胶过滤层析法所测得的分子量为4,400。
合成例F-2
在容量为1L的四颈烧瓶中，加入20克的季戊四醇四(巯基醋酸酯)(巯基0.19摩尔)、212克的二季戊四醇六丙烯酸酯与二季戊四醇五丙烯酸酯的混合物(碳-碳双键2.12摩尔)、0.1克的对苯二酚及0.01克的苯甲基二甲胺，并在60℃下反应12小时。对每一个反应生成物，通过碘滴定法确认巯基消失，即可获得多分支聚合物F-2。多分支聚合物F-2经凝胶过滤层析法所测得的分子量为11,000。
合成例F-3
在容量为1L的四颈烧瓶中，加入季戊四醇四(巯基醋酸酯)20克(巯基0.19摩尔)、212克的二季戊四醇六丙烯酸酯与二季戊四醇五丙烯酸酯的混合物(碳-碳双键2.12摩尔)、58克的丙二醇单甲醚醋酸酯(作为溶剂)、0.1克的对苯二酚及0.01克的苯甲基二甲胺，并在60℃下反应12小时。对每一个反应生成物，通过碘滴定法确认巯基消失，即可获得中间产物。将此中间产物经凝胶过滤层析法所测得的分子量为11,000。
接着，在四颈烧瓶中，加入20克(0.22摩尔)巯基乙酸，并在60℃下反应12小时。对每一个反应生成物，通过碘滴定法确认巯基消失，即可获得多分支聚合物F-3。多分支聚合物F-3经凝胶过滤层析法所测得的分子量为12,000。
感光性树脂组成物及膜的实施例与比较例
以下说明感光性树脂组成物及膜的实施例1至实施例15以及比较例1至比较例3：
实施例1
a.感光性树脂组成物
将100重量份的碱可溶性树脂A-1-1、20重量份的季戊四醇三丙烯酸酯与邻苯二甲酸的酯化物(简称为B-1-1)、10重量份由式(1-1)所表示的光起始剂(简称为C-1-1)、350重量份的黑色颜料MA100(简称E-1)以及4重量份的2,2'-偶氮二(2,4-二甲基戊腈)(简称为G-1)加入1000重量份的丙二醇单甲醚醋酸酯(简称为D-1)中，并且以摇动式搅拌器搅拌均匀后，即可制得实施例1的感光性树脂组成物。
b.成膜
将实施例1的感光性树脂组成物以旋转涂布方式涂布于素玻璃基板(尺寸为100mm×100mm×0.7mm)上，以形成厚度为约6μm的涂膜。接着，将涂膜在90℃下预烤2至3分钟。然后，在曝光机与涂膜之间置入光罩，并以100mJ/cm2的紫外线对预烤涂膜进行图案化曝光(曝光机型号为AG500-4N，由M&R奈米科技(M&R Nanotechnology)制造)。将经曝光的涂膜浸渍于0.05％的氢氧化钾水溶液45至90秒，以去除上述经曝光的涂膜的不需要的部分。然后，用水清洗素玻璃基材。最后，将涂膜在235℃下以烘箱进行后烤30分钟，即可获得上面形成实施例1的膜的玻璃基板。将实施例1的膜以后述各评价方式进行评价，其结果如表3所示。
实施例2至实施例15
实施例2至实施例15的感光性树脂组成物及膜是以与实施例1相同的步骤来制备，并且其不同处在于：改变感光性树脂组成物的成分种类及其使用量(如表3所示)。将所制得的膜以下列各评价方式进行评价，其结果如表3所示。
比较例1至比较例3
比较例1至比较例3的感光性树脂组成物及膜是以与实施例1相同的步骤来制备，并且其不同处在于：改变感光性树脂组成物的成分种类及其使用量(如表4所示)。将所制得的膜以下列各评价方式进行评价，其结果如表4所示。
表3及表4中标号所对应的化合物如下所示。
简称      中文名称
A-1-1     合成例A-1-1的碱可溶性树脂(A-1)
A-1-2    合成例A-1-2的碱可溶性树脂(A-1)
A-1-3    合成例A-1-3的碱可溶性树脂(A-1)
A-1-4    合成例A-1-4的碱可溶性树脂(A-1)
A-1-5    合成例A-1-5的碱可溶性树脂(A-1)
A-1-6    合成例A-1-6的碱可溶性树脂(A-1)
A-2-1    合成例A-2-1的碱可溶性树脂(A-2)
A-2-2    合成例A-2-2的碱可溶性树脂(A-2)
A-2-3    合成例A-2-3的碱可溶性树脂(A-2)
A-2-4    合成例A-2-4的碱可溶性树脂(A-2)
B-1-1    季戊四醇三丙烯酸酯与邻苯二甲酸的酯化物
B-1-2    二季戊四醇五甲基丙烯酸甲酯与琥珀酸的酯化物
B-1-3    二季戊四醇五甲基丙烯酸甲酯与邻苯二甲酸的酯化物
B-1-4    二季戊四醇五甲基丙烯酸酯与戊二酸的酯化物
B-2-1    三丙烯酸三羟甲基丙酯(trimethylolpropane triacrylate)
B-2-2    二季戊四醇六丙烯酸酯(dipentaerythritol hexacrylate)
C-1-1    
Figure PCTCN2015092009-appb-000164
所表示的光起始剂
C-1-2    
Figure PCTCN2015092009-appb-000165
所表示的光起始剂
C-1-3    
Figure PCTCN2015092009-appb-000166
所表示的光起始剂
C-1-4    
