WO2016058546A1 - 感光性树脂组成物、间隙体、保护膜以及液晶显示元件 - Google Patents

感光性树脂组成物、间隙体、保护膜以及液晶显示元件 Download PDF

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WO2016058546A1
WO2016058546A1 PCT/CN2015/092013 CN2015092013W WO2016058546A1 WO 2016058546 A1 WO2016058546 A1 WO 2016058546A1 CN 2015092013 W CN2015092013 W CN 2015092013W WO 2016058546 A1 WO2016058546 A1 WO 2016058546A1
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group
alkyl
phenyl
substituted
formula
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PCT/CN2015/092013
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English (en)
French (fr)
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蔡宇杰
谢岦庭
吴镇宇
陈奕光
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奇美实业股份有限公司
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Publication of WO2016058546A1 publication Critical patent/WO2016058546A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a photosensitive resin composition, a spacer, a protective film, and a liquid crystal display element.
  • a photosensitive resin composition having high-speed coating property, good adhesion during development, and excellent refractive index, hardness, and resolution, and a spacer or protective film formed using the composition, and a liquid crystal display element thereof .
  • the color-printed pixels and the black matrix on the surface of the color filter layer are uneven, and a protective film is generally formed on the surface of the color filter layer, thereby hiding the unevenness and thereby achieving the flattening requirement. .
  • the protective film In order for the protective film to have characteristics against the above treatment, the protective film needs to have excellent adhesion to the substrate, and also has high transparency, high surface hardness, and a smooth surface.
  • the protective film with high heat resistance and light resistance can also cause discoloration, yellowing or whitening deterioration under long-term use.
  • the protective film also needs to have good water resistance, chemical resistance, solvent resistance, acid resistance, alkali resistance and the like.
  • the gap body is formed by applying a photosensitive composition for the spacer body to the substrate, and then placing a mask of a predetermined shape between the substrate and the exposure source, and developing a gap body after exposure.
  • the finger can be outside the R, G, and B pixels.
  • the gap body is formed at a fixed position to solve the problems of the prior art; the cell gap can also be controlled by the thickness of the coating film formed by the photosensitive component, and the distance between the cell gaps can be easily controlled, and the precision is high.
  • the protective film or the spacer is formed on the color filter or the substrate, the transparency is extremely high. If the transparency of the protective film or the spacer is not good, when applied to a liquid crystal display element, the brightness of the liquid crystal display element is insufficient, which affects the display quality of the liquid crystal display element.
  • Japanese Patent Laid-Open Publication No. 2010-054561 discloses a photosensitive composition for a protective film comprising (A) an alkali-soluble binder resin; (B) a compound having an ethylenically unsaturated group; (C) a photoinitiator; and (D) a solvent; wherein the (B) ethylenically unsaturated group compound has an unsaturated equivalent of from 90 to 450 g/eq, and (B) ethylenic unsaturation In the compound, the unsaturated double bond of the single compound is between 2 and 4, and the weight average molecular weight of the (A) alkali-soluble binder resin is between 10,000 and 20,000.
  • Japanese Patent Laid-Open No. 2004-240241 discloses a photosensitive composition
  • a photosensitive composition comprising (A) a copolymer which is an ethylenically unsaturated carboxylic acid (anhydride) having an epoxy group-containing ethylenic property.
  • the photosensitive resin composition has a problem of poor adhesion, hardness, and coatability during development, and cannot meet the increasing demand for refractive index and resolution in the industry today.
  • the present invention provides a photosensitive resin composition, a spacer, a protective film, and a liquid crystal display element, wherein the photosensitive resin composition includes an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), and light-emitting Starting agent (C) and solvent (D).
  • the ethylenically unsaturated group-containing compound (B) comprises the first compound (B-1) having an ethylenically unsaturated group having the structure of the formula (II),
  • a 5 represents a hydrogen atom or a methyl group
  • a 6 represents a hydrogen atom, an acryloyl group or a methacryloyl group
  • r 3 to 4;
  • 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).
  • 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 of 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 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 ; 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 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)
  • the alkali-soluble resin (A) comprises an alkali-soluble resin (A-1), wherein the alkali-soluble resin (A-1) is an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a1) and other unsaturated compounds (a2) are copolymerized
  • the alkali-soluble resin (A) comprises a resin (A-2) having an unsaturated group, wherein the resin (A-2) having an unsaturated group is polymerized by a mixture.
  • the mixture comprises an epoxy compound (a-1-1) having at least two epoxy groups and having at least one carboxylic acid group And at least one ethylenically unsaturated group compound (a-1-2).
  • the epoxy compound (a-1-1) having at least two epoxy groups includes the structure represented by the formula (a-1), and the formula (a-2) Structure or both 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.
  • 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) comprises a polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group, and the polysiloxane polymer (A- 3) is obtained by hydrolyzing and partially condensing at least one silane monomer represented by the structure of formula (9):
  • w represents an integer from 1 to 3, and when w represents 2 or 3, the plurality of U 1 are each the same or different; and when 4-w represents 2 or 3, the plurality of U 2 are each the same or different;
  • U 1 represents at least one acid anhydride group substituted by a C 1 to C 10 alkyl group, the epoxy-substituted C 1 to C 10 alkyl group or a epoxy-substituted alkoxy group, U 1 represents a hydrogen and the remaining a C 1 to C 10 alkyl group, a C 2 to C 10 alkenyl group or a C 6 to C 15 aromatic group;
  • U 2 represents hydrogen, a C 1 to C 6 alkyl group, a C 1 to C 6 acyl group or a C 6 to C 15 aryl group.
  • the ethylenically unsaturated group-containing first compound (B-1) is used in an amount of 20 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). To 200 Parts by weight.
  • the ethylenically unsaturated group-containing compound (B) comprises the second compound (B-2) containing an ethylenically unsaturated group represented by the following formula (III);
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group
  • l represents an integer from 0 to 4.
  • the ethylenically unsaturated group-containing compound (B) includes the ethylenically unsaturated group-containing third compound (B-3) represented by the following formula (IV);
  • a 3 and A 4 each independently represent a hydrogen atom or a methyl group
  • v represents an integer from 0 to 4.
  • the ethylenically unsaturated group-containing compound (B) includes a fourth compound (B-4) having an ethylenically unsaturated group represented by the following formula (V) or the following formula (VI): );
  • B 1 to B 8 each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B 1 to B 8 includes an ethylenically unsaturated group as a substituent at the end thereof;
  • B 1 to B 6 each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B 1 to B 6 includes an ethylenically unsaturated group as a substituent at the end thereof.
  • the ethylenically unsaturated group-containing compound (B) comprises a fifth compound containing an ethylenically unsaturated group of a diacrylate or dimethacrylate having a linear diol. (B-5), and the linear diol has a carbon number of 2 to 12.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, a C 1 -C 20 alkyl group, or a 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 represented by the formula (5) The group represented;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group, a phenyl group or a naphthyl group
  • R 13 represents a C 1 -C 20 alkyl group, it is unsubstituted or substituted with one or more of the following groups: halogen, OR 17 , SR 18 , COOR 17 , CONR 19 R 20 or NR 19 R 20 , PO(OC k H 2k+1 ) 2 ;
  • R 13 represents a C 2 -C 20 alkyl group, it is unmixed or inter-mixed with at least one O, S, CO or NR 26 ;
  • R 13 is phenyl or naphthyl, each of them is unsubstituted or substituted by COR 16 or substituted by at least one group 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 or a C 1 -C 20 alkyl group;
  • R 15 represents a phenyl group, a naphthyl group or a C 3 -C 20 heteroaryl group, each of them is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C 1 -C 4 haloalkyl, OR 17 , SR 18 , intervening one or more O, S C 2 -C 20 alkyl groups, or C 1 -C 20 alkyl groups are 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 4 -C 20 heteroaryloxycarbonyl, OR 17 , SR 18 , NR 19 R 20 or PO(OC k H 2k+1 ) 2 ;
  • R 15 represents a C 1 -C 20 alkyl group, it 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 Aryl, 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 or a C 1 -C 20 alkyl group
  • R 16 represents a phenyl group, it is unsubstituted or substituted with one or more of the following groups: OR 17 , SR 18 , NR 19 R 20 , intermixed with one or more O, S or NR 26 C 2 - C 20 alkyl, or C 1 -C 20 alkyl, is unsubstituted or substituted with one or more of the following: halo, 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 ;
  • R 16 represents a C 1 -C 20 alkyl group, it 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 (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: 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, wherein the C 3 -C 10 cycloalkyl group is unmissoned or heterozygous with one or more O;
  • R 17 represents a C 2 -C 20 alkyl group, it is a hetero or 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 substituted with a group represented by formula (7);
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom
  • R 1 and R 2 , R 3 and R 4 , 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 , R 5 and R 6 is a group represented by the formula (5);
  • R 2 represents a group represented by COR 16 , NO 2 , formula (2) or a group represented by formula (3),
  • R 7 represents a group represented by COR 16 or formula (2)
  • R 9 , R 11 and R 12 independently of each other represent a hydrogen atom
  • R 10 represents a hydrogen atom, OR 17 , COR 16 ;
  • X represents CO or a direct bond
  • R 13 represents a C 1 -C 20 alkyl group or a phenyl group
  • R 13 represents a C 1 -C 20 alkyl group, it 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, it is a hetero or one or more O;
  • k represents an integer 2;
  • R 14 represents a C 1 -C 20 alkyl group or a thienyl group
  • R 15 represents phenyl, naphthyl, thienyl, O or C 1 -C 20 alkyl
  • R 15 represents phenyl or naphthyl, it is unsubstituted or substituted with one or more OR 17 or C 1 -C 20 alkyl groups;
  • R 15 represents a C 1 -C 20 alkyl group, it 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, it is interspersed with SO 2 ;
  • R 16 represents a phenyl group, a naphthyl group or a thienyl group
  • R 16 represents phenyl or naphthyl, it 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 17 represents a hydrogen atom, a C 1 -C 8 alkanoyl group or a C 1 -C 20 alkyl group
  • R 17 represents a C 1 -C 20 alkyl group, it is unsubstituted or substituted with one or more of the following groups: halogen, O(CO)-(C 1 -C 4 alkyl), O(CO) -(C 2 -C 4 alkenyl), or a C 3 -C 20 cycloalkyl group interspersed with one or more O;
  • R 17 represents a C 2 -C 20 alkyl group, it is a hetero or one or more O;
  • R 18 represents a C 3 -C 20 cycloalkyl group, a C 1 -C 20 alkyl group or a phenyl group;
  • R 18 represents C 3 -C 20 cycloalkyl or C 1 -C 20 alkyl, it 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, it 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 photoinitiator (C-1) represented by the formula (1) is used in an amount of 2 to 20, based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight.
  • the photoinitiator (C) comprises other O-acyl hydrazone compounds (C-2).
  • the other O-acyl hydrazone compound (C-2) comprises a photoinitiator (C-2-I) represented by the following structural formula (10):
  • D 4 and D 5 each independently represent a hydrogen atom, a cyclic, linear or branched alkyl or aryl group having 1 to 12 carbon atoms, and the alkyl or aryl group is not Substituted or substituted with a substituent which is selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group;
  • D 6 and D 7 each independently represent a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, and an alkane having 2 to 12 carbon atoms.
  • E1 and e2 are integers independently representing 0 to 5.
  • the other O-acyl hydrazone compound (C-2) comprises a photoinitiator (C-2-II) represented by the following structural formula (11):
  • J 1 represents a functional group of Ja, Jb-S, and Jc-O, wherein Ja, Jb, and Jc represent a hydrogen atom, an alkyl group, and an aromatic group; and J 2 represents a hydrogen atom, C 1 - C 4 Alkyl or halogen.
  • the ethylenically unsaturated group-containing compound (B) is used in an amount of 50 to 500 parts by weight based on 100 parts by weight of the alkali-soluble resin (A);
  • the photoinitiator (C) is used in an amount of 2 to 200 parts by weight;
  • the solvent (D) is used in an amount of 500 to 5000 parts by weight.
  • the photosensitive resin composition further comprises o-naphthoquinonediazide sulfonate (E).
  • the photosensitive resin composition further includes inorganic particles (F) which are oxides of a Group IV element as a main component.
  • the photosensitive resin composition further includes an organic acid (G), wherein the organic acid (G) has a molecular weight of 1,000 or less.
  • the present invention also provides a spacer body obtained by sequentially applying a pre-baked treatment, an exposure treatment, a development treatment, and a post-baking treatment to the photosensitive resin composition described above to obtain a spacer having a pattern.
  • the present invention also provides a protective film comprising a photosensitive resin composition as described above, which is sequentially subjected to a prebaking treatment, an exposure treatment, a development treatment, and a post-baking treatment to obtain a protective film having a pattern.
  • the present invention further provides a liquid crystal display element comprising the above-described interstitial body.
  • the present invention further provides a liquid crystal display element comprising the above protective film.
  • the present invention provides a photosensitive resin composition
  • a photosensitive resin composition comprising an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a solvent (D).
  • the photosensitive resin composition may further include o-naphthoquinonediazide sulfonate (E), inorganic particles (F), organic acid (G), and additive (H).
  • E o-naphthoquinonediazide sulfonate
  • F inorganic particles
  • organic acid G
  • additive additive
  • 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 a resin (A-2) having an alkali-soluble resin (A-1), an unsaturated group, and a polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group.
  • Alkali soluble resin (A-1) Alkali soluble resin (A-1)
  • the alkali-soluble resin (A-1) is obtained by copolymerizing an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a1) and another unsaturated compound (a2) in a solvent in the presence of a suitable polymerization initiator. .
  • the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) means a compound containing a carboxylic acid group or a carboxylic anhydride structure and an unsaturated bond for polymerization bonding, and the structure thereof is not particularly limited, for example, an unsaturated monocarboxylic acid compound, A saturated dicarboxylic acid compound, an unsaturated acid anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound, or a polycyclic unsaturated acid anhydride compound.
  • the unsaturated monocarboxylic acid compound is (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(meth)acryloyloxybutane Acid ester, 2-(meth)acryloyl ethoxy hexahydrophthalate, 2-(meth)acryloyl ethoxy phthalate, omega-carboxy polycaprolactone polyol monoacrylic acid Ester (trade name: ARONIX M-5300, manufactured by East Asia).
  • the unsaturated dicarboxylic acid compound is maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid or the like.
  • the unsaturated dicarboxylic anhydride compound is an acid anhydride compound of the above unsaturated dicarboxylic acid compound.
  • the polycyclic unsaturated carboxylic acid compound is 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2- Alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl Bicyclo [2.2.1] hept-2-ene.
  • the polycyclic unsaturated dicarboxylic acid compound is 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.
  • the polycyclic unsaturated dicarboxylic anhydride compound is an acid anhydride compound of the above polycyclic unsaturated dicarboxylic acid compound.
  • the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) is acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloyloxy succinate and 2- Methacryloyl ethoxy hexahydrophthalic acid.
  • the unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1) may be used singly or in combination of plural kinds.
  • composition ratio of the unsaturated carboxylic acid-containing or unsaturated carboxylic anhydride compound (a1) of the present invention is from 10 to 50 parts by weight, preferably from 12 to 45 parts by weight, more preferably from 15 to 40 parts by weight.
  • the other unsaturated compound (a2) has a constitution ratio of 50 to 90 parts by weight, preferably 55 to 88 parts by weight, more preferably 60 to 85 parts by weight.
  • the other unsaturated compound (a2) may comprise an epoxy group-containing unsaturated compound (a2-1) and other unsaturated compounds (a2-2).
  • epoxy group-containing unsaturated compound (a2-1) examples include an epoxy group-containing (meth) acrylate compound, an epoxy group-containing ⁇ -alkyl acrylate compound, and a glycidyl ether compound. .
  • the epoxy group-containing (meth) acrylate compound is glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, or (meth)acrylic acid. 3,4-epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxy ring (meth)acrylate Hexyl methyl ester.
  • the epoxy group-containing ⁇ -alkyl acrylate compound is ⁇ -ethyl methacrylate, ⁇ -n-propyl propylene acrylate, ⁇ -n-butyl acrylate epoxy.
  • the glycidyl ether compound is o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p- P-vinylbenzylglycidylether.
  • Preferred examples of the epoxy group-containing unsaturated compound (a2-1) of the present invention are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and methacrylic acid 6,7 - epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether.
  • the other unsaturated compound (a2-2) are an alkyl (meth)acrylate, an alicyclic (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, Methyl hydroxyalkyl acrylate, Polyethers of (meth) acrylate, aromatic vinyl compounds and other unsaturated compounds.
  • the alkyl (meth)acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, or isopropyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, and tertiary butyl (meth)acrylate.
  • the alicyclic (meth) acrylate is cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02, 6] ⁇ -8-yl (meth) acrylate (or dicyclopentanyl (meth) acrylate), dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate, (methyl) ) tetrahydrofurfuryl acrylate.
  • the aryl (meth)acrylate is phenyl (meth)acrylate or benzyl methacrylate.
  • the unsaturated dicarboxylic acid diester is diethyl maleate, diethyl fumarate or diethyl itaconate.
  • the hydroxyalkyl (meth)acrylate is 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.
  • the polyether of (meth) acrylate is polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.
  • the aromatic vinyl compound is styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.
  • the other unsaturated compound is acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, and different Pentadiene, 2,3-dimethyl1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N - succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimide-6 - Maleimide caproate, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide.
  • Preferred examples of the other unsaturated compound (a2-2) of the present invention are methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid Butyl methacrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyloxy (meth) acrylate, styrene, p-methoxy styrene.
  • Other unsaturated compounds (a2-2) according to the invention may be used singly or in combination.
  • the solvent used in the production of the alkali-soluble resin (A-1) of the present invention are an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a dipropylene glycol, a propylene glycol monoalkyl group.
  • the alcohol is methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, or 3-phenyl-1-propanol.
  • the ether is tetrahydrofuran.
  • the glycol ether is ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
  • the ethylene glycol alkyl ether acetate is ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, and ethylene glycol methyl ether acetate.
  • the diethylene glycol is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether. , diethylene glycol methyl ether.