Figure PCTCN2015092009-appb-000167
所表示的光起始剂
         乙烷酮,1-[9-乙基-6-(2-甲基苯甲酰基)-9氢-咔唑-3-取代
C-2-1    基]-1-(氧-乙酰肟)[商品名OXE-02；汽巴精化有限公司
         (Ciba Specialty Chemicals)制造]
C-2-2    2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮(商品名
         IRGACURE 907；汽巴精化有限公司制造)
D-1      丙二醇单甲醚醋酸酯
D-2      环己酮
E-1      MA100(三菱化学制)
E-2      MA230(三菱化学制)
F-1      合成例F-1的多分支聚合物F-1
F-2      合成例F-2的多分支聚合物F-2
F-3      合成例F-3的多分支聚合物F-3
G-1      2,2'-偶氮二(2,4-二甲基戊腈)
G-2      过氧化新癸酸异丙苯酯
G-3      萜烷过氧化氢
H-1      
Figure PCTCN2015092009-appb-000168
H-2      
Figure PCTCN2015092009-appb-000169
H-3      
Figure PCTCN2015092009-appb-000170
评价方式
a.高温及高湿下的信赖性
将上述各实施例及比较例制得的感光性树脂组成物利用涂布机(型号为MS-A150，购自新光贸易)，以旋转涂布的方式，涂布在长宽均为100毫米(mm)的玻璃基板上。然后，于约100毫米汞柱高(mmHg)的压力下，进行减压干燥约5秒钟。接着，将上述的玻璃基板置于100℃下预烤2分钟，以形成膜厚为1.2微米(μm)的预烤涂膜。
接着，使用曝光机(M&R Nano Technology公司制造，型号为AG500-4N)以100毫焦耳/平方厘米(mJ/cm2)的紫外光照射上述的预烤涂膜。使用紫外光照射后，将预烤涂膜浸渍于23℃的显影液(氢氧化钾，浓度为0.04％)中。经 过2分钟后，以纯水洗净，并将预烤涂膜放置于230℃下后烤60分钟，即可在玻璃基板上形成膜厚为1.0μm的遮光膜。
然后，将上述的遮光膜置于温度为121℃、压力为2大气压(atm)且相对湿度为100％的烘箱中，经过8小时后，根据JIS.5400(1900)8.5密着性试验法中的8.5.2的基盘目法测定遮光膜于高温高湿下的信赖性。首先，将上述的遮光膜以小刀切割成100个基盘目。然后，以胶带沾粘后撕下，观察基盘目残留的情形，并依据以下述基准进行评价：
◎：5B。
○：4B。
△：2B至3B。
╳：0B至1B。
其中，5B，无任何基盘目脱落。
4B，0％＜脱落的基盘目数量≤5％。
3B，5％＜脱落的基盘目数量≤15％。
2B，15％＜脱落的基盘目数量≤35％。
1B，35％＜脱落的基盘目数量≤65％。
0B，65％＜脱落的基盘目数量≤100％。
b.解析度
以旋转涂布方式将实施例以及比较例所制得的各种感光性树脂组成物，涂布于玻璃基板上。接着，在100℃下预烤2分钟，即可得到约1.2μm的预烤涂膜。然后，将上述预烤涂膜放置于线与间距的光罩(由日本惠尔康(Nibbon Filcon)制造)下，并且利用50mJ/cm2的紫外光(曝光机型号AG500-4N；由M&R Nano Technology制造)进行曝光。接着，以0.045％氢氧化钾水溶液于23℃下显影1分钟，以将基板上未曝光部份的涂膜除去。然后，将具有特定的图案的玻璃基板以水洗净。最后，将玻璃基板上所形成的图案的线条幅度的最小值定义为解析度。将线条幅度以下列方式评价。值得注意的是，最小图案线幅越小代表感光性树脂组成物的解析度越好。
◎：最小图案线幅≤4μm
○：4μm＜最小图案线幅≤6μm
△：6μm＜最小图案线幅≤8μm
╳：8μm＜最小图案线幅
c.耐热阻抗稳定性
使用高阻抗率计(型号为MCP-HT450型Hiresta-UP；三菱化学制)分别量测上述膜厚1.2μm的预烤涂膜。于上述预烤涂膜上任取三测定点，量测表面阻抗值的平均值(Ω1)。
接着，将该等预烤涂膜分别于指定的光罩下，以紫外光100mJ/cm2照射，之后浸渍于23℃的显影剂(0.04％氢氧化钾)2分钟，并以纯水洗净后，再于烘箱中以280℃后烤60分钟，可在玻璃基板上形成一膜厚为1.0μm的黑色矩阵。使用高阻抗率计于相同的三测定点上，量测表面阻抗值的平均值(Ω2)，最后经下式(IX)计算，并根据以下标准评价：
表面阻抗稳定性(RH)＝[(Ω2)/(Ω1)]×100％  (IX)
◎：RH＞97％
○：97％≥RH＞95％
△：95％≥RH＞90％
╳：RH≤90％
表3
Figure PCTCN2015092009-appb-000171
表3(续)
Figure PCTCN2015092009-appb-000172
表4
Figure PCTCN2015092009-appb-000173
<评价结果>
由表3以及表4得知，与使用含乙烯性不饱和基的化合物(B-1)的感光性树脂组成物所形成的膜(实施例1至实施例15)相比，使用不含乙烯性不饱和基的化合物(B-1)的感光性树脂组成物(比较例1、3)所形成的膜的解析度不佳。
另外，与使用含有光起始剂(C-1)的感光性树脂组成物所形成的膜(实施例 1至实施例15)相比，使用不含有光起始剂(C-1)的感光性树脂组成物所形成的膜(比较例2、3)所形成的膜的解析度不佳、耐热阻抗性不佳以及高温及高湿下的信赖性不佳。
综上所述，本发明的感光性树脂组成物由于包括具有乙烯性不饱和基的化合物(B)以及特定结构的光起始剂(C-1)，因此可以改善黑色矩阵的解析度、耐热阻抗性以及高温及高湿下的信赖性不佳的问题，进而适用于彩色滤光片以及液晶显示装置。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (18)

  1. 一种感光性树脂组成物，其特征在于，包括：
    碱可溶性树脂(A)；
    具有乙烯性不饱和基的化合物(B)；
    光起始剂(C)；
    溶剂(D)；
    黑色颜料(E)；
    其中，所述具有乙烯性不饱和基的化合物(B)包含具有酸性基及至少三个乙烯性不饱和基的化合物(B-1)；
    所述光起始剂(C)包括由式(1)表示的光起始剂(C-1)；
    Figure PCTCN2015092009-appb-100001
    其中R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、COR16、OR17、卤素、NO2、由式(2)所表示的基团或是由式(3)所表示的基团、
    Figure PCTCN2015092009-appb-100002
    Figure PCTCN2015092009-appb-100003
    或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地为经由式(4)所表示的基团取代的C2-C10烯基
    Figure PCTCN2015092009-appb-100004
    或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为—(CH2)p—Y—(CH2)q—；
    或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团；
    Figure PCTCN2015092009-appb-100005
    但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团，
    R9、R10、R11及R12彼此独立地为氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C1-C4-烷氧基、-(CO)OH或-(CO)O-(C1-C4烷基)；
    或R9、R10、R11及R12彼此独立地为未经取代的苯基或经一或多个以下基团取代的苯基：C1-C6烷基、卤素、CN、OR17、SR18或NR19R20；
    或R9、R10、R11及R12彼此独立地为卤素、CN、OR17、SR18、SOR18、SO2R18或NR19R20，其中该等取代基OR17、SR18或NR19R20视情况经由该等基团R17、R18、R19和/或R20与萘基环中一个碳原子形成5元或6元环；
    或R9、R10、R11及R12彼此独立地为COR1、6NO2或式(2)所表示的基团、
    Figure PCTCN2015092009-appb-100006
    Y表示O、S、NR26或直接键；
    p表示整数0、1、2或3；
    q表示整数1、2或3；
    X表示CO或直接键；
    R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、COOR17、OR17、SR18、CONR19R20、NR19R20、PO(OCkH2k+1)2或是式(6)所表示的基团；
    Figure PCTCN2015092009-appb-100007
    或R13表示C2-C20烷基，其间杂有一或多个O、S、SO、SO2、NR26或CO，或是C2-C12烯基，其是未经间杂或间杂有一或多个O、CO或NR26，其中该经间杂的C2-C20烷基及该未经间杂或经间杂的C2-C12烯基是未经取代或经一或多个卤素取代；
    或R13表示C4-C8环烯基、C2-C12炔基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C10环烷基；