  • the dipropylene glycol is dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether.
  • the propylene glycol monoalkyl ether is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, or propylene glycol monobutyl ether.
  • the propylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, or propylene glycol butyl ether acetate.
  • the propylene glycol alkyl ether propionate is propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate.
  • the aromatic hydrocarbon is toluene or xylene.
  • the ketone is methyl ethyl ketone, cyclohexanone, or diacetone alcohol.
  • the ester is methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxyl Ethyl 2-methylpropionate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ethyl ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Butyl ester, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, butyl ethoxy
  • the solvent used in the production of the alkali-soluble resin (A-1) of the present invention is preferably diethylene glycol dimethyl ether or propylene glycol methyl ether acetate.
  • the solvent used in the production of the other alkali-soluble resin (A-1) according to the present invention may be used singly or in combination.
  • the polymerization initiator used in the production of the alkali-soluble resin (A-1) according to the present invention is specifically an azo compound or a peroxide.
  • azo compound examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile, 4,4'-azobis(4-cyanovaleric acid), dimethyl Base 2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).
  • peroxide dibenzoyl peroxide, dodecyl peroxide, t-butyl peroxyvalerate, 1,1-bis(t-butylperoxy)cyclohexane, and hydrogen peroxide.
  • the polymerization initiators used in the production of the alkali-soluble resin (A-1) according to the present invention may be used singly or in combination.
  • the alkali-soluble resin (A-1) of the present invention has a weight average molecular weight of usually 3,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 60,000.
  • the molecular weight of the alkali-soluble resin (A-1) can be adjusted by using a single resin or a resin of two or more different molecular weights.
  • the alkali-soluble resin (A-1) is used in an amount of 30 to 100 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably 35 To 95 parts by weight; more preferably 40 to 90 parts by weight.
  • the unsaturated group-containing resin (A-2) is obtained by polymerizing a mixture, and the mixture includes an epoxy compound (a-1-1) having at least two epoxy groups and having at least one carboxylic acid group and at least one An ethylenically unsaturated group compound (a-1-2).
  • the epoxy compound (a-1-1) having at least two epoxy groups includes a structure represented by the formula (a-1), a structure represented by the formula (a-2) or the above two 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.
  • 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 an analogue thereof; (3) Commercial products 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.
  • the synthesis method of the epoxy compound having at least two epoxy groups containing the structure represented by the formula (a-2) is as follows: First, a compound having a structure of the following formula (a-2-II) is used in the presence of an acid catalyst. After condensation reaction with a phenol, a compound having the structure of the formula (a-2-I) is formed. Next, an excess of halogenated propylene oxide is added to carry out dehydrohalogenation of the halogenated propylene oxide with a compound having the structure of the formula (a-2-I), and the obtained formula (a-2) is obtained. An epoxy compound having at least two epoxy groups.
  • W 19 and W 20 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; B 1 and B; 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • the above halogen atom is preferably chlorine or bromine.
  • the above alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group.
  • the above alkoxy group is preferably a methoxy group or an ethoxy group.
  • phenols include: phenol, cresol, ethylphenol, n-propanol, isobutylphenol, t-butanol, octylphenol, nonylphenol, indophenol, methylbutylphenol, di-tert-butyl Phenol, vinyl phenol, propylene phenol, B Alkynol, cyclopentylphenol, cyclohexylphenol, cyclohexylcresol or the like.
  • the above phenols may be used singly or in combination of two or more.
  • the compound having the structure of the above formula (a-2-II) is used in an amount of 1 mol, and the phenol is used in an amount of 0.5 mol to 20 mol, and preferably 2 mol to 15 mol.
  • the acid catalyst examples include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride or the like.
  • the acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or a combination of the above compounds.
  • the acid catalysts may be used singly or in combination of two or more.
  • the amount of the above acid catalyst used is not particularly limited.
  • the use amount of the compound having the structure of the above formula (a-2-II) is 100% by weight (wt%), and the acid catalyst is preferably used in an amount of from 0.1% by weight to 30% by weight.
  • the above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent.
  • specific examples of the above organic solvent include toluene, xylene, methyl isobutyl ketone or the like.
  • the above organic solvents may be used singly or in combination of two or more.
  • the organic solvent is used in an amount of 50% by weight to 300% by weight, preferably 100% by weight to 250% by weight based on the total weight of the compound having the formula (a-2-II) and the phenol. Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the condensation reaction has an operation time of 1 hour to 8 hours.
  • a neutralization treatment or a water washing treatment may be performed.
  • the above neutralization treatment is to adjust the pH of the solution after the reaction to pH 3 to pH 7, and preferably pH 5 to pH 7.
  • the above water washing treatment can be carried out using a neutralizing agent, wherein the neutralizing agent is an alkaline substance, and specifically includes: an alkali metal hydroxide of sodium hydroxide, potassium hydroxide or the like; calcium hydroxide and hydrogen An alkaline earth metal hydroxide of magnesium oxide or the like; an organic amine of diethylenetriamine, triethylenetetramine, aniline, phenylenediamine or the like; ammonia, sodium dihydrogen phosphate or a combination of the above compounds.
  • the neutralizing agent is an alkaline substance, and specifically includes: an alkali metal hydroxide of sodium hydroxide, potassium hydroxide or the like; calcium hydroxide and hydrogen An alkaline earth metal hydroxide of magnesium oxide or the like; an organic amine of diethylenetriamine, triethylenetetramine
  • the above neutralizing agents may be used singly or in combination of two or more.
  • the above water washing treatment can be carried out by a conventional method, for example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be repeated. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent can be distilled off by heat treatment under reduced pressure, and concentrated, so that a compound having the structure of the formula (a-2-I) can be obtained. .
  • halogenated propylene oxide examples include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or a combination of the above compounds.
  • An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added during the reaction before the dehydrohalogenation reaction.
  • Dehydrohalogenation reaction described above The operating temperature is from 20 ° C to 120 ° C and the operating time ranges from 1 hour to 10 hours.
  • the alkali metal hydroxide added in the above dehydrohalogenation reaction may also be an aqueous solution thereof.
  • water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing. Water, and the halogenated propylene oxide can be continuously refluxed into the reaction system.
  • a quaternary ammonium salt of tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like may be added as a catalyst, and at 50 ° C to 150 ° C After the reaction is carried out at ° C for 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Next, the reaction is allowed to proceed for 1 hour to 10 hours at a temperature of from 20 ° C to 120 ° C to carry out a dehydrohalogenation reaction.
  • the above-mentioned halogenated propylene oxide is used in an amount of from 1 equivalent to 20 equivalents, and preferably from 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the compound having the structure of the formula (a-2-I).
  • the total equivalent weight of the hydroxyl group in the compound having the structure of the formula (a-2-I) is 1 equivalent, and the amount of the alkali metal hydroxide added in the above dehydrohalogenation reaction is 0.8 to 15 equivalents, and It is preferably from 0.9 equivalents to 11 equivalents.
  • an alcohol of methanol, ethanol or the like may be added.
  • an aprotic polar solvent of dimethyl sulfone, dimethyl sulfoxide or the like may be added to carry out the reaction.
  • the total amount of the halogenated propylene oxide based on the above is 100% by weight, and the alcohol is used in an amount of 2% by weight to 20% by weight, and preferably 4% by weight to 15% by weight.
  • the total amount of the halogenated propylene oxide is 100% by weight, and the aprotic polar solvent is used in an amount of 5 wt% to 100 wt%, and preferably 10 wt% to 90 wt%. %.
  • a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and depressurizing, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.
  • the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone or an alkali metal hydroxide aqueous solution such as sodium hydroxide or potassium hydroxide. And the dehydrohalogenation reaction is carried out again.
  • the total hydroxyl group equivalent weight in the compound having the structure of the above formula (a-2-I) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, and preferably 0.05 mole to 0.2 mole.
  • the above dehydrohalogenation reaction has an operating temperature range of 50 ° C to 120 ° C, and the operating time range is 0.5 small. It takes up to 2 hours.
  • the salts are removed by filtration, washing, and the like. Further, by evaporating a solvent such as toluene or methyl isobutyl ketone by heating and pressure reduction, an epoxy having at least two epoxy groups having a structure represented by the formula (a-2) can be obtained.
  • a solvent such as toluene or methyl isobutyl ketone
  • Specific examples of the 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.
  • the compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from one of the groups 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-hydroxyl group Ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate or the like Things.
  • carboxylic anhydride compound described herein may be selected from one of the groups consisting of the following (1) to (2):
  • succinic anhydride maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, A a dicarboxylic anhydride compound of hexahydrophthalic anhydride, methyl bridgedmethylenetetrahydrophthalic anhydride, chlorinic anhydride, glutaric anhydride, trimellitic anhydride or the like;
  • the alkali-soluble resin (A-2) of the present invention has a weight average molecular weight of usually 600 to 10,000, preferably 800 to 8,000, more preferably 1,000 to 6,000.
  • the molecular weight of the alkali-soluble resin (A-2) can be adjusted by using a single resin or a resin of two or more different molecular weights.
  • the resin (A-2) having an unsaturated group is used in an amount of from 0 to 70 parts by weight, preferably from 5 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). It is preferably 10 to 50 parts by weight.
  • the resin (A-2) having an unsaturated group is used as the photosensitive resin composition, the hardness of the protective film/gap body obtained by the photosensitive resin composition is preferable.
  • Polysiloxane polymer having an acid anhydride group or an epoxy group (A-3) having an acid anhydride group or an epoxy group (A-3)
  • the alkali-soluble resin (A) includes a polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group, and the polysiloxane polymer (A-3) is polymerized by a reactant [ That is, a hydrolysis and a partial condensation reaction are formed, and the reactant may include a silane monomer, a siloxane prepolymer, or a silane monomer and a poly A combination of silicone prepolymers.
  • the polysiloxane polymer (A-3) is obtained by hydrolyzing and partially condensing at least one silane monomer having the structure of the formula (9):
  • w represents an integer from 1 to 3, and when w represents 2 or 3, the plurality of U 1 are each the same or different; and when 4-w represents 2 or 3, the plurality of U 2 are each the same or different;
  • U 1 represents at least one acid anhydride group substituted by a C 1 to C 10 alkyl group, the epoxy-substituted C 1 to C 10 alkyl group or a epoxy-substituted alkoxy group, U 1 represents a hydrogen and the remaining a C 1 to C 10 alkyl group, a C 2 to C 10 alkenyl group or a C 6 to C 15 aromatic group;
  • U 2 represents hydrogen, a C 1 to C 6 alkyl group, a C 1 to C 6 acyl group or a C 6 to C 15 aryl group.
  • C 1 to C 10 alkyl group substituted with an acid anhydride group are, for example, ethyl succinic anhydride, propyl succinic anhydride or propyl glutaric anhydride.
  • epoxy-substituted C 1 to C 10 alkyl group such as oxetanylpentyl or 2-(3,4-epoxycyclohexyl)ethyl [2-(3) , 4-epoxycyclohexyl)ethyl] and the like.
  • epoxy group-substituted oxyalkyl group examples include, for example, glycidoxypropyl or 2-oxetanylbutoxy.
  • the aforementioned alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl or n-butyl groups and the like.
  • Acyl groups can include, but are not limited to, acetyl groups.
  • the aryl group can include, but is not limited to, a phenyl group.
  • the silane monomer represented by the formula (9) may include, but is not limited to, 3-glycidoxypropyltrimethoxysilane (TMS-GAA), 3-glycidoxypropyltriethoxylate.
  • the siloxane monomer includes, but is not limited to, the structure shown by the following structural formula (9-1):
  • U 9 represents a group selected from the group consisting of a hydrogen atom, a C 1 to C 10 alkyl group, a C 2 to C 10 alkenyl group, and a C 6 to C 15 aryl group, wherein the C 1 to C 10 alkyl group Does not contain a carboxylic anhydride substituent;
  • U 10 is a group independently selected from the group consisting of a hydrogen atom, a C 1 to C 6 alkyl group, a C 1 to C 6 acyl group, and a C 6 to C 15 aryl group;
  • u represents an integer from 1 to 3; when u represents 2 or 3, the plural U 9 may be the same or different; when (4-u) represents 2, 3 or 4, the plural U 10 may be the same or different.
  • the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-butyl, trifluoromethyl, 3,3. , 3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl or 3-isocyanatopropyl, and the like.
  • the alkenyl group may include, but is not limited to, a vinyl group, a 3-acryloxypropyl group, a 3-methacryloxypropyl group, and the like.
  • the aryl group may include, but is not limited to, phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl, 4-hydroxy-5- ( p-Hydroxyphenylcarbonyloxy)pentyl or naphthyl and the like.
  • the alkyl group may include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like.
  • Acyl groups can include, but are not limited to, acetyl groups.
  • the aryl group can include, but is not limited to, a phenyl group.
  • the silane monomer represented by the formula (9-1) may include, but is not limited to, tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl Tri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyl Triethoxysilane, mercaptotrime
  • the carboxylic anhydride contained in the compound (9) is self-opened to have a hydrophilic carboxylate.
  • the polysiloxane polymer (A-3) obtained above has better developability to an alkaline developer.
  • the temperature of the polymerization reaction is such that the carboxylic anhydride is sufficiently ring-opened, and it is preferred to carry out the reaction at a temperature higher than 100 ° C for 30 minutes.
  • the amount of carboxylic acid anhydride ring opening is increased relative to the polysiloxane.
  • the silicon atom in the compound (A-3) is not limited, and is preferably more than 10 mol%.
  • the carboxylate is less than 10 mol%, the hydrophilicity of the polysiloxane polymer (A-1) is insufficient. Therefore, when the applied pattern is developed in an alkaline developing solution, low photosensitivity and developability are caused.
  • the content of the carboxylate can be determined by, for example, but not limited to, the following method.
  • a benzene standard and a polysiloxane polymer (A-1) were mixed for elemental analysis and 1 H-NMR measurement, and the number of moles of benzene to Si atoms in the elemental analysis was calculated.
  • the peak area of the carboxylic acid and the peak area of benzene were measured by 1 H-NMR (using 1 H-NMR: CDCl 3 solvent), and the carboxylic acid anhydride of the silicon atom in the polysiloxane polymer (A-1) was opened. The amount can be calculated by the number of moles of benzene.
  • the polymerization reactant of the aforementioned polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group may comprise a polysiloxane prepolymer represented by the following formula (9-2):
  • U 11 , U 12 , U 13 and U 14 may be the same or different and are respectively selected from a hydrogen atom, a C 1 to C 10 alkyl group, a C 2 to C 6 alkenyl group and a C 6 to C 15 group .
  • the group may include, but is not limited to, methyl, ethyl or n-propyl groups and the like.
  • the alkenyl group may include, but is not limited to, a vinyl group, an acryloxypropyl group or a methacryloxypropyl group, and the like.
  • the aromatic group may include, but is not limited to, a phenyl group, a tolyl group or a naphthyl group;
  • v is an integer between 1 and 1000; preferably, v is an integer between 3 and 300; more preferably, v is an integer between 5 and 200.
  • U 15 and U 16 are each selected from the group consisting of a hydrogen atom, a C 1 to C 6 alkyl group, a C 1 to C 6 acyl group, and a C 6 to C 15 aryl group; wherein the alkyl group, the acyl group or The aryl group preferably contains a substituent.
  • alkyl groups are, for example but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like; acyl groups such as, but not limited to, acetyl; aryl groups such as, but not limited to, phenyl.
  • the polysiloxane prepolymer represented by the formula (9-2) may include, but is 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 manufactured by Gelest Silanol terminal polysiloxanes of the type DM-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (minutes) The amount is 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 499000) , DMS-S38 (molecular weight 58000), DMS-S42 (molecular weight 77000
  • the polysiloxane polymer can be prepared by polymerization by the aforementioned silane monomer and/or polysiloxane prepolymer, or by combining silicon dioxide particles via copolymerization. preparation.
  • the average particle diameter of the silica particles is not particularly limited, and the average particle diameter thereof ranges from 2 nm to 250 nm. Preferably, the average particle size ranges from 5 nm to 200 nm. More preferably, the average particle diameter ranges from 10 nm to 100 nm.
  • the silica particles may include, but are not limited to, those manufactured by Catalyst Chemical Co., Ltd., model number OSCAR 1132 (particle diameter: 12 nm, and dispersant is methanol), OSCAR 1332 (particle diameter: 12 nm, and dispersant is n-propanol) , OSCAR 105 (particle size is 60 nm, and the dispersant is ⁇ -butyrolactone) or OSCAR 106 (particle size is 120 nm, and the dispersant is diacetone alcohol); manufactured by Fuso Chemical Co., Ltd., model Quartron PL -1-IPA (particle size 13 nm, and dispersant is isopropanone), Quartron PL-1-TOL (particle size 13 nm, and dispersant is toluene), Quartron PL-2L-PGME (particle size 18 nm, and The dispersant is propylene glycol monomethyl ether) or Quartron PL
  • IPA-ST particle size is 12 nm, and dispersed.
  • the agent is isopropanol
  • EG-ST particle size is 12nm
  • the dispersant is ethylene glycol
  • IPA-ST-L particle size is 45nm
  • the dispersant is isopropanol
  • IPA-ST-ZL Production of particle size: 100 nm, and dispersant is isopropyl alcohol.
  • the silica particles may be used singly or in combination of plural kinds.
  • a general method can be used, for example, a solvent and water are added to the silane monomer, and a catalyst can be selectively added. Next, the mixture is heated and stirred at 50 ° C to 150 ° C for 0.5 hour to 120 hours. When stirring, the reaction can remove by-products (alcohols, water, etc.) by distillation.
  • the solvent is not particularly limited and may be the same as or different from the solvent (D) contained in the photosensitive resin composition of the present invention.
  • the solvent is used in an amount of 15 g to 1200 g based on the total amount of the silane monomer used in an amount of 100 g.
  • the solvent is used in an amount of from 20 grams to 1100 grams. More preferably, the solvent is used in an amount of from 30 g to 1000 g.
  • the water used for hydrolysis is hydrolyzed
  • the amount used is from 0.5 moles to 2 moles.