    或R13表示苯基或萘基，其各为未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、COR16、CN、NO2、卤素、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、S、CO或NR26的C2-C20烷基或式(7)表示的基团、
    Figure PCTCN2015092009-appb-100008
    或其各经C3-C10环烷基或间杂有一或多个O、S、CO或NR26的C3-C10环烷基取代；
    k表示整数1至10；
    R14表示氢、C3-C8环烷基、C2-C5烯基、C1-C20烷氧基或C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、苯基、C1-C20烷基苯基或 CN；
    或R14表示苯基或萘基，其各未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基、卤素、CN、OR17、SR18和/或NR19R20；
    或R14表示C3-C20杂芳基、C1-C8烷氧基、苄氧基或苯氧基，该苄氧基及苯氧基是未经取代或经一或多个以下基团取代：C1-C6烷基、C1-C4卤代烷基和/或卤素；
    R15表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20、PO(OCkH2k+1)2、SO-C1-C10烷基、SO2-C1-C10烷基、间杂有一或多个O、S或NR26的C2-C20烷基；或其各经C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
    或R15表示氢、C2-C12烯基、未经间杂或间杂有一或多个O、CO或NR26的C3-C8环烷基；或R15表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OR17、SR18、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、NR19R20、COOR17、CONR19R20、PO(OCkH2k+1)2、苯基、式(6)所表示的基团或式(8)所表示的基团、
    Figure PCTCN2015092009-appb-100009
    或该C1-C20烷基是经苯基取代，该苯基是经卤素、C1-C20烷基、C1-C4卤代烷基、OR17、SR18或NR19R20取代；
    或R15表示C2-C20烷基，其间杂有一或多个O、SO或SO2，且该经间杂的C2-C20烷基是未经取代或经一或多个以下基团取代：卤素、OR17、COOR17、CONR19R20、苯基或经OR17、SR18或NR19R20取代的苯基；
    或R15表示C2-C20烷酰基或苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、苯基、OR17、SR18或NR19R20；或R15表示未经取代或经一或多个OR17取代的萘甲酰基或是C3-C14杂芳基羰基；
    或R15表示C2-C12烷氧基羰基，其是未经间杂或间杂有一或多个O且该经间杂或未经间杂的C2-C12烷氧基羰基是未经取代或经一或多个羟基取代；
    或R15表示苯氧基羰基，其是未经取代或经一或多个以下基团取代： C1-C6烷基、卤素、C1-C4卤代烷基、苯基、OR17、SR18或NR19R20；
    或R15表示CN、CONR19R20、NO2、C1-C4卤代烷基、S(O)m-C1-C6烷基、未经取代或经C1-C12烷基或SO2-C1-C6烷基取代的S(O)m-苯基；
    或R15表示SO2O-苯基，其是未经取代或经C1-C12烷基取代；或是二苯基膦酰基或二-(C1-C4烷氧基)-膦酰基；
    m表示1或2；
    R'14具有针对R14所给出含义中的一个；
    R'15具有针对R15所给出含义中的一个；
    X1表示O、S、SO或SO2；
    X2表示O、CO、S或直接键；
    R16表示C6-C20芳基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、CN、NO2、OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C1-C20烷基；或其各经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C3-C20杂芳氧基羰基、OR17、SR18或NR19R20；
    或R16表示氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4)烷基、O(CO)-(C1-C4烷基)、O(CO)-苯基、(CO)OH或(CO)O(C1-C4烷基)；