  • the above catalyst is not particularly limited.
  • the catalyst may be selected from an acid catalyst or a base catalyst.
  • the acid catalyst may include, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, or an ion exchange resin or the like.
  • the base catalyst may include, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, Potassium hydroxide, an alkoxysilane having an amine group, an ion exchange resin, or the like.
  • the catalyst is used in an amount ranging from 0.005 g to 15 g based on the total amount of the silane monomer being 100 g.
  • the catalyst is used in an amount ranging from 0.01 g to 12 g. More preferably, the catalyst is used in an amount ranging from 0.05 g to 10 g.
  • the polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group obtained by a condensation reaction is preferably free from by-products (such as alcohols or water) and a catalyst, and thus The polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group can be selectively purified.
  • the purification method is not particularly limited, and it is preferred to dilute the polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group using a hydrophobic solvent, followed by concentrating the organic layer washed several times with water by an evaporator. To remove alcohol or water. Alternatively, the catalyst can be removed using an ion exchange resin.
  • the alkali-soluble resin (A-3) of the present invention has a weight average molecular weight of usually 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 3,000 to 30,000.
  • the molecular weight of the alkali-soluble resin (A-3) can be adjusted by using a single resin or a resin of two or more different molecular weights.
  • the polysiloxane polymer (A-3) having an acid anhydride group or an epoxy group is used in an amount of from 0 to 70 parts by weight, preferably from 0 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). 5 to 60 parts by weight, more preferably 10 to 50 parts by weight.
  • the high-speed coating property of the protective film/gap body obtained by the photosensitive resin composition is preferable.
  • the other alkali-soluble resin (A-4) means a resin which is soluble in an aqueous alkaline solution, and the configuration thereof is not particularly limited.
  • the other alkali-soluble resin ( A-4) means a carboxylic acid group-containing resin, a phenol-novolac resin, or the like.
  • the ethylenically unsaturated group-containing compound (B) includes a first compound (B-1) containing an ethylenically unsaturated group, a second compound (B-2) containing an ethylenically unsaturated group, and an ethylenically unsaturated group.
  • the ethylenically unsaturated group-containing first compound (B) includes the ethylenically unsaturated group-containing compound (B-1) having the structure of the formula (II).
  • a 5 represents a hydrogen atom or a methyl group
  • a 6 represents a hydrogen atom, an acryloyl group or a methacryloyl group
  • r 3 to 4.
  • the ethylenically unsaturated group-containing first compound (B-1) includes, but is not limited to, pentaerythritol pentoxide (meth) acrylate, pentaerythritol deca (meth) acrylate, and five Any combination of the above compounds of pentaerythritol eleven (meth) acrylate or pentaerythritol tetra(meth) acrylate.
  • the ethylenically unsaturated group-containing first compound (B-1) is used in an amount of from 20 parts by weight to 200 parts by weight, based on 100 parts by weight based on the total amount of the alkali-soluble resin (A), preferably 30 parts by weight.
  • the portion is 150 parts by weight, more preferably 40 parts by weight to 100 parts by weight.
  • the ethylenically unsaturated group-containing compound (B) includes a second compound (B-2) containing an ethylenically unsaturated group.
  • the second unsaturated compound-containing compound (B-2) includes a (meth) acrylate compound monomer represented by the following formula (III).
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group
  • l represents an integer from 0 to 4.
  • the ethylenically unsaturated group-containing second compound (B-2) is used in an amount of 15 to 150 parts by weight, preferably 20 to 130 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 25 to 110 parts by weight.
  • the second resin (B-2) containing an ethylenically unsaturated group is used as the photosensitive resin composition, the protective film/gap body obtained by the photosensitive resin composition is excellent in adhesion and refractive index during development. .
  • the ethylenically unsaturated group-containing compound (B) includes a third compound (B-3) containing an ethylenically unsaturated group.
  • the third compound (B-3) containing an ethylenically unsaturated group includes a (meth) acrylate compound monomer represented by the following formula (IV).
  • a 3 and A 4 each independently represent a hydrogen atom or a methyl group
  • v represents an integer from 0 to 4.
  • v In the formula (IV), represents the average number of additions per molecule of the alkyleneoxy group.
  • the ethylenically unsaturated group-containing third compound (B-3) is used in an amount of 15 to 150 parts by weight, preferably 20 to 130 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 25 to 110 parts by weight.
  • the third resin (B-3) containing an ethylenically unsaturated group is used as the photosensitive resin composition, the protective film/gap body obtained by the photosensitive resin composition is excellent in adhesion and refractive index during development. .
  • the ethylenically unsaturated group-containing compound (B) includes a fourth compound (B-4) containing an ethylenically unsaturated group.
  • the ethylenically unsaturated group-containing fourth compound (B-4) includes a dioxane-based unsaturated compound such as a 1,3-dioxane skeleton and/or a 1,3-dioxolane skeleton. .
  • the structure of the dioxane-based unsaturated compound containing a 1,3-dioxane skeleton is represented by the following formula (V); and the dioxane-based unsaturated compound containing a 1,3-dioxolane skeleton
  • V The structure is as shown in the following formula (VI):
  • B 1 to B 8 each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B 1 to B 8 includes an ethylenically unsaturated group as a substituent at its end;
  • B 1 to B 6 each independently represent a hydrogen atom or a hydrocarbon group, and at least one of B 1 to B 6 includes an ethylenically unsaturated group as a substituent at the end thereof.
  • B 1 to B 8 are a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 18 carbon atoms. Specific examples thereof are an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a cycloalkyl group and the like; and among them, an alkyl group is preferred.
  • B 1 to B 8 are an alkyl group, it is preferably a linear or branched alkyl group having 1 to 8 carbon atoms; more preferably a linear alkyl group having 1 to 4 carbon atoms; Methyl or ethyl.
  • At least one of B 1 to B 8 has a substituent having an ethylenically unsaturated group at its end; or in the formula (VI), at least one of B 1 to B 6 contains an ethyl group at its end.
  • the substituent of the unsaturated group, wherein the use of the ethylenically unsaturated substituent is not limited.
  • At least one of B 1 to B 8 has a substituent having an ethylenically unsaturated group at its end; or in the formula (VI), at least one of B 1 to B 6 contains an ethyl group at its end.
  • a substituent of an unsaturated group, wherein the ethylenically unsaturated substituent is preferably a (meth)acryloyloxy group or an (meth)acrylamide group, and its reactivity and polymerization result are obtained.
  • the softness of the product is preferred.
  • the substitution at the end of B 1 to B 8 of formula (V) or B 1 to B 6 in formula (VI) is based on the inclusion of 1 to 2 (meth)acrylic acid derivatives in one molecule, then the compound The viscosity and the physical properties after hardening are preferred.
  • the ethylenically unsaturated group-containing fourth compound (B-4) has a structure represented by the following formulas (b4-1) to (b4-23):
  • a preferred embodiment of the ethylenically unsaturated group-containing fourth compound (B-4) of the present invention is the above formula (b4-2), formula (b4-3), formula (b4-4), and formula (b4). -13) and a compound represented by the formula (b4-15).
  • the ethylenically unsaturated group-containing fourth compound (B-4) is used in an amount of 5 to 50 parts by weight, preferably 7 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 10 to 30 parts by weight.
  • the fourth compound (B-4) containing an ethylenically unsaturated group is used as the photosensitive resin composition, the hardness of the protective film/gap body obtained by the photosensitive resin composition is preferable.
  • the ethylenically unsaturated group-containing compound (B) includes a fifth compound (B-5) containing an ethylenically unsaturated group.
  • the fifth compound (B-5) containing an ethylenically unsaturated group includes a diacrylate or dimethacrylate having a linear diol.
  • the diacrylate or dimethacrylate of the chain diol has two reactive unsaturated functional groups, and such functional groups are bonded by molecular chains having no cyclic structure.
  • the aforementioned molecular chain is preferably a straight chain and has a carbon number of 2 or more.
  • the carbon number of the aforementioned molecular chain is preferably 12 or less.
  • the fifth compound (B-5) containing an ethylenically unsaturated group is preferably ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butylene.
  • the ethylenically unsaturated group-containing fifth compound (B-5) is used in an amount of 10 to 150 parts by weight, preferably 20 to 120 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); more preferably It is 30 to 100 parts by weight.
  • the fifth unsaturated compound-containing compound (B-5) is used as the photosensitive resin composition, the high-speed coating property of the protective film/gap obtained by the photosensitive resin composition is preferable.
  • the ethylenically unsaturated group-containing compound (B) may also optionally include another ethylenically unsaturated group-containing compound (B-6).
  • the other ethylenically unsaturated group-containing compound (B-6) may include, but is not limited to, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(methyl) ) acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modified tri ( Tris(hydroxy)ethyl isocyanate, trimethylolpropyl tris(meth)acrylate, ethylene oxide (referred to as EO) modified tris(hydroxy)acrylic acid Propyl acrylate, propylene oxide modified (PO) trimethylol propyl tris(meth)acrylate, tripropylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, pentaerythritol Tris (meth) acrylate
  • the total amount of the ethylenically unsaturated group-containing compound (B) to be used is 50 parts by weight to 500 parts by weight, preferably 60 parts by weight to 450 parts, based on 100 parts by weight of the total amount of the alkali-soluble resin (A).
  • the parts by weight are more preferably from 70 parts by weight to 400 parts by weight.
  • the photoinitiator (C) includes a photoinitiator (C-1), other O-acyl hydrazone compounds (C-2), and other photoinitiators (C-3).
  • 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).
  • 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 of 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 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 ; 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 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)
  • the compound of formula (1) 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 formula (5) The group represented.
  • C 1 -C 20 alkyl group is a straight chain or branched and is (e.g.) 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 group is 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-have alkoxycarbonyl 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.
  • the C 6 -C 20 aryl group is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, fluorenyl, tetracylphenyl, tert-triphenyl, etc., especially phenyl or naphthyl, preferably Is a phenyl group.
  • 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.
  • Substituted aryl is 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 time, respectively , 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.
  • the compound of formula (1) is characterized in that at least one phenyl ring is partially fused to the carbazole to form a "naphthyl" ring. That is, one of the above structures is given by the formula (1). .
  • 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 thicker than 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 correspondingly Ring, for example
  • 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 the same species or different species More than one hetero atom.
  • Suitable 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.
  • 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, 3rd) Various methods are described in Volume, Academic Press).
  • a polar solvent eg dimethylacetamide (DMA), DMA
  • DMA dimethylacetamide
  • the aldehyde or ketone is reacted with hydroxylamine or a salt thereof in an aqueous solution, ethanol or aqueous ethanol solution.
  • 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. These 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 independently of one another hydrogen, C 1 -C 20 alkyl, said C 1 -C 20 alkyl group is unsubstituted or substituted with one or more of the following radicals: halogen , 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 with one of the carbon atoms of 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 said meta-hetero C 2 -C 20 alkyl group and said un- or hetero- or hetero-C 2 -C 12 alkenyl group are unsubstituted or one or more Halogen substitution;
  • 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 or more O, S or NR C 2 -C 20 alkyl 26; each warp or a C 1 -C 20 alkyl, said C 1 -C 20 alkyl group is unsubstituted or substituted with one or more Substituted by: halogen, COOR 17 , CONR 19 R 20 , phenyl, C 3 -C 8 cycloalkyl, C 3 -C 20 heteroaryl, C 6
  • 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 , (6) the indicated group
  • Phenyl; or the C 1 -C 20 alkyl group is substituted by a phenyl group which is halogen, C 1 -C 20 alkyl, C 1 -C 4 haloalkyl, OR 17 , SR 18 or NR 19 R 20 substitution;
  • R 15 represents a C 2 -C 20 alkyl group in which one or more O, SO or SO 2 are heterogeneous, and the meta-hetero C 2 -C 20 alkyl group is unsubstituted or has one or more of the following groups Group substitution: 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 meta- or un-doped C 2 -C 12 alkoxycarbonyl group is unsubstituted or Substituted by one or more hydroxyl groups;
  • 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' 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 20
  • R 16 represents hydrogen, C 1 -C 20 alkyl, said C 1 -C 20 alkyl group 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 said group R 18 represents a direct bond to said phenyl or naphthyl ring bonded to said oxazole moiety to which said 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 said C 2 -C 12 alkenyl, C 3 -C 20 ring An alkyl or phenyl-C 1 -C 3 alkyl group having 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 1 2 enoyl, 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 not
  • 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 not
  • the saturated 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, interrupted by one or more O, CO or NR C 2 -C 20 alkyl 26 or interrupted by intermingled without 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, which are unsubstituted or substituted by COR 16 or via one or more Replace
  • 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 of which is substituted by one or more C 1 -C 20 alkyl groups, said 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 aryloxy a carbonyl group, a C 4 -C 20 heteroaryloxycarbonyl group, 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 , 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, a C 1 -C 20 alkyl 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 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.
  • a further object of the invention is a compound of the 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 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 formula (5);
  • R 2 represents a group represented by COR 16 , NO 2 , formula (2) or a group represented by formula (3);
  • R 7 represents 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, said C 1 -C 20 alkyl 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;
  • 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 or a group represented by formula (2)
  • 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 independently of each other are a group represented by the formula (5)
  • R 3 and R 4 or R 1 and R 2 together are a group represented by formula (5)
  • R 3 and R 4 and R 5 and R 6 together are a group represented by formula (5)
  • R 3 and R 4 especially together are a group represented by the formula (5)
  • R 1 , R 5 , R 6 and R 8 represent hydrogen.
  • R 7 is especially hydrogen, a group represented by formula (2) Or COR 16 .
  • R 7 is a group represented by formula (2)
  • R 2 is especially a group represented by the formula (2)
  • R 2 together with R 1 is a group represented by formula (5)
  • R 2 is especially COR 16 .
  • 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, which is unsubstituted or substituted with one two 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 is unsubstituted or substituted with 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 (7)
  • 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 Substituted by a plurality of halogens or phenyl groups; or R 14 represents a phenyl or naphthyl group, which are 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 ; 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, said C 3 -C 8 naphthenic 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-carbonyl, NR 19 R
  • 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 alkyl, said C 1 -C 20 alkyl 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 5 -C 20 heteroaryl, C 6 -C 20 aryloxycarbonyl, C 5 -C 20 heteroaryloxycarbonyl,
  • 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 groups, (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, said ring system Substituted or substituted with one or more of the following groups: a C 1 -C 20 alkyl group, a C 1 -C 4 haloalkyl group,
  • 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 .
  • the preferred of R 25 is 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 amount of (C-1) used is 2 to 20 parts by weight, preferably 2 parts by weight to 15 parts by weight, more preferably 2 parts by weight to 10 parts by weight.
  • the photosensitive resin composition does not use the photoinitiator (C-1)
  • the protective film/gap body obtained by the photosensitive resin composition has poor adhesion and resolution during development.
  • the photoinitiator (C) also includes other O-acyl hydrazone compounds (C-2).
  • the other O-acyl hydrazone compound (C-2) includes a photoinitiator (C-2-I) represented by the following structural formula (10):
  • D 4 and D 5 each independently represent a hydrogen atom, a cyclic, linear or branched alkyl or aryl group having 1 to 12 carbon atoms, and the alkyl or aryl group is not Substituted or substituted with a substituent which is selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group;
  • D 6 and D 7 are each independently a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, and having 2 to 12 carbons.
  • E1 and e2 are integers independently representing 0 to 5.
  • a specific example of the photoinitiator (C-2-I) is: 1-[4-(phenylthio)phenyl]-propane-3-cyclopentane-1,2-dione 2-( O-benzoyl hydrazine), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyl hydrazine), 1-[4-(phenyl sulfonate) Phenyl)-octane-1,2-dione 2-(O-benzoylhydrazine); the above photoinitiator (C-2-I) can be used alone or in combination, depending on the actual Need to be determined.
  • the other O-acyl hydrazone compound (C-2) further includes a photoinitiator (C-2-II) represented by the following structural formula (11):
  • J 1 represents a functional group of Ja, Jb-S, and Jc-O, wherein Ja, Jb, and Jc represent a hydrogen atom, an alkyl group, and an aromatic group; and J 2 represents a hydrogen atom, C 1 - C 4 Alkyl or halogen.
  • Preferred photoinitiators (C-2-II) of the present invention are, for example, ethane ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9hydro-carbazole- 3-Substituent]-, 1-(oxy-acetyl oxime) (Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime )) (formula is represented by formula (11-1)), ethane ketone, 1-[9-ethyl-6-(2-chloro-4benzenesulfobenzoyl)-9hydro-carbazole- 3-Substituent]-, 1-(oxy-acetyl oxime) (Ethanone, 1-[9-ethyl-6-(2-chloro-4-benzyl sulfonyl benzoyl)-9H-carbazole-3
  • the other O-acyl hydrazone compound (C-2) is used in an amount of 5 to 50 parts by weight, preferably 5 parts by weight to 45 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), more preferably Good for 5 The amount is made up to 40 parts by weight.
  • a photoinitiator of another O-acyl hydrazone compound (C-2) is used as the photosensitive resin composition, the protective film/gap body obtained by the photosensitive resin composition has better adhesion during development. The hardness of the resulting protective film/gap body is preferred.
  • the photoinitiator (C) also includes other photoinitiators (C-3).
  • the other photoinitiator (C-3) include, but are not limited to, triazabenzene compounds, acetophenone compounds, diimidazole compounds, benzophenone compounds, and ⁇ -diketone compounds.
  • triazabenzene compounds may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituted)-4,6-bis-halo A bis-s-triazabenzene compound and a 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound.
  • vinyl-halomethyl-s-triazabenzene compound examples include: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triaza Benzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene, 2-trichloro Methyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.
  • 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazabenzene compound are: 2-(naphtho-1-substituted)-4 ,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazole Heterobenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-butoxy-naphtho -l-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-di-halomethyl-s-triazabenzene compound are: 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-methyl -p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[p-N,N- Bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(chloroethyl) Aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl
  • triazabenzene compound is 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s. Triazine, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene and the like are preferred.
  • the above-mentioned triazabenzene compounds may be used singly or in combination of plural kinds, depending on actual needs.