    或R16表示C2-C12烷基，其间杂有一或多个O、S或NR26；或R16表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C12烯基或C3-C8环烷基；
    或R16表示经SR18取代的苯基，其中该基团R18表示键结至该COR16基团所附接的该咔唑部分的该苯基或萘基环的直接键；
    n表示1至20；
    R17表示氢、苯基-C1-C3烷基、C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-苯基、(CO)OH、(CO)O(C1-C4烷基)、C3-C20环烷基、SO2-(C1-C4卤代烷基)、O(C1-C4卤代烷基)或间杂有一或多个O的C3-C20环烷基；
    或R17表示C2-C20烷基，其间杂有一或多个O、S或NR26；
    或R17表示(CH2CH2O)n+1H、(CH2CH2O)n(CO)-(C1-C8烷基)、C1-C8烷酰基、C2-C12烯基、C3-C6烯酰基或未经间杂或间杂有一或多个O、S、CO或NR26的C3-C20环烷基；
    或R17表示C1-C8烷基-C3-C10环烷基，其是未经间杂或间杂有一或多个O；
    或R17表示苯甲酰基，其是未经取代或经一或多个C1-C6烷基、卤素、OH或C1-C3烷氧基取代；
    或R17表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、OH、C1-C12烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基-胺基或式(7)所表示的基团；
    Figure PCTCN2015092009-appb-100010
    或R17形成键结至该具有由式(2)所表示的基团、或是式(7)所表示的基团所处的苯基或萘基环的其中一个碳原子的直接键、
    Figure PCTCN2015092009-appb-100011
    R18表示氢、C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基，其中该C2-C12烯基、C3-C20环烷基或苯基-C1-C3烷基是未经间杂或间杂有一或多个O、S、CO、NR26或COOR17；或R18是C1-C20烷基，其是未经取代或经一或多个以下基团取代：OH、SH、CN、C3-C6烯氧基、OCH2CH2CN、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C2-C4)烯基、O(CO)-(C1-C4烷基)、O(CO)-苯基或(CO)OR17；
    或R18表示C2-C20烷基，其间杂有一或多个O、S、CO、NR26或COOR17；
    或R18表示(CH2CH2O)nH、(CH2CH2O)n(CO)-(C1-C8烷基)、C2-C8烷酰基或C3-C6烯酰基；
    或R18表示苯甲酰基，其是未经取代或经一或多个以下基团取代：C1-C6烷基、卤素、OH、C1-C4烷氧基或C1-C4烷基硫基；
    或R18表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C12烷基、C1-C4卤代烷基、C1-C12烷氧基、CN、NO2、苯基-C1-C3烷氧基、苯氧基、C1-C12烷基硫基、苯基硫基、N(C1-C12烷基)2、二苯基胺基、(CO)O(C1-C8烷基)、(CO)-C1-C8烷基、(CO)N(C1-C8烷基)2或式(7)所表示的基团
    Figure PCTCN2015092009-appb-100012
    R19及R20彼此独立地为氢、C1-C20烷基、C2-C4羟基烷基、C2-C10烷氧基烷基、C2-C5烯基、C3-C20环烷基、苯基-C1-C3烷基、C1-C8烷酰基、C1-C8烷酰基氧基、C3-C12烯酰基、SO2-(C1-C4卤代烷基)或苯甲酰基；
    或R19及R20表示苯基、萘基或C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：卤素、C1-C4卤代烷基、C1-C20烷氧基、C1-C12烷基、苯甲酰基或C1-C12烷氧基；
    或R19及R20与其所附接的N原子一起形成未经间杂或间杂有O、S或NR17的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、NO2、卤素、C1-C4-卤代烷基、CN、苯基、未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基、或式(7)表示的基团
    Figure PCTCN2015092009-appb-100013
    或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统是未经取代或经一或多个以下基团取代：C1-C20烷基、C1-C4卤代烷基、C1-C20烷氧基、＝O、OR17、SR18、NR21R22、(CO)R23、卤素、NO2、CN、苯基或未经间杂或间杂有一或多个O、S、CO或NR17的C3-C20环烷基、或式(7)表示的基团
    Figure PCTCN2015092009-appb-100014
    R21及R22彼此独立地为氢、C1-C20烷基、C1-C4卤代烷基、C3-C10环烷基或苯基；
    或R21及R22与其所附接的N原子一起形成未经间杂或间杂有O、S或NR26的5元或6元饱和或不饱和环，且该5元或6元饱和或不饱和环是未稠合或该5元或6元饱和或不饱和环与苯环稠合；
    R23表示氢、OH、C1-C20烷基、C1-C4卤代烷基、间杂有一或多个O、CO或NR26的C2-C20烷基、未经间杂或间杂有O、S、CO或NR26的C3-C20环烷基，或R23表示苯基、萘基、苯基-C1-C4烷基、OR17、SR18或NR21R22；
    R24表示(CO)OR17、CONR19R20、(CO)R17；或R24具有针对R19及R20所给出含义中的一个；
    R25表示COOR17、CONR19R20、(CO)R17；或R25具有针对R17所给出含义中的一个；
    R26表示氢、C1-C20烷基、C1-C4卤代烷基、C2-C20烷基，其间杂有一或多个O或CO；或是苯基-C1-C4烷基、C3-C8环烷基，其是未经间杂或间杂有一或多个O或CO；或是(CO)R19；或是苯基，其是未经取代或经一或多个以下基团取代：C1-C20烷基、卤素、C1-C4卤代烷基、OR17、SR18、NR19R20或式(7)表示的基团
    Figure PCTCN2015092009-appb-100015
    但条件为在该分子中存在至少一个式(2)或是式(7)所表示的基团
    Figure PCTCN2015092009-appb-100016
  2. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述所述R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢、C1-C20烷基、COR16、NO2或由式(2)表示的基团；
    Figure PCTCN2015092009-appb-100017
    或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地共同为式(5)所表示的基团；
    Figure PCTCN2015092009-appb-100018
    但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是由式(5)所表示的基团；
    X表示CO或直接键；
    R13表示C-1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OR-17、SR18、COOR17、CONR19R20或PO(OCkH2k+1)2；
    或R13表示C2-C20烷基，其间杂有一或多个O、S、NR26或CO；
    或R13表示苯基或萘基，此两个是未经取代或经COR16取代或由一或多个式(7)表示的基团取代；
    Figure PCTCN2015092009-appb-100019
    R14表示C1-C20烷基、苯基或C1-C8烷氧基；
    R15表示苯基、萘基、C3-C20杂芳基，其各是未经取代或经一或多个以下基团取代：苯基、卤素、C1-C4卤代烷基、OR17、SR18或C2-C20烷基，其间杂有一或多个O或S；或其各经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C4-C20杂芳氧基羰基、OR17、SR18、NR19R20或PO(OCkH2k+1)2；
    或R15表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：OR17、SR18、C3-C8环烷基、C3-C20杂芳基、NR19R20、COOR17、CONR19R20或PO(OCkH2k+1)2；
    R'14具有针对R14所给出含义中之一的；
    R'15具有针对R15所给出含义中之一的；
    R16表示苯基，其是未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或间杂有一或多个O、S或NR26的C2-C20烷基；
    或R16表示苯基，其是经一或多个C1-C20烷基取代，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、COOR17、CONR19R20、苯基、C3-C8环烷基、C3-C20杂芳基、C6-C20芳氧基羰基、C4-C20杂芳氧基羰基、OR17、SR18或NR19R20；