  • acetophenone-based compound examples include: p-dimethylaminoketone, ⁇ , ⁇ '-dimethoxyoxyazopropenone, 2,2'-dimethyl-2- Phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl- 2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like.
  • the aforementioned acetophenone compound is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-dimethyl Amine-1-(4-morpholinophenyl)-1-butanone or the like is preferred.
  • the above-mentioned acetophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.
  • diimidazole compounds are: 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'-tetraphenyl Imidazole, 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 '-Bis(2,2',4,4'-tetramethoxy
  • the above diimidazole compound is preferably 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.
  • the above-mentioned diimidazole compounds may be used singly or in combination of plural kinds, depending on actual needs.
  • benzophenone compounds are: thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethyl Amine) benzophenone, 4,4'-bis(diethylamine) benzophenone, and the like.
  • the above benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone.
  • the above benzophenone compounds may be used singly or in combination of plural kinds, depending on actual needs.
  • Specific examples of the above ⁇ -diketone compound are phenacyl group, acetyl group and the like.
  • a specific example of the above ketol compound is benzophenone.
  • Specific examples of the above ketol ether compound are benzophenone methyl ether, benzophenone ethyl ether, and diphenylethanol ketone isopropyl ether.
  • Specific examples of the above acylphosphine oxide-based compound are: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzene) Acyl)-2,4,4-trimethylphenylphosphine oxide and the like.
  • terpenoids are: hydrazine, 1,4-naphthoquinone, and the like.
  • Specific examples of the above halogen-containing compound are benzoylmethyl chloride, tribromomethylphenylsulfone, tris(trichloromethyl)-s-triazabenzene, and the like.
  • Specific examples of the above peroxides include di-tert-butyl peroxide and the like.
  • the above-mentioned ⁇ -diketone compound, keto alcohol compound, keto alcohol ether compound, acylphosphine oxide compound, anthraquinone compound, halogen-containing compound, peroxide, or the like may be used alone or in combination of plural kinds. It depends on actual needs.
  • the photoinitiator (C) is used in an amount of 2 to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).
  • the organic solvent (D) of the present invention means an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and the following o-naphthoquinonediazidesulfonic acid.
  • the organic solvent preferably has a suitable volatility.
  • the organic solvent (D) may include, but is not limited to, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, Triethylene glycol ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol (tripropylene glycol) (poly)alkylene glycol monoalkyl ether solvent such as monomethyl ether) or tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate
  • the organic solvent (D) is used in an amount of 500 to 5000 parts by weight, preferably 600 parts by weight to 4,500 parts by weight, more preferably 700 parts by weight to 4,000 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight.
  • the photosensitive resin composition of the present invention further includes o-naphthoquinonediazide sulfonate (E).
  • the o-naphthoquinonediazide sulfonate (E) is not particularly limited and may be generally used.
  • the o-naphthoquinonediazide sulfonate (E) may be a fully esterified or partially esterified esterified product.
  • the o-naphthoquinonediazide sulfonate (E) is prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a hydroxy compound.
  • the o-naphthoquinonediazide sulfonate (E) is prepared by reacting o-naphthoquinonediazidesulfonic acid or a salt thereof with a polyvalent hydroxy compound.
  • the aforementioned o-naphthoquinonediazidesulfonic acid may include, but is not limited to, o-naphthoquinonediazide-4-sulfonic acid, o-naphthoquinonediazide-5-sulfonic acid, o-naphthoquinonediazide-6-sulfonic acid. Wait.
  • the above salts of o-naphthoquinonediazidesulfonic acid may include, but are not limited to, o-naphthoquinonediazidesulfonic acid halide salts.
  • hydroxy compound may be used singly or in combination, and the hydroxy compound may include, but is not limited to:
  • hydroxybenzophenone compound may include, but are not limited to, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxyl Benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4'- Pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,5 , 3', 5'-pentahydroxybenzophenone, 2,3,4,3',4',5'-hexahydroxybenzophenone and the like.
  • a hydroxyaryl compound which may include, but is not limited to, a hydroxyaryl compound represented by the following formula (E-1):
  • Q 1 to Q 3 represent a hydrogen atom or a C 1 to C 6 alkyl group
  • Q 4 to Q 9 represent a hydrogen atom, a halogen atom, a C 1 to C 6 alkyl group, C 1 to C alkoxy (alkoxy) 6, the aliphatic alkenyl group (alkenyl of) a C 1 to C 6 or a cycloalkyl group (cycloalkyl)
  • Q 10 and Q 11 represents a hydrogen atom, a halogen atom and a C 1 to C 6 Alkyl
  • g, h and i represent an integer from 1 to 3
  • j represents 0 or 1.
  • hydroxyaryl compound represented by the above formula (E-1) may include, but are not limited to, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)- 4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2- Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxybenzene Methane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxy Phenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenyl
  • (hydroxyphenyl) hydrocarbon compound which may include, but is not limited to, a (hydroxyphenyl) hydrocarbon compound represented by the following formula (E-2):
  • Q 12 and Q 13 represent a hydrogen atom or a C 1 to C 6 alkyl group, and c and d represent an integer of 1 to 3.
  • (hydroxyphenyl) hydrocarbon compound represented by the above formula (E-2) may include, but are not limited to, 2-(2,3,4-trihydroxyphenyl)-2-(2',3', 4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2 -(4'-Hydroxyphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, and the like.
  • aromatic hydroxy compounds may include, but are not limited to, phenol, p-methoxyphenol, dimethyl phenol, hydroquinone, bisphenol A, naphthol, catechol, 1, 2, 3 - benzenetriol methyl ether, 1,2,3-benzenetriol-1,3-dimethyl ether, 3,4,5-trihydroxybenzoic acid, partially esterified or partially etherified 3,4 , 5-trihydroxybenzoic acid, 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, and the like.
  • the above hydroxy compound is selected from the group consisting of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene] Phenol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-(2,3,4-trihydroxyphenyl)-2-(2) ',3',4'-trihydroxyphenyl)propane and a group consisting of any combination of the above.
  • the above-mentioned o-naphthoquinonediazidesulfonic acid or a salt thereof is usually reacted with the above-mentioned hydroxy compound in organic compounds such as dioxane, N-pyrrolidone, and acetamide. It is preferably carried out in a solvent while being carried out in the presence of an alkaline condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.
  • the degree of esterification of the aforementioned o-naphthoquinonediazide sulfonate (E) is 50% or more, that is, the total amount of hydroxyl groups in the aforementioned hydroxy compound is 100 mol% (mol%). More than 50 mol% of the hydroxyl groups in the hydroxy compound are esterified with o-naphthoquinonediazidesulfonic acid or a salt thereof. More preferably, the quinonediazide compound (B) has a degree of esterification of 60% or more.
  • the o-naphthoquinonediazide sulfonate (E) is used in an amount of 0.2 to 15 parts by weight, preferably 0.3 parts by weight to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Good for 0.4 weight The amount is made up to 6 parts by weight.
  • the o-naphthoquinonediazide sulfonate (E) is used as the photosensitive resin composition, the resolution of the protective film/gap body obtained by the photosensitive resin composition is preferable.
  • the photosensitive resin composition of the present invention further includes inorganic particles (F).
  • the inorganic particles (F) are mainly composed of an oxide of a Group IV element.
  • the inorganic particles (F) have a particle size of from 1 nm to 100 nm.
  • the measurement method of the particle diameter may be an existing measurement method, for example, measured by dynamic light scattering particles, and the particle diameter thereof is preferably from 1 nm to 50 nm; more preferably from 5 nm to 15 nm.
  • the particle diameter is less than 1 nm, the obtained film is liable to undergo secondary aggregation and may cause whitening; when the particle diameter is larger than 100 nm, the uniformity of the surface of the formed film may be affected.
  • the oxide particles which can be used as the inorganic particles (F) are preferably titanium oxide, zirconium oxide, cerium oxide, and composite particles of these metal oxides and silicon oxide and tin oxide, and the obtained film product
  • the refractive index is increased, and more preferably titanium oxide or zirconium oxide, that is, the fourth group element of the inorganic particles (F) is titanium or zirconium.
  • the crystalline form of titanium oxide has both an anatase type and a rutile type, preferably a rutile type, which has a high refractive index and excellent light resistance.
  • titanium oxide has photocatalytic activity, it is difficult to be used as an optical application, and therefore it is preferred to cover the surface of the particles with silicon oxide.
  • the inorganic particles (F) according to the present invention may be in the form of a powder or a dispersed sol form in which oxide particles are dispersed in a dispersion medium.
  • the dispersion medium is, for example, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, or ethoxyethanol.
  • the commercially available titanium oxide particles are manufactured by CIKasei, Japan, NanoTek TiO 2 (dispersant is methyl isobutyl ketone, anatase type); South Korea NanoCMS, Lot No.: S111109 (dispersed)
  • the agent is ethoxyethanol, rutile type); Japan's daily wave catalytic formation, Red Lake series (dispersant is methanol, anatase type); manufactured by Tayca, TS series (dispersant is methyl ethyl ketone, rutile type) ).
  • zirconia particles are manufactured by Osaka Cement Co., Japan, HXU-120JC (dispersant is methyl ethyl ketone) or Mikuni Color Ltd., and have an average particle diameter of 13.00 nm.
  • the inorganic particles (F) are used in an amount of 40 to 300 parts by weight, preferably 50 parts by weight to 250 parts by weight, more preferably 60 parts by weight to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight.
  • the refractive index of the protective film/gap body obtained by the photosensitive resin composition is preferable.
  • the photosensitive resin composition of the present invention further includes an organic acid (G) wherein the organic acid (G) has a molecular weight of 1,000 or less.
  • the organic acid having a molecular weight of 1,000 or less includes, but is not limited to, an aliphatic carboxylic acid, an alicyclic carboxylic acid or an aromatic carboxylic acid.
  • aliphatic carboxylic acid examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and pivalic acid. ), caproic acid, diethyl acetic acid, heptanoic acid, octanoic acid, 2-furoic acid, etc.; oxalic acid Acid), malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid , azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethyl malonate acid, dimethyl Dimethyl malonic acid, methyl succinic acid, tetramethyl succinic acid, itaconic acid, methyl methacrylate Citraconic acid, maleic acid, fumaric acid, methyl Dicarboxylic acid such as methyl fumaric acid; 1,2,3-propanetricarboxylic acid, aconitic acid, camphoronic acid And other tricarbox
  • Examples of the alicyclic carboxylic acid include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid, and lithocholate, and an adamantanecarboxylic acid derivative.
  • adamantane carboxylic acid derivatives adamantane dicarboxylic acid, cyclohexyl carboxylic acid, cyclohexyl dicarboxylic acid, and the like.
  • the aromatic carboxylic acid may, for example, be an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group or a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain, and specific examples thereof include benzoic acid.
  • toluic acid cumin acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid
  • Group of monocarboxylic acids phthalic acid, isophthalic acid, terephthalic acid and other aromatic dicarboxylic acids; trimellitic acid, 1,3 , 1,3,5-benzene tricarboxylic acid, 1,2,3,5-pyromellitic acid, pyromellitic acid More than 3 yuan of aromatic polycarboxylic acid; and phenyl acetic acid, hydrogenic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid (phenyl succinic acid), atropic acid, cinnaimic acid, cinnamylideneacetic acid, coumaric acid, umbellic acid, and other aromatic carboxylic acids .
  • the aforementioned organic acids may be used singly or in combination.
  • the organic acid is preferably malonic acid, adipic acid, or methylene, from the viewpoints of improvement in transparency of the coating film, alkali solubility, solubility in a solvent, and residue in a region other than a portion where a pixel is formed.
  • Succinic acid methyl maleic acid, 2-furancarboxylic acid, fumaric acid, methyl fumaric acid.
  • the organic acid (G) is used in an amount of 1 to 10 parts by weight, preferably 1.5 parts by weight to 9 parts by weight, more preferably 2 parts by weight to 8 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight.
  • the organic acid (G) is used as the photosensitive resin composition, the resolution of the obtained protective film/gap body is preferable.
  • the photosensitive resin composition of the present invention may optionally contain the additive (H) without affecting the efficacy of the present invention.
  • the additive (H) may include a filler, a polymer other than the alkali-soluble resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-aggregation agent.
  • Specific examples of the aforementioned filler may include, but are not limited to, glass or aluminum.
  • polystyrene resin examples include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or any combination of the above polymers.
  • adhesion promoter may include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and nitrogen-(2-aminoethyl) --3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropoxypropyltrimethoxysilane, 3-thiolpropyltrimethyl Oxysilane or any combination of the above
  • antioxidants may include, but are not limited to, 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or any combination of the above compounds. .
  • ultraviolet absorber may include, but are not limited to, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide or alkoxyphenone (alkoxy phenone). Or any combination of the above compounds.
  • anti-aggregation agent may include, but are not limited to, sodium polyacrylate or the like.
  • the additive (H) is used in an amount of 0.01 to 5 parts by weight, preferably 0.05 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Share.
  • a method for preparing a photosensitive resin composition for example, placing an alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), and a solvent (D) in a stirrer for stirring , uniformly mixing into a solution state, and if necessary, adding o-naphthoquinonediazide sulfonate (E), inorganic particles (F), organic acid (G), and additive (H), and uniformly mixing them.
  • a photosensitive resin composition in a solution state can be obtained.
  • 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 ethylenically unsaturated group-containing compound (B) in a part of the organic solvent (D) to form a dispersion solution; and then Mixing the remaining alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), the organic solvent (D), the o-naphthoquinonediazide sulfonate (E), and the inorganic Particle (F), organic acid (G), and additive (H).
  • the present invention provides a protective film and a spacer which are formed using the above-described photosensitive resin composition.
  • the preparation method thereof will be described in detail below.
  • the protective film of the present invention is formed by forming a pixel layer composed of a red, green, and blue colored layer on a transparent substrate, and then coating the transparent photosensitive resin composition described above to form red, green, blue, or the like. After the substrate of the pixel colored layer is subjected to exposure, development, and post-baking, the solvent is removed to form a color filter protective film.
  • a transparent conductive film is formed on a transparent substrate on which a protective film and a pixel layer have been formed, and the transparent photosensitive resin composition is applied onto the transparent conductive film.
  • the steps of exposure, development, and post-baking are performed, whereby the solvent therein is removed to form a spacer.
  • the photosensitive resin composition is applied onto the pixel layer on the substrate; and if the spacer is to be formed, the photosensitive resin composition is applied onto the transparent conductive film on the substrate. .
  • the above coating method may be, for example, a spray method, a roller coating method, a spin coating method, a bar coating method, or an ink jet method. .
  • the above coating method may preferably be carried out by a spin coater, a spin loess coating machine, a slit-die coating machine or the like.
  • the pre-bake conditions described above vary depending on the type of each component and the blending ratio, and usually pre-baked is carried out at a temperature of 70 ° C to 90 ° C for 1 minute to 15 minutes.
  • the thickness of the prebaked coating film is from 0.15 ⁇ m to 8.5 ⁇ m, preferably from 0.15 ⁇ m to 6.5 ⁇ m, more preferably from 0.15 ⁇ m to 4.5 ⁇ m. It can be understood that the thickness of the above pre-baked coating film refers to the thickness after removing the solvent.
  • the prebaking coating film After the prebaking coating film is formed, it is heat-treated by a heating device such as a hot plate or an oven.
  • the heat treatment temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 30 minutes, and the heating time in the oven is from 30 minutes to 90 minutes.
  • a curable resin composition When a photoinitiator is used as the curable resin composition, if necessary, a curable resin composition may be applied onto the surface of the substrate, and the solvent may be removed by pre-baking to form a pre-baked coating film. The prebaked coating film is subjected to exposure treatment.
  • the light used in the above exposure treatment may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like, and light having ultraviolet light having a wavelength of 190 nm to 450 nm is preferred.
  • the heat treatment temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 30 minutes, and the heating time in the oven is from 30 minutes to 90 minutes.
  • the protective film and the spacer of the present invention are not limited to being formed on the pixel layer or the transparent conductive film, and It can be formed on various components on or on the substrate.
  • the method for producing a color filter of the present invention is, for example, after forming a pixel colored layer such as red, green, or blue, and a protective film, in a vacuum environment having a temperature between 220 ° C and 250 ° C. Sputtering is performed on the surface of the protective film layer to form an ITO protective film. If necessary, the ITO protective film is etched and wired, and then an alignment film is coated on the surface of the ITO protective film to manufacture the present invention.
  • a color filter of a cured product obtained by curing a photosensitive resin composition.
  • 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 of inorganic substances or organic substances may be used, and the present invention is not limited thereto.
  • a nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a 1000-ml four-necked flask. After introducing nitrogen, 10 parts by weight of acrylic acid and 30 parts by weight of acrylic ring were added. Oxypropyl propyl ester, 20 parts by weight of 2-hydroxyethyl methacrylate, 35 parts by weight of styrene, 5 parts by weight of 1,3-butadiene, 2.4 parts by weight of 2,2'-azobis-2 - methylbutyronitrile and 240 parts by weight of diethylene glycol dimethyl ether solvent. Next, the above ingredients were slowly stirred to raise the temperature to 85 ° C, and polymerization was carried out at this temperature for 5 hours. Then, after the solvent is devolatilized, an alkali-soluble resin (A-1-1) can be obtained.
  • the alkali-soluble resin of Synthesis Example A-1-2 to Synthesis Example A-1-6 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 alkali-soluble resin and The amount used, the reaction time, and the reaction temperature (as shown in Table 1).
  • DMDMS dimethyldimethoxysilane
  • PTMS phenyltrimethoxysilane
  • TMS-GLY glycidoxypropyltrimethoxysilane
  • DAA diacetone alcohol
  • the polysiloxane polymer of Synthesis Example A-3-2 to Synthesis Example A-3-4 was prepared in the same manner as in Synthesis Example A-3-1, and was distinguished by changing the polymerization of polysiloxane.
  • the type and amount of raw materials used and the polymerization conditions (as shown in Table 2).