    或R16表示C1-C20烷基，其是未经取代或经以下基团取代：卤素、苯基、OH、SH、CN、C3-C6烯氧基、OCH2CH2(CO)O(C1-C4烷基)、O(CO)-(C1-C4烷基)或(CO)O(C1-C4烷基)；
    R17表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、OCH2CH2(CO)O(C1-C4烷基)、O(C1-C4烷基)、(CO)O(C1-C4烷基)、C3-C20环烷基或间杂有一或多个O的C3-C20环烷基；
    或R17表示C2-C20烷基，其间杂有一或多个O；
    R18表示经COOR17取代的甲基；
    R19及R20彼此独立地为氢、苯基、C1-C20烷基、C1-C8烷酰基或C1-C8烷酰基氧基；
    或R19及R20与其所附接的N原子一起形成杂芳香族环系统，该环系统是未经取代或经由式(7)表示的基团取代；
    Figure PCTCN2015092009-appb-100020
    但条件为在该分子中存在至少一个式(2)或是式(7)所表示的基团
    Figure PCTCN2015092009-appb-100021
  3. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述R1、R2、R3、R4、R5、R6、R7及R8彼此独立地为氢，或R1及R2、R3及R4或R5及R6彼此独立地共同为式(5)所表示的基团；
    Figure PCTCN2015092009-appb-100022
    但条件为R1及R2、R3及R4或R5及R6中的至少一对是由式(5)所表示的基团；
    或R2表示COR16、NO2或是由式(2)所表示的基团或是由式(3)所表示的基团；
    Figure PCTCN2015092009-appb-100023
    或R7表示COR16或是由式(2)所表示的基团；
    R9、R11及R12表示氢；
    R-10表示氢、OR17或COR16；
    X表示CO或直接键；
    R13表示C1-C20烷基，其是未经取代或经一或多个以下基团取代：卤素、R17、OR17、SR18或PO(OCkH2k+1)2；
    或R13表示C2-C20烷基，其间杂有一或多个O；
    或R13表示苯基；
    k表示整数2；
    R14表示C1-C20烷基或噻吩基；
    R15表示苯基或萘基，其各是未经取代或经一或多个OR17或C1-C20烷基取代；
    或R15表示噻吩基、氢、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：OR17、SR18、C3-C8环烷基、NR19R20或COOR17；
    或R15表示C2-C20烷基，其间杂有SO2；
    R16表示苯基或萘基，其各是未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20或C1-C20烷基；
    或R16表示噻吩基；
    R17表示氢、C1-C8烷酰基、C1-C20烷基，该C1-C20烷基是未经取代或经一或多个以下基团取代：卤素、O(CO)-(C1-C4烷基)、O(CO)-(C2-C4烯基)或间杂有一或多个O的C3-C20环烷基；
    或R17表示C2-C20烷基，其间杂有一或多个O；
    R18表示C3-C20环烷基、C1-C20烷基，其是未经取代或经一或多个OH、O(CO)-(C2-C4烯基)或(CO)OR17取代；
    或R18表示苯基，其是未经取代或经一或多个卤素取代；
    R19及R20彼此独立地为C1-C8烷酰基或C1-C8烷酰基氧基；
    或R19及R20与其所附接的N原子一起形成间杂有O的5元或6元饱和环；
    但条件为在该分子中存在至少一个由式(2)所表示的基团；
    Figure PCTCN2015092009-appb-100024
  4. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述碱可溶性树脂(A)包括碱可溶性树脂(A-1)，其中所述碱可溶性树脂(A-1)是由混合物聚合而得，并且所述混合物包括:
    含有聚合性不饱和基的二醇化合物(a-1-1)；
    四羧酸或其酸二酐(a-1-2)；以及
    二羧酸或其酸酐(a-1-3)；
    所述含有聚合性不饱和基的二醇化合物(a-1-1)是由具有至少二个环氧基的环氧化合物及具有至少一个羧酸基及至少一个乙烯性不饱和基的化合物反应而得，且具有至少二个环氧基的环氧化合物包括式(a-1)所示的结构、式(a-2)所示的结构或上述两种结构，
    Figure PCTCN2015092009-appb-100025