  • A-1-1 an alkali-soluble resin of Synthesis Example A-1-1 (hereinafter abbreviated as A-1-1), 20 parts by weight of pentaerythritol ⁇ (meth)acrylate (hereinafter abbreviated as B-1-1), 30 parts by weight of p-cumylcumylphenyl (meth) acrylate (hereinafter abbreviated as B-2-1), and 1 part by weight of a compound represented by the formula (1-1) (hereinafter abbreviated as C) -1-1), 0.2 parts by weight of 4,4'-[1-[4[-1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and its neighbors
  • E-1 o-naphthoquinonediazide sulfonate formed by naphthoquinonediazide-5-sulfonic acid is added to 500 parts by weight of propylene glycol methyl ether a
  • the photosensitive resin compositions of Examples 2 to 15 were prepared in the same manner as in Example 1, and were different in that the composition of the photosensitive resin composition and the amount thereof were changed (as shown in Table 3). ), wherein the compounds corresponding to the labels in Table 3 are as follows.
  • the obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 3.
  • the photosensitive resin compositions of Comparative Examples 1 to 7 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 used (as shown in Table 4). ). The obtained photosensitive resin composition was evaluated for each evaluation method described later, and the results are shown in Table 4.
  • the photosensitive resin composition was applied to a rectangular glass substrate of 100 mm x 100 mm by a screen printing machine (manufactured by Toyo Seiki Co., Ltd., AT-45PA) to apply a coating film of 80 mm x 80 mm. Observe the surface of the coating film, and the evaluation criteria are as follows:
  • ⁇ The surface after coating is flat, and no irregular lines appear.
  • ⁇ The surface after coating is flat, but a few irregular lines appear.
  • the prebaked coating film was placed between the specified mask patterns, and irradiated with ultraviolet light (exposure model AG500-4N; manufactured by M&R Nano Technology) having an energy of 100 mJ/cm 2 to perform an exposure process. Thereafter, the exposed coating film was immersed in a 0.05% KOH aqueous solution for 45 seconds, and after removing the unexposed portion, 100 cylinders having a diameter of 15 ⁇ m were developed. After washing with pure water, the number of developable cylinders was observed with a microscope (for example, Eclipse 50i, manufactured by Nikon).
  • a microscope for example, Eclipse 50i, manufactured by Nikon
  • the photosensitive resin composition was applied onto a glass substrate of 100 mm ⁇ 100 mm by spin coating, and dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, followed by prebaking at a temperature of 80 ° C and time 3. After a minute, it was irradiated with ultraviolet light (exposure machine Canon PLA-501F) at a light amount of 300 mJ/cm 2 , and then immersed in a developing solution at 23 ° C for 2 minutes, washed with pure water, and baked at 200 ° C for 80 minutes. A photosensitive resin layer having a film thickness of 2.0 ⁇ m was formed on a glass substrate, and the photosensitive resin layer was analyzed by a pencil hardness tester (Mitsubishi/P-247).
  • a pencil hardness tester Mitsubishi/P-247
  • the measurement was performed using a weight of 500 g, and a pencil was used to divide the lens at a rate of 0.5 mm/s at six angles of 60 degrees, 120 degrees, 180 degrees, 240 degrees, 300 degrees, and 360 degrees, respectively. Long, when more than two of the six lines (including two) draw a score, the judge is unqualified.
  • the refractive index of the film formed on the silicon substrate was measured using a PC-2010 prism coupling type (manufactured by Metricon Co., Ltd.) in a thermostatic chamber at 25 °C.
  • the light source is a laser of 633 nm.
  • the obtained photosensitive resin composition was applied by spin coating on a glass substrate, and prebaked at 100 ° C for 2 minutes to obtain a prebaked coating film of about 1 ⁇ m.
  • the pre-baked film was placed in a line and space mask (manufactured by Filcon, Japan), and irradiated with ultraviolet light of 50 mJ/cm 2 (exposure model AG500-4N; manufactured by M&R Nano Technology). Thereafter, the film was developed with a 0.84% potassium hydroxide aqueous solution at 23 ° C for 1 minute to remove the coating film on the unexposed portion of the substrate, and then washed with pure water, and the minimum value of the line width formed was determined as an analysis. degree.
  • the photosensitive resin composition including the first compound (B-1) containing an ethylenically unsaturated group does not include ethylene-containing properties.
  • the high-speed coating property and hardness of the photosensitive resin composition (Comparative Example 1 to Comparative Example 4) of the saturated first compound (B-1) were not high. good.
  • a photosensitive film containing no photoinitiator (C-1) was used as compared with a film formed using a photosensitive resin composition containing a photoinitiator (C-1) (Examples 1 to 15).
  • the film formed of the resin composition (Comparative Example 4 to Comparative Example 7) had poor adhesion and resolution at high temperature and development.
  • the photosensitive resin composition of the present invention includes the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), and the specific structure of the photoinitiator (C), ortho-naphthoquinone Since the sulfonate (E), the inorganic particles (F), and the organic acid (G) are formed, a photosensitive resin having high-speed coating properties, adhesion during development, hardness, refractive index, and resolution can be formed. Things.

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Abstract

一种感光性树脂组成物，其包括碱可溶性树脂（A）、含乙烯性不饱和基的化合物（B）、光起始剂（C）以及溶剂（D）。含乙烯性不饱和基的化合物（B）包括具有式（II）结构的含乙烯性不饱和基的第一化合物（B-1）。所述光起始剂（C）包括由式（1）表示的光起始剂（C-1）。

Description

感光性树脂组成物、间隙体、保护膜以及液晶显示元件 技术领域
本发明涉及一种感光性树脂组成物、间隙体、保护膜以及液晶显示元件。特别涉及一种具备高速涂布性、显影时密着性佳、折射率、硬度与解析度均佳的感光性树脂组成物及使用所述组成物所形成的间隙体或保护膜及其液晶显示元件。
背景技术
一般而言，彩色滤光层表面的彩色印刷的像素与黑色矩阵会产生凹凸不平的处，一般是在彩色滤光层的表面形成保护膜，藉此隐藏不平的处，进而达到平坦化的要求。
然而，在制造液晶显示元件或固态成像装置等光学元件中，会遇到严苛条件下的处理程序，例如在基板表面以酸性溶剂或碱性溶液浸泡的处理或以溅镀(Sputtering)形成配线电极层时，会造成局部腐蚀或高温的产生。因此，需在这些元件的表面上铺设保护膜，以防止制造时元件受损。为使保护膜具有抵御上述处理的特性，该保护膜需要与基板间具有优异的附着力、也需具有高透明度、高表面硬度与平滑的表面。而具高耐热性与耐光性的保护膜也可在长期使用下不会有变色、黄化或白化等变质情况发生。此外，该保护膜还需具有良好的耐水性、耐化性、耐溶剂性、耐酸性、耐碱性等特性。
另一方面，在现有技术中，彩色液晶显示元件中，为了维持两个基板间固定的层间距(细胞间隙)，是在整个基板上随机喷洒如聚苯乙烯珠或硅珠，其中该珠的直径为两基板间的间距。然而，此现有方式因喷珠的位置及密度分布并不均匀，造成背光源的光线受喷珠影响而散射，进一步使得显示元件的对比度降低。因此，以光微影制程(photolithography)方式所开发出的间隙体用感光性组成物，遂成为业界的主流。该间隙体的形成方式，乃将该间隙体用的感光性组成物先涂布至基板，再在基板与曝光源间放入一指定形状光罩，可在曝光后再经显影形成一间隙体。依据此方法，可在R、G、B像素外的指 定位置上形成间隙体，以解决现有技术的问题；细胞间隙也可利用感光性成分形成的涂膜厚度来控制，使细胞间隙的距离变得容易控制，具有精度高的优点。
由于该保护膜或间隙体是形成在彩色滤光片或是基板上，对透明度的要求极高。若保护膜或间隙体的透明度不佳，当应用于液晶显示元件时，将造成液晶显示元件的亮度不足，而影响液晶显示元件的显示品质。
为提高保护膜或间隙体的透明度，日本特开2010-054561号专利揭示一保护膜用的感光组成物，其包含(A)碱可溶性粘结树脂；(B)乙烯性不饱和基的化合物；(C)光起始剂；及(D)溶剂；其中该(B)乙烯性不饱和基的化合物中不饱和键的结合当量为介于90至450g/eq，且(B)乙烯性不饱和的的化合物中，单一化合物的不饱和双键为介于2至4个的间，及该(A)碱可溶性粘结树脂的重量平均分子量为介于10,000至20,000间。另一方面，日本特开2004-240241号专利揭示一感光组成物，其包含(A)共聚合物，该共聚物是由乙烯性不饱合羧酸(酐)、具环氧基的乙烯性不饱合基的化合物及其他乙烯性不饱合基的化合物；(B)乙烯性不饱合基的聚合物所共聚合而得；及(C)光起始剂，其为2-丁二酮-[4-甲硫基苯]-2-(O-肟醋酸盐)、1,2-丁二酮-1-(4-吗啉基苯基)-2-(O-苯甲酰肟)、1,2-辛二酮-1-[4-苯硫基苯]-2-[O-(4-甲基苯甲酰)肟]或其类似物。然而，所述感光性树脂组成物却有显影时密着性、硬度及涂布性不佳的问题，且无法满足现今业界对折射率及解析度日益升高的需求。
因此，如何同时达到目前业界对显影时密着性、硬度、涂布性、折射率及解析度均佳的要求，为本发明所属技术领域中努力研究的目标。
发明内容
本发明提供一种感光性树脂组成物、间隙体、保护膜以及液晶显示元件，其中，感光性树脂组成物包括碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)、光起始剂(C)以及溶剂(D)。其中，所述含乙烯性不饱和基的化合物(B)包括具有式(II)结构的含乙烯性不饱和基的第一化合物(B-1)，
Figure PCTCN2015092013-appb-000001
其中，A5表示氢原子或甲基；
A6表示氢原子、丙烯酰基或甲基丙烯酰基；及
r表示3至4；
所述光起始剂(C)包括由式(1)表示的光起始剂(C-1)
Figure PCTCN2015092013-appb-000002
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 PCTCN2015092013-appb-000003
Figure PCTCN2015092013-appb-000004
或R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8彼此独立地为经由式(4)所表示的基团取代的C2-C10烯基
Figure PCTCN2015092013-appb-000005
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 PCTCN2015092013-appb-000006
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 PCTCN2015092013-appb-000007
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；
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 PCTCN2015092013-appb-000009
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 PCTCN2015092013-appb-000010
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 PCTCN2015092013-appb-000011
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 PCTCN2015092013-appb-000012
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 PCTCN2015092013-appb-000013
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 PCTCN2015092013-appb-000014
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 PCTCN2015092013-appb-000015
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 PCTCN2015092013-appb-000016
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 PCTCN2015092013-appb-000017
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)是由不饱和羧酸或不饱和羧酸酐化合物(a1)及其他不饱和化合物(a2)所共聚合而得
在本发明的一实施例中，所述碱可溶性树脂(A)包括具有不饱和基的树脂(A-2)，其中所述具有不饱和基的树脂(A-2)是由一混合物聚合而得，并且所述混合物包括具有至少二个环氧基的环氧化合物(a-1-1)与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(a-1-2)。
在本发明的一实施例中，所述具有至少二个环氧基的环氧化合物(a-1-1)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 PCTCN2015092013-appb-000018
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 PCTCN2015092013-appb-000019
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。
在本发明的一实施例中，所述碱可溶性树脂(A)包括具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)，且所述聚硅氧烷聚合物(A-3)是由至少一具有式(9)结构所表示的硅烷单体经加水分解及部分缩合而得：
Si(U1)w(OU2)4-w  式(9)
w表示1至3的整数，且当w表示2或3时，复数个U1各自为相同或不同；且当4-w表示2或3时，复数个U2各自为相同或不同；
至少一个U1表示经酸酐基取代的C1至C10的烷基、经环氧基取代的C1至C10的烷基或经环氧基取代的烷氧基，且其余U1表示氢、C1至C10的烷基、C2至C10的烯基或C6至C15的芳香基；及
U2表示氢、C1至C6的烷基、C1至C6的酰基或C6至C15的芳香基。
在本发明的一实施例中，基于所述碱可溶性树脂(A)的使用量为100重量份，所述含乙烯性不饱和基的第一化合物(B-1)的使用量为20重量份至200 重量份。
在本发明的一实施例中，所述含乙烯性不饱和基的化合物(B)包括下式(III)所示的含乙烯性不饱和基的第二化合物(B-2)；
Figure PCTCN2015092013-appb-000020
其中：
式(III)中，
A1和A2各自独立代表氢原子或甲基；及
l表示0至4的整数。
在本发明的一实施例中，所述含乙烯性不饱和基的化合物(B)包括下式(IV)所示的含乙烯性不饱和基的第三化合物(B-3)；
Figure PCTCN2015092013-appb-000021
式(IV)中，
A3和A4各自独立代表氢原子或甲基；及
v表示0至4的整数。
在本发明的一实施例中，所述含乙烯性不饱和基的化合物(B)包括如下式(V)或如下式(VI)所示含乙烯性不饱和基的第四化合物(B-4)；
Figure PCTCN2015092013-appb-000022
其中：
式(V)中，B1至B8各自独立代表氢原子或烃基，且B1至B8中至少一个在其端部包括乙烯性不饱和基作为取代基；及
式(VI)中，B1至B6各自独立代表氢原子或烃基，且B1至B6中至少一个在其端部包括乙烯性不饱和基作为取代基。
在本发明的一实施例中，所述含乙烯性不饱和基的化合物(B)包括具有直链状二醇的二丙烯酸酯或二甲基丙烯酸酯的含乙烯性不饱和基的第五化合物(B-5)，且所述直链状二醇的碳数为2至12。
在本发明的一实施例中，其中所述R1、R2、R3、R4、R5、R6、R7及R8分别独立代表氢原子、C1-C20烷基、COR16、NO2或由式(2)所表示的基团、
Figure PCTCN2015092013-appb-000023
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 PCTCN2015092013-appb-000024
但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是是由式(5)所表示的基团；
X表示CO或直接键；
R13表示C1-C20烷基、苯基或萘基；
当R13表示C1-C20烷基时，其是未经取代或经一或多个以下基团取代：卤素、OR17、SR18、COOR17、CONR19R20或NR19R20、PO(OCkH2k+1)2；
当R13表示C2-C20烷基时，其是未经间杂或间杂有至少一O、S、CO或NR26；
当R13是苯基或萘基时，其各为未经取代或经COR16取代或经至少一式(7)表示的基团所取代；
Figure PCTCN2015092013-appb-000025
R14表示C1-C20烷基、苯基或C1-C8烷氧基；
R15表示苯基、萘基、C3-C20杂芳基或C1-C20烷基；
当R15表示苯基、萘基或C3-C20杂芳基时，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、间杂有一或多个O、S的C2-C20烷基，或者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；
当R15表示C1-C20烷基时，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所给出含义中的一个；
R'15具有针对R15所给出含义中的一个；
R16表示苯基或C1-C20烷基；
当R16表示苯基时，其是未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、间杂有一或多个O、S或NR26的C2-C20烷基，或者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；
当R16表示C1-C20烷基时，其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、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：OCH2CH2(CO)O(C1-C4烷基)、O(C1-C4烷基)、(CO)O(C1-C4烷基)、C3-C20环烷基，其中C3-C10环烷基是未经间杂或间杂有一或多个O；
当R17表示C2-C20烷基时，其是间杂有一或多个O；
R18表示经(CO)OR17取代的甲基；
R19及R20彼此独立为氢、苯基、C1-C20烷基、C1-C8烷酰基或C1-C8烷酰基氧基；
R19及R20与其所附接的N原子一起形成杂芳香族环系统，所述环系统是未经取代或经式(7)表示的基团取代；
Figure PCTCN2015092013-appb-000026
其中如所述式(1)所示的结构的光起始剂(C-1)中存在至少一个式(2)或是式(7)所表示的基团
Figure PCTCN2015092013-appb-000027
在本发明的一实施例中，所述R1、R2、R3、R4、R5、R6、R7及R8分别独立代表氢原子；
R1及R2、R3及R4、R5及R6彼此独立地共同为式(5)所表示的基团；
Figure PCTCN2015092013-appb-000028
但条件为R1及R2、R3及R4、R5及R6中的至少一对是是由式(5)所表示的基团；
R2表示COR16、NO2、式(2)所表示的基团或是由式(3)所表示的基团、
Figure PCTCN2015092013-appb-000029
R7表示COR16或式(2)所表示的基团
Figure PCTCN2015092013-appb-000030
R9、R11及R12彼此独立代表氢原子；
R10表示氢原子、OR17、COR16；
X表示CO或直接键；
R13表示C1-C20烷基或苯基；
当R13表示C1-C20烷基时，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；
当R13表示C2-C20烷基时，其是间杂有一或多个O；
k表示整数2；
R14表示C1-C20烷基或噻吩基；
R15表示苯基、萘基、噻吩基、O或C1-C20烷基；
当R15表示苯基或萘基时，其是未经取代或经一或多个OR17或C1-C20烷基取代；
当R15表示C1-C20烷基时，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、NR19R20或COOR17；
当R15表示C2-C20烷基时，其是间杂有SO2；
R16表示苯基、萘基或噻吩基；
当R16表示苯基或萘基时，其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；
R17表示氢原子、C1-C8烷酰基或C1-C20烷基；
当R17表示C1-C20烷基时，其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；
当R17表示C2-C20烷基时，其是间杂有一或多个O；
R18表示C3-C20环烷基、C1-C20烷基或苯基；
当R18表示C3-C20环烷基或C1-C20烷基时，其是未经取代或经一或多个OH、O(CO)-(C2-C4烯基)或(CO)OR17取代；
当R18表示苯基时，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；
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；
其中如所述式(1)所示的结构的光起始剂(C-1)中存在至少一个式(2)所表 示的基团
Figure PCTCN2015092013-appb-000031
在本发明的一实施例中，基于所述碱可溶性树脂(A)的使用量为100重量份，所述式(1)表示的光起始剂(C-1)的使用量为2至20重量份。
在本发明的一实施例中，所述光起始剂(C)，包括其他O-酰基肟类化合物(C-2)。
在本发明的一实施例中，所述其他O-酰基肟类化合物(C-2)包括由下述结构式(10)所示的光起始剂(C-2-I)：
Figure PCTCN2015092013-appb-000032
其中，D4及D5各自独立代表氢原子、具有1至12个碳原子数的环状、直链状或支链状的烷基或芳基，且所述烷基或芳基为未经取代或经取代基取代，所述取代基是选自由卤素原子、具有1至6个碳原子数的烷氧基及芳基所组成的群；
D6及D7各自独立代表卤素原子、具有1至12个碳原子数的烷基、环戊基、环己基、苯基、芐基、苯甲酰基、具有2至12个碳原子数的烷酰基、具有2至12个碳原子数的烷氧羰基、或苯氧基羰基；以及
e1及e2是独立代表0至5的整数。
在本发明的一实施例中，所述其他O-酰基肟类化合物(C-2)包括由下述结构式(11)所示的光起始剂(C-2-II)：
Figure PCTCN2015092013-appb-000033
式(11)中，J1表示Ja、Jb-S、Jc-O的官能基，其中Ja、Jb、Jc表示氢原子、烷基、芳香族基；J2表示氢原子、C1-C4烷基或卤素。
在本发明的一实施例中，基于所述碱可溶性树脂(A)的使用量为100重量份，所述含乙烯性不饱和基的化合物(B)的使用量为50至500重量份；所述光起始剂(C)的使用量为2至200重量份；所述溶剂(D)的使用量为500至5000重量份。
在本发明的一实施例中，所述的感光性树脂组成物还包括邻萘醌二叠氮磺酸酯(E)。
在本发明的一实施例中，所述的感光性树脂组成物还包括无机粒子(F)，所述无机粒子(F)是以第四族元素的氧化物为主成分。
在本发明的一实施例中，所述的感光性树脂组成物还包括有机酸(G)，其中所述有机酸(G)的分子量为1000以下。
本发明还提供一种间隙体，其是由上述的感光性树脂组成物，依序施予预烤处理、曝光处理、显影处理及后烤处理而制得具有图案的间隙体。
本发明还提供一种保护膜，其是由上述的感光性树脂组成物，依序施予预烤处理、曝光处理、显影处理及后烤处理而制得具有图案的保护膜。
本发明另提供一种液晶显示元件，包括上述的间隙体。
本发明另提供一种液晶显示元件，包括上述的保护膜。
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，并做详细说明如下。
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)、含乙烯性不饱和基的化合物(B)、光起始剂(C)以及溶剂(D)。此外，感光性树脂组成物可进一步包括邻萘醌二叠氮磺酸酯(E)、无机粒子(F)、有机酸(G)以及添加剂(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)包括具有碱可溶性树脂(A-1)、不饱和基的树脂(A-2)以及具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)。
碱可溶性树脂(A-1)
所述碱可溶性树脂(A-1)是由不饱和羧酸或不饱和羧酸酐化合物(a1)及其他不饱和化合物(a2)在适当的聚合起始剂存在下在溶剂中所共聚合而得。
不饱和羧酸或不饱和羧酸酐化合物(a1)是指包含羧酸基或羧酸酐结构及聚合结合用的不饱和键的化合物，其结构并无特别限制，例如不饱和单羧酸化合物、不饱和二羧酸化合物、不饱和酸酐化合物、多环型不饱和羧酸化合物、多环型不饱和二羧酸化合物、多环型不饱和酸酐化合物。
在本发明的具体例中，不饱和单羧酸化合物为(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-(甲基)丙烯酰乙氧基丁二酸酯、2-(甲基)丙烯酰乙氧基六氢化苯二甲酸酯、2-(甲基)丙烯酰乙氧基苯二甲酸酯、omega-羧基聚己内酯多元醇单丙烯酸酯(商品名为ARONIX M-5300，东亚合成制)。
在本发明的具体例中，不饱和二羧酸化合物为马来酸、富马酸、甲基富马酸、衣康酸、柠康酸等。在本发明的具体例中，不饱和二羧酸酐化合物为前述不饱和二羧酸化合物的酸酐化合物。
在本发明的具体例中，多环型不饱和羧酸化合物为5-羧基双环[2.2.1]庚-2-烯、5-羧基-5-甲基双环[2.2.1]庚-2-烯、5-羧基-5-乙基双环[2.2.1]庚-2-烯、5-羧基-6-甲基双环[2.2.1]庚-2-烯、5-羧基-6-乙基双环[2.2.1]庚-2-烯。
在本发明的具体例中，多环型不饱和二羧酸化合物为5,6-二羧酸二环[2.2.1]庚-2-烯。在本发明的具体例中，多环型不饱和二羧酸酐化合物为前述多环型不饱和二羧酸化合物的酸酐化合物。
在本发明的较佳具体例中，不饱和羧酸或不饱和羧酸酐化合物(a1)为丙烯酸、甲基丙烯酸、马来酸酐、2-甲基丙烯酰乙氧基丁二酸酯及2-甲基丙烯酰基乙氧基六氢化苯二甲酸。所述不饱和羧酸或不饱和羧酸酐化合物(a1)可单独或混合复数种使用。
本发明含不饱和羧酸或不饱和羧酸酐化合物(a1)的构成比例为10至50重量份，较佳为12至45重量份，更佳为15至40重量份。
其他不饱和化合物(a2)的构成比例为50至90重量份，较佳为55至88重量份，更佳为60至85重量份。其中该其他不饱和化合物(a2)可包含含环氧基的不饱和化合物(a2-1)及其他不饱和化合物(a2-2)。
上述含环氧基的不饱和化合物(a2-1)的具体例为：含环氧基的(甲基)丙烯酸酯化合物、含环氧基的α-烷基丙烯酸酯化合物、环氧丙醚化合物。
在本发明的具体例中，含环氧基的(甲基)丙烯酸酯化合物为(甲基)丙烯酸环氧丙酯、(甲基)丙烯酸2-甲基环氧丙酯、(甲基)丙烯酸3,4-环氧丁酯、(甲基)丙烯酸6,7-环氧庚酯、(甲基)丙烯酸3,4-环氧环己酯、(甲基)丙烯酸3,4-环氧环己基甲酯。
在本发明的具体例中，含环氧基的α-烷基丙烯酸酯化合物为α-乙基丙烯酸环氧丙酯、α-正丙基丙烯酸环氧丙酯、α-正丁基丙烯酸环氧丙酯、α-乙基丙烯酸6,7-环氧庚酯。
在本发明的具体例中，环氧丙醚化合物为邻-乙烯基苯甲基环氧丙醚(o-vinylbenzylglycidylether)、间-乙烯基苯甲基环氧丙醚(m-vinylbenzylglycidylether)、对-乙烯基苯甲基环氧丙醚(p-vinylbenzylglycidylether)。
本发明含环氧基的不饱和化合物(a2-1)较佳具体例为甲基丙烯酸环氧丙酯、(甲基)丙烯酸3,4-环氧环己基甲酯、甲基丙烯酸6,7-环氧庚酯、邻-乙烯基苯甲基环氧丙醚、间-乙烯基苯甲基环氧丙醚及对-乙烯基苯甲基环氧丙醚。
其他不饱和化合物(a2-2)的具体例为(甲基)丙烯酸烷基酯、(甲基)丙烯酸脂环族酯、(甲基)丙烯酸芳基酯、不饱和二羧酸二酯、(甲基)丙烯酸羟烷酯、 (甲基)丙烯酸酯的聚醚、芳香乙烯化合物及其他不饱和化合物。
在本发明的具体例中，(甲基)丙烯酸烷基酯为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸二级丁酯、(甲基)丙烯酸三级丁酯。
在本发明的具体例中，(甲基)丙烯酸脂环族酯为(甲基)丙烯酸环己酯、(甲基)丙烯酸-2-甲基环己酯、三环[5.2.1.02，6]癸-8-基(甲基)丙烯酸酯(或称为(甲基)丙烯酸双环戊酯)、(甲基)丙烯酸二环戊氧基乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸四氢呋喃酯。
在本发明的具体例中，(甲基)丙烯酸芳基酯为(甲基)丙烯酸苯基酯、甲基丙烯酸苯甲酯。
在本发明的具体例中，不饱和二羧酸二酯为马来酸二乙酯、富马酸二乙酯、衣康酸二乙酯。
在本发明的具体例中，(甲基)丙烯酸羟烷酯为(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-2-羟基丙酯。
在本发明的具体例中，(甲基)丙烯酸酯的聚醚为聚乙二醇单(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯。
在本发明的具体例中，芳香乙烯化合物为苯乙烯、α-甲基苯乙烯、间-甲基苯乙烯，对-甲基苯乙烯、对-甲氧基苯乙烯。
在本发明的具体例中，其他不饱和化合物为丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯酰胺、甲基丙烯酰胺、乙烯乙酯、1,3-丁二烯、异戊二烯、2,3-二甲基1,3-丁二烯、N-环己基马来酰亚胺、N-苯基马来酰亚胺、N-芐基马来酰亚胺、N-丁二酰亚胺基-3-马来酰亚胺苯甲酸酯、N-丁二酰亚胺基-4-马来酰亚胺丁酸酯、N-丁二酰亚胺基-6-马来酰亚胺己酸酯、N-丁二酰亚胺基-3-马来酰亚胺丙酸酯、N-(9-吖啶基)马来酰亚胺。
本发明的其他不饱和化合物(a2-2)较佳具体例为(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸三级丁酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸双环戊酯、(甲基)丙烯酸二环戊氧基乙酯、苯乙烯、对-甲氧基苯乙烯。根据本发明其他不饱和化合物(a2-2)可单独或组合使用。
本发明的碱可溶性树脂(A-1)在制造时所使用溶剂的具体例为醇、醚、二醇醚、乙二醇烷基醚醋酸酯、二乙二醇、二丙二醇、丙二醇单烷基醚、丙二 醇烷基醚醋酸酯、丙二醇烷基醚丙酸酯、芳香烃、酮、酯。
在本发明的具体例中，醇为甲醇、乙醇、苯甲醇、2-苯乙醇、3-苯基-1-丙醇。
在本发明的具体例中，醚为四氢呋喃。
在本发明的具体例中，二醇醚为乙二醇单丙醚、乙二醇单甲醚、乙二醇单乙醚。
在本发明的具体例中，乙二醇烷基醚醋酸酯为乙二醇丁醚醋酸酯、乙二醇乙醚醋酸酯、乙二醇甲醚醋酸酯。
在本发明的具体例中，二乙二醇为二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲乙醚。
在本发明的具体例中，二丙二醇为二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇二甲醚、二丙二醇二乙醚、二丙二醇甲乙醚。
在本发明的具体例中，丙二醇单烷基醚为丙二醇单甲醚、丙二醇单乙醚、丙二醇单丙醚、丙二醇单丁醚。
在本发明的具体例中，丙二醇烷基醚醋酸酯为丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯、丙二醇丙醚醋酸酯、丙二醇丁醚醋酸酯。
在本发明的具体例中，丙二醇烷基醚丙酸酯为丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯。
在本发明的具体例中，芳香烃为甲苯、二甲苯。
在本发明的具体例中，酮为甲乙酮、环己酮、二丙酮醇。
在本发明的具体例中，酯为乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羟基丙酸乙酯、2-羟基-2-甲基丙酸甲酯、2-羟基-2-甲基丙酸乙酯、羟乙酸甲酯、羟乙酸乙酯、羟乙酸丁酯、乳酸甲酯、乳酸丙酯、乳酸丁酯、3-羟基丙酸甲酯、3-羟基丙酸乙酯、3-羟基丙酸丙酯、3-羟基丙酸丁酯、2-羟基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、3-甲氧基丁基乙酸酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、 2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯。
本发明的碱可溶性树脂(A-1)在制造时所使用溶剂较佳为二乙二醇二甲醚、丙二醇甲醚醋酸酯。根据本发明其他碱可溶性树脂(A-1)在制造时所使用溶剂可单独或组合使用。
根据本发明的碱可溶性树脂(A-1)在制造时所使用的聚合起始剂，其具体例为偶氮化合物或过氧化物。
偶氮化合物的具体例为2,2'-偶氮双异丁腈、2,2'-偶氮双(2,4-二甲基戊腈)、2,2'-偶氮双(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮双-2-甲基丁腈、4,4'-偶氮双(4-氰基戊酸)、二甲基2,2'-偶氮双(2-甲基丙酸酯)、2,2'-偶氮双(4-甲氧基-2,4-二甲基戊腈)。
过氧化物的具体例为过氧化二苯甲酰、过氧化十二酰、叔丁基过氧化叔戊酸酯、1,1-双(叔丁基过氧化)环己烷、过氧化氢。
根据本发明的碱可溶性树脂(A-1)在制造时所使用的聚合起始剂可单独或组合使用。
本发明的碱可溶性树脂(A-1)的重量平均分子量一般为3,000至100,000，较佳为4,000至80,000，更佳为5,000至60,000。碱可溶性树脂(A-1)的分子量调整，可使用单一树脂，也可使用两种或两种以上不同分子量的树脂并用来达成。
在本发明的一具体例中，基于所述碱可溶性树脂(A)的使用量为100重量份，所述碱可溶性树脂(A-1)的使用量为30至100重量份；较佳为35至95重量份；更佳为为40至90重量份。
具有不饱和基的树脂(A-2)
具有不饱和基的树脂(A-2)是由一混合物聚合而得，并且所述混合物包括具有至少二个环氧基的环氧化合物(a-1-1)与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(a-1-2)。
所述具有至少二个环氧基的环氧化合物(a-1-1)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 PCTCN2015092013-appb-000034
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。
详言的，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 PCTCN2015092013-appb-000035
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 PCTCN2015092013-appb-000036
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如下：首先，在酸催化剂存在下，使用具有下式(a-2-II)结构的化合物与酚(phenol)类进行缩合反应后，形成具有式(a-2-I)结构的化合物。接着，加入过量的卤化环氧丙烷，以使卤化环氧丙烷与具有式(a-2-I)结构的化合物进行脱卤化氢反应(dehydrohalogenation)，而获得含有式(a-2)所表示的结构的具有至少二个环氧基的环氧化合物。
Figure PCTCN2015092013-appb-000037
在上式(a-2-II)中，W19与W20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；B1及B2各自独立表示卤素原子、碳数为1至6的烷基或碳数为1至6的烷氧基。上述的卤素原子较佳为氯或溴。上述的烷基较佳为甲基、乙基或第三丁基。上述的烷氧基较佳为甲氧基或乙氧基。
酚类的具体例包括：酚、甲酚、乙酚、n-丙酚、异丁酚、t-丁酚、辛酚、壬基苯酚、茬酚、甲基丁基苯酚、二第三丁基酚、乙烯苯酚、丙烯苯酚、乙 炔苯酚、环戊苯酚、环己基酚、环己基甲酚或其类似物。上述的酚类可单独使用或组合多种来使用。
基于上述具有式(a-2-II)结构的化合物的使用量为1摩尔，酚类的使用量为0.5摩尔至20摩尔，且较佳为2摩尔至15摩尔。
酸催化剂的具体例包括：盐酸、硫酸、对甲苯磺酸、草酸、三氟化硼、无水氯化铝、氯化锌或其类似物。酸催化剂较佳为对甲苯磺酸、硫酸、盐酸或上述化合物的组合。酸催化剂可单独使用或组合多种来使用。
另外，上述的酸催化剂的使用量虽无特别的限制。但是，基于上述具有式(a-2-II)结构的化合物的使用量为100重量百分比(wt％)，酸催化剂的使用量较佳为0.1wt％至30wt％。
上述的缩合反应可在无溶剂或是在有机溶剂的存在下进行。又，上述的有机溶剂的具体例包括：甲苯、二甲苯、甲基异丁基酮或其类似物。上述的有机溶剂可单独使用或组合多种来使用。
基于具有式(a-2-II)结构的化合物及酚类的总重量为100wt％，上述的有机溶剂的使用量为50wt％至300wt％，较佳为100wt％至250wt％。此外，上述的缩合反应的操作温度为40℃至180℃，且缩合反应的操作时间为1小时至8小时。
在完成上述的缩合反应后，可进行中和处理或水洗处理。上述的中和处理是将反应后的溶液的pH值调整为pH 3至pH 7，且较佳为pH 5至pH 7。上述的水洗处理可使用中和剂来进行，其中此中和剂为碱性物质，且其具体包括：氢氧化钠、氢氧化钾或其类似物的碱金属氢氧化物；氢氧化钙、氢氧化镁或其类似物的碱土类金属氢氧化物；二亚乙三胺、三亚乙四胺、苯胺、苯二胺或其类似物的有机胺；氨、磷酸二氢钠或上述化合物的组合。上述的中和剂可单独使用或组合多种来使用。上述的水洗处理可采用现有方法进行，例如在反应后的溶液中加入含中和剂的水溶液，并且反复进行萃取即可。经中和处理或水洗处理后，可经减压加热处理将未反应的酚类及溶剂予以馏除，并进行浓缩，如此一来，便可获得具有式(a-2-I)结构的化合物。
卤化环氧丙烷的具体例包括：3-氯-1,2-环氧丙烷、3-溴-1,2-环氧丙烷或上述化合物的组合。在进行上述的脱卤化氢反应之前，可预先添加或在反应过程中添加氢氧化钠、氢氧化钾等的碱金属氢氧化物。上述的脱卤化氢反应的 操作温度为20℃至120℃，其操作时间范围为1小时至10小时。
在一实施例中，上述脱卤化氢反应中所添加的碱金属氢氧化物也可为其水溶液。在此实施例中，将上述的碱金属氢氧化物水溶液连续添加至脱卤化氢反应系统内的同时，可在减压或常压下，连续蒸馏出水及卤化环氧丙烷，藉此分离并除去水，并且可将卤化环氧丙烷连续地回流至反应系统内。
上述的脱卤化氢反应进行前，也可添加氯化四甲铵、溴化四甲铵、三甲基苄基氯化铵或其类似物的四级铵盐作为催化剂，并且在50℃至150℃下，反应1小时至5小时后，加入碱金属氢氧化物或其水溶液。接着，在20℃至120℃的温度下，其使反应1小时至10小时，以进行脱卤化氢反应。
基于上述的具有式(a-2-I)结构的化合物中的羟基总当量为1当量，上述的卤化环氧丙烷的使用量为1当量至20当量，且较佳为2当量至10当量。基于上述的具有式(a-2-I)结构的化合物中的羟基总当量为1当量，上述的脱卤化氢反应中添加的碱金属氢氧化物的使用量为0.8当量至15当量，且较佳为0.9当量至11当量。
此外，为了使上述的脱卤化氢反应顺利进行，也可添加甲醇、乙醇或其类似物的醇类。除此之外，也可添加二甲砜、二甲亚砜或其类似物的非质子性的极性溶剂来进行反应。在使用醇类的情况下，基于上述的卤化环氧丙烷的总量为100wt％，醇类的使用量为2wt％至20wt％，且较佳为4wt％至15wt％。在使用非质子性的极性溶剂的情况下，基于卤化环氧丙烷的总量为100wt％，非质子性的极性溶剂的使用量为5wt％至100wt％，且较佳为10wt％至90wt％。
在完成脱卤化氢反应后，可选择性地进行水洗处理。之后，利用加热减压的方式，例如在温度为110℃至250℃且压力为1.3kPa(10mmHg)以下，除去卤化环氧丙烷、醇类及非质子性的极性溶剂。
为了避免形成的环氧树脂含有加水分解性的卤素，可将脱卤化氢反应后的溶液加入甲苯、甲基异丁基酮等溶剂以及氢氧化钠、氢氧化钾等碱金属氢氧化物水溶液，并且再次进行脱卤化氢反应。在脱卤化氢反应中，基于上述的具有式(a-2-I)结构的化合物中的羟基总当量为1当量，碱金属氢氧化物的使用量为0.01摩尔至0.3摩尔，且较佳为0.05摩尔至0.2摩尔。另外，上述的脱卤化氢反应的操作温度范围为50℃至120℃，且其操作时间范围为0.5小 时至2小时。