    式(a-1)中，W1、W2、W3以及W4各自独立表示氢原子、卤素原子、碳数为1至5的烷基、碳数为1至5的烷氧基、碳数为6至12的芳基或碳数为6至12的芳烷基，
    Figure PCTCN2015092009-appb-100026
    式(a-2)中，W5至W18各自独立表示氢原子、卤素原子、碳数为1至8的烷基或碳数为6至15的芳香基，s表示0至10的整数；
    且该碱可溶性树脂(A-1)的数量平均分子量为1000～8000。
  5. 根据权利要求4所述的感光性树脂组成物，其特征在于，所述四羧酸或其酸二酐(a-1-2)以及所述二羧酸或其酸酐(a-1-3)中，至少一个含有氟原子。
  6. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述碱可溶性树脂(A)包括碱可溶性树脂(A-2)，所述碱可溶性树脂(A-2)是由硅烷单体进行聚缩合来合成，或是使用硅烷单体及其他可聚合用的化合物进行聚缩合来形成。
  7. 根据权利要求1所述的感光性树脂组成物，其特征在于，还包括多分支聚合物(F)，所述多分支聚合物(F)是由式(F2)表示的多巯基化合物与由式(F1)表示的多官能基(甲基)丙烯酸酯反应而形成，
    Figure PCTCN2015092009-appb-100027
    式(F1)中，M1表示氢原子或碳数为1至4的烷基；
    M2表示具有h个羟基的含羟基的化合物中的g个羟基经酯化后的残基，其中h≥g，g表示2至20的整数，
    所述含羟基的化合物为M3(OH)h或所述M3(OH)h经环氧丙烷、环氧氯丙烷、烷基、烷氧基或丙烯酸羟丙酯改性的化合物，
    M3(OH)h为具有碳数为2至18的多元醇、由所述多元醇所形成的多元醇醚、由所述多元醇与酸反应而形成的酯类、或硅酮，
    Figure PCTCN2015092009-appb-100028
    式(F2)中，M4表示单键、碳数为1的烃基、或碳数为2至22的直链或支链的烃基，M4的骨架中可还包括硫原子或构成酯基中的氧原子，
    i表示2至6的整数，其中当M4表示单键时，i表示2；当M4表示碳数为1的烃基时，i表示2至4的整数；当M4表示碳数为2至22的直链或支链的烃基时，i表示2至6的整数。
  8. 根据权利要求1所述的感光性树脂组成物，其特征在于，还包括热起始剂(G)，所述热起始剂(G)是选自由偶氮化合物、过氧化物以及过氧化氢化合物所组的族群的至少一种。
  9. 根据权利要求1所述的感光性树脂组成物，其特征在于，还包括式(10)表示的化合物(H)；
    Figure PCTCN2015092009-appb-100029
    式(10)中，
    Z1、Z2及Z3各自独立代表经亚烷基或亚芳基结合的三烷氧基硅烷基。
  10. 根据权利要求1所述的感光性树脂组成物，其特征在于，基于所述碱可溶性树脂(A)100重量份，所述具有乙烯性不饱和基的化合物(B)的使用量为15重量份至200重量份，所述具有酸性基及至少三个乙烯性不饱和基的化合物(B-1)的使用量为15重量份至150重量份，所述光起始剂(C)的使用量为10重量份至80重量份，所述由式(1)表示的光起始剂(C-1)的使用量为10重量份至70重量份，所述溶剂(D)的使用量为1000至8000重量份，所述黑色颜料(E)的使用量为150至1200重量份。
  11. 根据权利要求4所述的感光性树脂组成物，其特征在于，基于所述碱可溶性树脂(A)100重量份，所述碱可溶性树脂(A-1)的使用量为50重量份至100重量份。
  12. 根据权利要求6所述的感光性树脂组成物，其特征在于，基于所述碱可溶性树脂(A)100重量份，所述具碱可溶性树脂(A-2)的使用量为0重量份至50重量份。
  13. 根据权利要求7所述的感光性树脂组成物，其特征在于，基于所述碱可溶性树脂(A)100重量份，所述多分支聚合物(F)的使用量为3重量份至35重量份。
  14. 根据权利要求8所述的感光性树脂组成物，其特征在于，基于所述碱可溶性树脂(A)100重量份，所述热起始剂(G)的使用量为4重量份至40重量份。
  15. 根据权利要求9所述的感光性树脂组成物，其特征在于，基于所述碱可溶性树脂(A)100重量份，所述式(10)表示的化合物(H)的使用量为1重量份至10重量份。
  16. 一种黑色矩阵，其特征在于，是由权利要求1至15所述的感光性树脂组成物而形成。
  17. 一种彩色滤光片，其特征在于，包括权利要求16所述的黑色矩阵。
  18. 一种液晶显示器，其特征在于，包括权利要求17所述的彩色滤光片。
PCT/CN2015/092009 2014-10-15 2015-10-15 感光性树脂组成物、彩色滤光片及其液晶显示元件 WO2016058545A1 (zh)

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