在完成脱卤化氢反应后，通过过滤及水洗等步骤去除盐类。此外，可利用加热减压的方式，将甲苯、甲基异丁基酮等溶剂予以馏除，则可得到含有式(a-2)所表示的结构的具有至少二个环氧基的环氧化合物。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。
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(a-1-2)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可选自于由以下(1)至(2)所组成的族群的其中一种：
(1)丁二酸酐、顺丁烯二酸酐、衣康酸酐、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基桥亚甲基四氢邻苯二甲酸酐、氯茵酸酐、戊二酸酐、偏三苯甲酸酐或其类似物的二元羧酸酐化合物；以及
(2)二苯甲酮四甲酸二酐、双苯四甲酸二酐、双苯醚四甲酸二酐或其类似 物的四元羧酸酐化合物。
本发明的碱可溶性树脂(A-2)的重量平均分子量一般为600至10,000，较佳为800至8,000，更佳为1,000至6,000。碱可溶性树脂(A-2)的分子量调整，可使用单一树脂，也可使用两种或两种以上不同分子量的树脂并用来达成。
基于碱可溶性树脂(A)的使用量为100重量份，前述具有不饱和基的树脂(A-2)的使用量为重量份0至70重量份，较佳为5至60重量份为，更佳为10至50重量份。当感光性树脂组成物使用具有不饱和基的树脂(A-2)时，该感光性树脂组成物所制得的保护膜/间隙体的硬度较佳。
具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)
碱可溶性树脂(A)包括一具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)，且所述聚硅氧烷聚合物(A-3)是由一反应物进行聚合[即水解(hydrolysis)及部分缩合(partially condensation)]反应来形成，且所述反应物可包含硅烷单体(silane monomer)、聚硅氧烷预聚物(siloxane prepolymer)，或者硅烷单体与聚硅氧烷预聚物的组合。
所述聚硅氧烷聚合物(A-3)是由至少一具有式(9)结构的硅烷单体经加水分解及部份缩合而得：
Si(U1)w(OU2)4-w  式(9)
w表示1至3的整数，且当w表示2或3时，复数个U1各自为相同或不同；且当4-w表示2或3时，复数个U2各自为相同或不同；
至少一个U1表示经酸酐基取代的C1至C10的烷基、经环氧基取代的C1至C10的烷基或经环氧基取代的烷氧基，且其余U1表示氢、C1至C10的烷基、C2至C10的烯基或C6至C15的芳香基；及
U2表示氢、C1至C6的烷基、C1至C6的酰基或C6至C15的芳香基。
所述经酸酐基取代的C1至C10烷基的具体例，如：乙基丁二酸酐、丙基丁二酸酐或丙基戊二酸酐等。
所述经环氧基取代的C1至C10烷基的具体例，如：环氧丙烷基戊基(oxetanylpentyl)或2-(3,4-环氧环己基)乙基[2-(3,4-epoxycyclohexyl)ethyl]等。
所述经环氧基取代的氧烷基的具体例，如：环氧丙氧基丙基(glycidoxypropyl)或2-环氧丙烷基丁氧基(2-oxetanylbutoxy)等。
在U2中，前述的烷基可包含但不限于甲基、乙基、正丙基、异丙基或正 丁基等。酰基可包含但不限于乙酰基。芳香基则可包含但不限于苯基。
式(9)所示的硅烷单体可包含但不限于3-环氧丙氧基丙基三甲氧基硅烷(3-glycidoxypropyltrimethoxysilane；TMS-GAA)、3-环氧丙氧基丙基三乙氧基硅烷(3-glycidoxypropyltriethoxysilane)、2-(3,4-环氧环己基)乙基三甲氧基硅烷[2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane]、2-环氧丙烷基丁氧基丙基三苯氧基硅烷(2-oxetanylbutoxypropyltriphenoxysilane)、3-(三苯氧基硅基)丙基丁二酸酐、3-(三甲氧基硅基)丙基戊二酸酐(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[diisopropoxy-di(2-oxetanylbutoxy propyl)silane；DIDOS]、二(3-环氧丙烷基戊基)二甲氧基硅烷[di(3-oxetanylpentyl)dimethoxy silane]、(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-glycidoxypropyldimethylmethoxysilane)、3-环氧丙氧基丙基二甲基乙氧基硅烷(3-glycidoxypropyldimethylethoxysilane)、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[di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxy silane]、三(2-环氧丙烷基戊基)甲氧基硅烷[tri(2-oxetanylpentyl)methoxy silane]、(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)、2-环氧丙烷基丁氧基丙基三甲氧基硅烷(2-oxetanylbutoxypropyltrimethoxysilane)、2-环氧丙烷基丁氧基丙基三乙氧基硅烷(2-oxetanylbutoxypropyltriethoxysilane)、3-乙基-3-{[3-(三甲氧基硅基)丙氧基]甲基}环氧丙烷、3-(三甲氧基硅基)丙基丁二酸酐、3-(三乙氧基硅基)丙基丁二酸酐等。上述式(9)所示的硅烷单体可单独一种使用或混合复数种使用。
在本发明的另一较佳具体例中，所述硅氧烷单体包含但不限于下列结构式(9-1)所示的结构：
Si(U9)u(OU10)4-u  式(9-1)
其中，U9表示选自由氢原子、C1至C10的烷基、C2至C10的烯基及C6至C15的芳基所组成的群，其中C1至C10的烷基不含有羧酸酐取代基；
U10是独立选自由氢原子、C1至C6的烷基、C1至C6的酰基及C6至C15的芳基所组成的群；及
u表示1至3的整数；当u代表2或3时，复数的U9可相同也可不同；当(4-u) 代表2、3或4时，复数的U10可相同或相异。
在U9中，烷基可包含但不限于甲基、乙基、正丙基、异丙基、正丁基、第三丁基、正己基、正葵基、三氟甲基、3,3,3-三氟丙基、3-胺丙基、3-巯丙基或3-异氰酸丙基等。烯基可包含但不限于乙烯基、3-丙烯酰氧基丙基或3-甲基丙烯酰氧基丙基等。芳香基可包含但不限于苯基、甲苯基、对-羟基苯基、1-(对-羟基苯基)乙基、2-(对-羟基苯基)乙基、4-羟基-5-(对-羟基苯基羰氧基)戊基或萘基等。
在U10中，烷基可包含但不限于甲基、乙基、正丙基、异丙基、正丁基等。酰基可包含但不限于乙酰基。芳香基可包含但不限于苯基。
式(9-1)所示的硅烷单体可包含但不限于四甲氧基硅烷、四乙氧基硅烷、四乙酰氧基硅烷、四苯氧基硅烷、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、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、二苯基二甲氧基硅烷、三甲基甲氧基硅烷、三正丁基乙氧基硅烷、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等。前述式(9-1)所示的硅烷单体可单独一种使用或混合复数种使用。
在本发明的一具体例中，当进行如结构式(9)化合物的共聚合反应时，化合物(9)所含的羧酸酐将自行开环，使其具有亲水性的羧酸根。上述所获得的聚硅氧烷聚合物(A-3)，对碱性显影液有较佳的显影性。其中聚合反应的温度系为可使羧酸酐充分开环的，较佳是在高于100℃反应30分钟。
根据本发明，当进行羧酸酐开环反应时，羧酸酐开环量相对聚硅氧烷聚 合物(A-3)中的硅原子并不受限制，较佳是大于10mol％。当羧酸根少于10mol％时，聚硅氧烷聚合物(A-1)的亲水性则不足。因此，当所涂布而成的图案于碱性显影液中显影时，将造成低感光性与显影性不佳。羧酸根的含量可如但不限于下述方法测定。
首先，将1重量％苯标准品及聚硅氧烷聚合物(A-1)混合，以进行元素分析及1H-NMR测定，并于元素分析中计算苯摩尔数对Si原子的摩尔数。并以1H-NMR测定(使用1H-NMR:CDCl3溶剂)羧酸的峰面积及苯的峰面积，相对聚硅氧烷聚合物(A-1)中的硅原子的羧酸酐开环量可通过苯摩尔数而计算得。
较佳地，前述的具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)的聚合用反应物可包含如下式(9-2)所示的聚硅氧烷预聚物：
Figure PCTCN2015092013-appb-000038
其中，U11、U12、U13及U14可为相同或不同，且分别选自由氢原子、C1至C10的烷基、C2至C6的烯基及C6至C15的芳基所组成的群；其中所述烷基、烯基或芳基较佳是含有取代基；其中每个U11可为相同或不同，且每个U12可为相同或不同；前述的烷基可包含但不限于甲基、乙基或正丙基等。烯基可包含但不限于乙烯基、丙烯酰氧基丙基或甲基丙烯酰氧基丙基等。芳香基可包含但不限于苯基、甲苯基或萘基等；
v为介于1至1000间的整数；较佳地，v为介于3至300间的整数；更佳地，v为介于5至200间的整数。
U15及U16是分别选自由氢原子、C1至C6的烷基、C1至C6的酰基及C6至C15的芳基所组成的群；其中所述烷基、酰基或芳基较佳是含有取代基。较佳地，烷基例如但不限于甲基、乙基、正丙基、异丙基、正丁基等；酰基例如但不限于乙酰基；芳基例如但不限于苯基。
式(9-2)所示的聚硅氧烷预聚物可包含但不限于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Gelest公司制造的硅烷醇末端聚硅氧烷，其型号分别为DM-S12(分子量为400至700)、DMS-S15(分子量为1500至2000)、DMS-S21(分 子量为4200)、DMS-S27(分子量为18000)、DMS-S31(分子量为26000)、DMS-S32(分子量为36000)、DMS-S33(分子量为43500)、DMS-S35(分子量为49000)、DMS-S38(分子量为58000)、DMS-S42(分子量为77000)或PDS-9931(分子量为1000至1400)等。式(9-2)所示的聚硅氧烷聚合物可单独一种使用或混合复数种使用。
较佳地，所述聚硅氧烷聚合物可通过前述的硅烷单体和/或聚硅氧烷预聚物经由聚合反应来制备，或组合二氧化硅(silicon dioxide)粒子经由共聚合反应来制备。所述二氧化硅粒子的平均粒径并无特别的限制，其平均粒径范围为2nm至250nm。较佳地，其平均粒径范围为5nm至200nm。更佳地，其平均粒径范围为10nm至100nm。
所述二氧化硅粒子可包含但不限于触媒化成株式会社制造，型号为OSCAR 1132(粒径为12nm，且分散剂为甲醇)、OSCAR 1332(粒径为12nm，且分散剂为正丙醇)、OSCAR 105(粒径为60nm，且分散剂为γ-丁内酯)或OSCAR 106(粒径为120nm，且分散剂为二丙酮醇)等的商品；扶桑化学株式会社制造，型号为Quartron PL-1-IPA(粒径为13nm，且分散剂为异丙酮)、Quartron PL-1-TOL(粒径为13nm，且分散剂为甲苯)、Quartron PL-2L-PGME(粒径为18nm，且分散剂为丙二醇单甲醚)或Quartron PL-2L-MEK(粒径为18nm，且分散剂为甲乙酮)等的商品；日产化学株式会社制造，型号为IPA-ST(粒径为12nm，且分散剂为异丙醇)、EG-ST(粒径为12nm，且分散剂为乙二醇)、IPA-ST-L(粒径为45nm，且分散剂为异丙醇)或IPA-ST-ZL(粒径为100nm，且分散剂为异丙醇)等的商品。所述二氧化硅粒子可单独一种使用或混合复数种使用。
前述的部分缩合反应可使用一般的方法，例如：在硅烷单体中添加溶剂及水，且可选择性地添加催化剂。接着，在50℃至150℃下加热搅拌0.5小时至120小时。搅拌时，反应可通过蒸馏去除副产物(醇类或水等)。
上述溶剂并没有特别限制，且可与本发明感光性树脂组成物中所包含的溶剂(D)为相同或不同。基于所述硅烷单体的总使用量为100克，所述溶剂的使用量为15克至1200克。较佳地，所述溶剂的使用量为20克至1100克。更佳地，所述溶剂的使用量为30克至1000克。
基于所述硅烷单体中所含的可水解基团为1摩尔，水解所使用的水的使 用量为0.5摩尔至2摩尔。
上述的催化剂没有特别的限制。较佳地，所述催化剂可选自于酸催化剂或碱催化剂。所述酸催化剂可包含但不限于盐酸、硝酸、硫酸、氟酸、草酸、磷酸、醋酸、三氟醋酸、蚁酸、多元羧酸或其酐类，或者离子交换树脂等。所述碱催化剂可包含但不限于二乙胺、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、具有胺基的烷氧基硅烷或离子交换树脂等。
基于硅烷单体的总量为100克，所述催化剂的使用量范围为0.005克至15克。较佳地，所述催化剂的使用量范围为0.01克至12克。更佳地，所述催化剂的使用量范围为0.05克至10克。
基于安定性的观点，经缩合反应后所制得具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)以不含副产物(如醇类或水)及催化剂为佳，因此所制得具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)可选择性地进行纯化。纯化方法并无特别限制，较佳可使用疏水性溶剂稀释所述具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)，接着以蒸发器浓缩经水洗涤数回的有机层，以除去醇类或水。另外，可使用离子交换树脂除去催化剂。
本发明的碱可溶性树脂(A-3)的重量平均分子量一般为1,000至50,000，较佳为2,000至40,000，更佳为3,000至30,000。碱可溶性树脂(A-3)的分子量调整，可使用单一树脂，也可使用两种或两种以上不同分子量的树脂并用来达成。
基于碱可溶性树脂(A)的使用量为100重量份，前述具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)的使用量为重量份0至70重量份，较佳为5至60重量份为，更佳为10至50重量份。当感光性树脂组成物使用聚硅氧烷聚合物(A-3)时，则该感光性树脂组成物所制得的保护膜/间隙体的高速涂布性较佳。
其他碱可溶性树脂(A-4)
根据本发明的其他碱可溶性树脂(A-4)是指可溶于碱性水溶液中的树脂，其构造并无特别限制，在本发明的一较佳具体例中，所述其他碱可溶性树脂(A-4)是指含羧酸基的树脂、苯酚-酚醛清漆(phenol-novolac)树脂等。
含乙烯性不饱和基的化合物(B)
含乙烯性不饱和基的化合物(B)包括含乙烯性不饱和基的第一化合物(B-1)、含乙烯性不饱和基的第二化合物(B-2)、含乙烯性不饱和基的第三化合物(B-3)、含乙烯性不饱和基的第四化合物(B-4)、含乙烯性不饱和基的第五化合物(B-5)以及其他乙烯性不饱和基的化合物(B-6)。
含乙烯性不饱和基的第一化合物(B-1)
所述含乙烯性不饱和基的第一化合物(B)包括具有式(II)结构的含乙烯性不饱和基的化合物(B-1)。
Figure PCTCN2015092013-appb-000039
其中，A5表示氢原子或甲基；
A6表示氢原子、丙烯酰基或甲基丙烯酰基；及
r表示3至4。
在本发明的具体例中，所述含乙烯性不饱和基的第一化合物(B-1)包含但不限于四季戊四醇九(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、五季戊四醇十一(甲基)丙烯酸酯或五季戊四醇十二(甲基)丙烯酸酯上述化合物的任意组合。
基于碱可溶性树脂(A)的总使用量为100重量份，所述含乙烯性不饱和基的第一化合物(B-1)的使用量为20重量份至200重量份，较佳为30重量份至150重量份，更佳为40重量份至100重量份。当感光性树脂组成物不使用含 乙烯性不饱和基的第一化合物(B-1)时，则该感光性树脂组成物所制得的保护膜/间隙体的的高速涂布性、硬度不佳。
含乙烯性不饱和基的第二化合物(B-2)
含乙烯性不饱和基的化合物(B)包括含乙烯性不饱和基的第二化合物(B-2)。所述含乙烯性不饱和基的第二化合物(B-2)包括下式(III)所示的(甲基)丙烯酸酯化合物单体。
Figure PCTCN2015092013-appb-000040
式(III)中，
A1和A2各自独立代表氢原子或甲基；以及
l表示0至4的整数。
l在式(III)中，表示亚烷氧基每分子平均加成数。
上述式(III)的具体例为：p-枯基苯基(甲基)丙烯酸酯(p-cumylphenyl(meth)acrylate)和p-枯基苯氧基乙基(甲基)丙烯酸酯等，其中以p-枯基苯基(甲基)丙烯酸酯和p-枯基苯氧基乙基(甲基)丙烯酸酯为佳。
基于碱可溶性树脂(A)为100重量份，所述含乙烯性不饱和基的第二化合物(B-2)的使用量为15至150重量份；较佳为20至130重量份；更佳为25至110重量份。当感光性树脂组成物使用含乙烯性不饱和基的第二化合物(B-2)时，则该感光性树脂组成物所制得的保护膜/间隙体在显影时密着性以及折射率较佳。
含乙烯性不饱和基的第三化合物(B-3)
含乙烯性不饱和基的化合物(B)包括含乙烯性不饱和基的第三化合物(B-3)。所述含乙烯性不饱和基的第三化合物(B-3)包括下式(IV)所示的(甲基)丙烯酸酯化合物单体。
Figure PCTCN2015092013-appb-000041
式(IV)中，
A3和A4各自独立代表氢原子或甲基；及
v表示0至4的整数。
v在式(IV)中，表示亚烷氧基每分子平均加成数。
上述式(IV)的具体例为：o-苯基苯基(甲基)丙烯酸酯(p-phenylphenyl(meth)acrylate)、m-苯基苯基(甲基)丙烯酸酯、p-苯基苯基(甲基)丙烯酸酯、o-苯基苯氧乙基(甲基)丙烯酸酯(p-phenylphenyl(meth)acrylate)、m-苯基苯氧乙基(甲基)丙烯酸酯及p-苯基苯氧乙基(甲基)丙烯酸酯等，其中以o-苯基苯基(甲基)丙烯酸酯及o-苯基苯氧乙基(甲基)丙烯酸酯为佳。
基于碱可溶性树脂(A)为100重量份，所述含乙烯性不饱和基的第三化合物(B-3)的使用量为15至150重量份；较佳为20至130重量份；更佳为25至110重量份。当感光性树脂组成物使用含乙烯性不饱和基的第三化合物(B-3)时，则该感光性树脂组成物所制得的保护膜/间隙体在显影时密着性以及折射率较佳。
含乙烯性不饱和基的第四化合物(B-4)
含乙烯性不饱和基的化合物(B)包括含乙烯性不饱和基的第四化合物(B-4)。所述含乙烯性不饱和基的第四化合物(B-4)包括二恶烷类不饱和化合物如包含1,3-二恶烷骨架和/或1,3-二恶戊烷(dioxolane)骨架。所述包含1,3-二恶烷骨架的二恶烷类不饱和化合物的结构如下式(V)所示；所述包含1,3-二恶戊烷骨架的二恶烷类不饱和化合物的结构则如下式(VI)所示：
Figure PCTCN2015092013-appb-000042
式(V)中，B1至B8各自独立代表氢原子或烃基，且B1至B8中至少一个在其端部包括乙烯性不饱和基作为取代基；以及
式(VI)中，B1至B6各自独立代表氢原子或烃基，且B1至B6中至少一个在其端部包括乙烯性不饱和基作为取代基。
当B1至B8为烃基时，其较佳为具有1至18个碳原子的烃基。其具体例为烷基、芳基、芳烷基(aralkyl)、烯基、环烷基等；其中较佳为烷基。
当B1至B8为烷基时，其较佳为具有1至8个碳原子的直链或支链烷基；更佳为具有1至4个碳原子的直链烷基；尤佳为甲基或乙基。
式(V)中，B1至B8中至少一个在其端部包含乙烯性不饱和基的取代基；或式(VI)中，B1至B6中至少一个在其端部包含乙烯性不饱和基的取代基，其中所述乙烯性不饱和基取代基的使用并无限制。
式(V)中，B1至B8中至少一个在其端部包含乙烯性不饱和基的取代基；或式(VI)中，B1至B6中至少一个在其端部包含乙烯性不饱和基的取代基，其中所述乙烯性不饱和基取代基较佳为(甲基)丙烯酰氧基(acryloxy)或(甲基)丙烯酰胺基(acrylamide)，其反应性及所聚合所得产物的柔软性较佳。
较佳地，在式(V)的B1至B8或式(VI)中的B1至B6的端部取代基于一分子中包含1至2个(甲基)丙烯酸衍生物，则化合物本身的粘性及硬化后的物性较佳。
本发明的较佳具体实施例中，所述含乙烯性不饱和基的第四化合物(B-4)具有如下示式(b4-1)至(b4-23)所示的结构：
Figure PCTCN2015092013-appb-000043
Figure PCTCN2015092013-appb-000044
Figure PCTCN2015092013-appb-000045
本发明的含乙烯性不饱和基的第四化合物(B-4)的较佳具体实施例为上述式(b4-2)、式(b4-3)、式(b4-4)、式(b4-13)及式(b4-15)所表示的化合物。
基于碱可溶性树脂(A)为100重量份，所述含乙烯性不饱和基的第四化合物(B-4)的使用量为5至50重量份；较佳为7至40重量份；更佳为10至30重量份。当感光性树脂组成物使用含乙烯性不饱和基的第四化合物(B-4)时，该感光性树脂组成物所制得的保护膜/间隙体的硬度较佳。
含乙烯性不饱和基的第五化合物(B-5)
含乙烯性不饱和基的化合物(B)包括含乙烯性不饱和基的第五化合物(B-5)。含乙烯性不饱和基的第五化合物(B-5)包括具有直链状二醇的二丙烯酸酯或二甲基丙烯酸酯。
所述链状二醇的二丙烯酸酯或二甲基丙烯酸酯具有两个反应性不饱和官能基，且此些官能基的间是以不具有环状结构的分子链键结。基于反应性的观点，前述的分子链较佳为直链，且其碳数为2以上。基于互溶性的观点，前述分子链的碳数较佳是12以下。
含乙烯性不饱和基的第五化合物(B-5)较佳为乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二丙烯酸酯或1,9-壬二醇二甲基丙烯酸酯。
基于碱可溶性树脂(A)为100重量份，所述含乙烯性不饱和基的第五化合物(B-5)的使用量为10至150重量份；较佳为20至120重量份；更佳为30至100重量份。当感光性树脂组成物使用所述含乙烯性不饱和基的第五化合物(B-5)时，则该感光性树脂组成物所制得的保护膜/间隙体的高速涂布性较佳。
其他乙烯性不饱和基的化合物(B-6)
含乙烯性不饱和基的化合物(B)还可选择性地包括其他乙烯性不饱和基的化合物(B-6)。
其他乙烯性不饱和基的化合物(B-6)可包含但不限于二(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、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(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、三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(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[di(trimethylolpropane)tetra(meth)acrylate]、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、经环氧丙烷改性的甘油三(甲基)丙烯酸酯、经环氧乙烷改性的双酚F二(甲基)丙烯酸酯、酚醛清漆聚缩水甘油醚(甲基)丙烯酸酯等。前述其他乙烯性不饱和基的化合物(B-6)可单独一种或混合复数种使用。
基于碱可溶性树脂(A)的总使用量为100重量份，所述含乙烯性不饱和基的化合物(B)的总使用量为50重量份至500重量份，较佳为60重量份至450重量份，更佳为70重量份至400重量份。
光起始剂(C)
光起始剂(C)包括光起始剂(C-1)、其他O-酰基肟类化合物(C-2)以及其它光起始剂(C-3)。
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 PCTCN2015092013-appb-000046
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 PCTCN2015092013-appb-000047
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 PCTCN2015092013-appb-000048
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 PCTCN2015092013-appb-000049
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 PCTCN2015092013-appb-000050
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 PCTCN2015092013-appb-000051
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 PCTCN2015092013-appb-000052
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 PCTCN2015092013-appb-000053
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 PCTCN2015092013-appb-000054
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 PCTCN2015092013-appb-000055
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 PCTCN2015092013-appb-000056
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 PCTCN2015092013-appb-000057
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 PCTCN2015092013-appb-000058
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 PCTCN2015092013-appb-000059
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 PCTCN2015092013-appb-000060
式(1)化合物在咔唑部分上包含一或多个成环(annelated)不饱和环。换言的，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 PCTCN2015092013-appb-000061
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。所述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 PCTCN2015092013-appb-000062
以及相对应的环。其他实例是诸如
Figure PCTCN2015092013-appb-000063
Figure PCTCN2015092013-appb-000064
(例如
Figure PCTCN2015092013-appb-000065
)或是
Figure PCTCN2015092013-appb-000066
等结构、以及侨联或稠合环系统，举例而言，所述术语也意欲涵盖:
Figure PCTCN2015092013-appb-000067
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 PCTCN2015092013-appb-000068
(例如
Figure PCTCN2015092013-appb-000069
Figure PCTCN2015092013-appb-000070
Figure PCTCN2015092013-appb-000071
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 PCTCN2015092013-appb-000072
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 PCTCN2015092013-appb-000073
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。所述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、联伸三苯基等，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 PCTCN2015092013-appb-000074
则形成例如以下(Ia)-(Ii)结构:
Figure PCTCN2015092013-appb-000075
Figure PCTCN2015092013-appb-000076
较佳为结构(Ia)。
式(1)化合物的特征在于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 PCTCN2015092013-appb-000077
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 PCTCN2015092013-appb-000078
Figure PCTCN2015092013-appb-000079
等结构。
若R17形成键结至其上具有基团
Figure PCTCN2015092013-appb-000080
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 PCTCN2015092013-appb-000081
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 PCTCN2015092013-appb-000082
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，且苯环视情况与所述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 PCTCN2015092013-appb-000083
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，则所述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 PCTCN2015092013-appb-000084
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。
此等反应为本领域技术人员所熟知，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 PCTCN2015092013-appb-000085
因此，本发明的目标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 PCTCN2015092013-appb-000086
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)或专着(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。此等反应为本领域技术人员所熟知。
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)二个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 PCTCN2015092013-appb-000087
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 PCTCN2015092013-appb-000088
OR17、卤素、NO2或是由式(3)所表示的基团、
Figure PCTCN2015092013-appb-000089
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 PCTCN2015092013-appb-000090
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 PCTCN2015092013-appb-000091
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 PCTCN2015092013-appb-000092
R9、R10、R11及R12彼此独立地为氢、C1-C20烷基，所述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，其中所述等取代基OR17、SR18或NR19R20视情况经由所述等基团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 PCTCN2015092013-appb-000093
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 PCTCN2015092013-appb-000094
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，其中所述经间杂的C2-C20烷基及所述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 PCTCN2015092013-appb-000095
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，所述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、式(6)所表示的基团
Figure PCTCN2015092013-appb-000096
苯基；或所述C1-C20烷基是经苯基取代，所述苯基是经卤素、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，且所述经间杂的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且所述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，所述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，所述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，其中所述基团R18表示键结至所述COR16基团所附接的所述咔唑部分的所述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 PCTCN2015092013-appb-000097
或R17形成键结至其上具有基团、
Figure PCTCN2015092013-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，其中所述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 PCTCN2015092013-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，且所述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 PCTCN2015092013-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，所述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 PCTCN2015092013-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，且所述5元或6元饱和或不饱和环是未稠合或所述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 PCTCN2015092013-appb-000102
但条件为在所述分子中存在至少一个基团
Figure PCTCN2015092013-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 PCTCN2015092013-appb-000104
)皆替换为相应游离肟基团
Figure PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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，此二个未经取代或经COR16取代或经一或多个
Figure PCTCN2015092013-appb-000109
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，所述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，所述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，所述环系统未经取代或经
Figure PCTCN2015092013-appb-000110
取代；但条件为在所述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 PCTCN2015092013-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、COR16、NO2或式(2)所表示的基团
Figure PCTCN2015092013-appb-000112
R3及R4一起为式(5)所表示的基团
Figure PCTCN2015092013-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。
但条件为在所述分子中存在至少一个由式(2)所表示的基团
Figure PCTCN2015092013-appb-000114
本发明的目标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 PCTCN2015092013-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 PCTCN2015092013-appb-000116
或R2表示COR16、NO2、式(2)所表示的基团或是由式(3)所表示的基团；
Figure PCTCN2015092013-appb-000117
或R7表示COR16或式(2)所表示的基团
Figure PCTCN2015092013-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，所述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；
但条件为在所述分子中存在至少一个式(2)所表示的基团
Figure PCTCN2015092013-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或由式(2)所表示的基团
Figure PCTCN2015092013-appb-000120
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 PCTCN2015092013-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 PCTCN2015092013-appb-000122
或R3及R4及R5及R6共同为式(5)所表示的基团
Figure PCTCN2015092013-appb-000123
R3及R4尤其共同为式(5)所表示的基团
Figure PCTCN2015092013-appb-000124
举例而言，R1、R5、R6及R8表示氢。
R7尤其为氢、式(2)所表示的基团
Figure PCTCN2015092013-appb-000125
或COR16。
或R7为式(2)所表示的基团
Figure PCTCN2015092013-appb-000126
或COR16，尤其为式(2)所表示的基团。
R2尤其为式(2)所表示的基团
Figure PCTCN2015092013-appb-000127
COR16或是由式(3)所表示的基团
Figure PCTCN2015092013-appb-000128
或R2与R1一起为式(5)所表示的基团
Figure PCTCN2015092013-appb-000129
R2尤其为COR16。
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 PCTCN2015092013-appb-000130
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 PCTCN2015092013-appb-000131
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 PCTCN2015092013-appb-000132
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，此二个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、或是式(7)表示的基团
Figure PCTCN2015092013-appb-000133
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，此二个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 PCTCN2015092013-appb-000134
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，此二个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，所述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 PCTCN2015092013-appb-000135
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，所述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，所述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 PCTCN2015092013-appb-000136
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，所述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 PCTCN2015092013-appb-000137
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的较佳者是如针对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 PCTCN2015092013-appb-000138
Figure PCTCN2015092013-appb-000139
Figure PCTCN2015092013-appb-000140
Figure PCTCN2015092013-appb-000141
Figure PCTCN2015092013-appb-000142
Figure PCTCN2015092013-appb-000143
Figure PCTCN2015092013-appb-000144
Figure PCTCN2015092013-appb-000145
Figure PCTCN2015092013-appb-000146
Figure PCTCN2015092013-appb-000147
Figure PCTCN2015092013-appb-000148
Figure PCTCN2015092013-appb-000149
Figure PCTCN2015092013-appb-000150
Figure PCTCN2015092013-appb-000151
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2至20重量份，较佳为2重量份至15重量份，更佳为2重量份至10重量份。当感光性树脂组成物不使用光起始剂(C-1)时，则该感光性树脂组成物所制得的保护膜/间隙体的在显影时密着性与解析度不佳。
其他O-酰基肟类化合物(C-2)
光起始剂(C)还包括其他O-酰基肟类化合物(C-2)。其他O-酰基肟类化合物(C-2)包括由下述结构式(10)所示的光起始剂(C-2-I)：
Figure PCTCN2015092013-appb-000152
其中，D4及D5各自独立代表氢原子、具有1至12个碳原子数的环状、直链状或支链状的烷基或芳基，且所述烷基或芳基为未经取代或经取代基取代，所述取代基是选自由卤素原子、具有1至6个碳原子数的烷氧基及芳基所组成的群；
D6及D7是各自独立代表卤素原子、具有1至12个碳原子数的烷基、环戊基、环己基、苯基、芐基、苯甲酰基(benzoyl)、具有2至12个碳原子数的烷酰基(alkanoyl)、具有2至12个碳原子数的烷氧羰基(alkoxycarbonyl)、或苯氧基羰基(phenoxycarbonyl)；以及
e1及e2是独立代表0至5的整数。
所述光起始剂(C-2-I)的具体例为：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)；上述光起始剂(C-2-I)可单独一种或混合复数种使用，端视实际需要而定。
其他O-酰基肟类化合物(C-2)还包括由下述结构式(11)所示的光起始剂(C-2-II)：
Figure PCTCN2015092013-appb-000153
式(11)中，J1表示Ja、Jb-S、Jc-O的官能基，其中Ja、Jb、Jc表示氢原子、烷基、芳香族基；J2表示氢原子、C1-C4烷基或卤素。
本发明的光起始剂(C-2-II)较佳的具体例如：乙烷酮,1-[9-乙基-6-(2-甲基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)(Ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime))(构造式如式(11-1)所示)、乙烷酮,1-[9-乙基-6-(2-氯-4苯磺基苯甲酰基)-9氢-咔唑-3-取代基]-,1-(氧-乙酰肟)(Ethanone,1-[9-ethyl-6-(2-chloro-4-benzyl sulfonyl benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime))(结构式如式(11-2)所示)。
Figure PCTCN2015092013-appb-000154
基于所述碱可溶性树脂(A)为100重量份，所述其他O-酰基肟类化合物(C-2)的使用量为5至50重量份，较佳为5重量份至45重量份，更佳为5重 量份至40重量份。当感光性树脂组成物使用了其他O-酰基肟类化合物(C-2)的光起始剂时，则感光性树脂组成物所制得的保护膜/间隙体的显影时密着性较佳，所制得的保护膜/间隙体的硬度较佳。
其他光起始剂(C-3)
光起始剂(C)还包括其他光起始剂(C-3)。其他光起始剂(C-3)的具体例包括但不限于：三氮杂苯系化合物、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、酮醇类化合物、酮醇醚类化合物、酰膦氧化物类化合物、醌类化合物、含卤素类化合物、过氧化物等。
上述的三氮杂苯系化合物可包括但不限于乙烯基-卤代甲基-s-三氮杂苯化合物、2-(萘并-1-取代基)-4,6-双-卤代甲基-s-三氮杂苯化合物及4-(对-胺基苯基)-2,6-二-卤代甲基-s-三氮杂苯化合物等。
前述的乙烯基-卤代甲基-s-三氮杂苯化合物的具体例为：2,4-双(三氯甲基)-6-对-甲氧基苯乙烯基-s-三氮杂苯、2,4-双(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-三氮杂苯等。
前述的2-(萘并-1-取代基)-4,6-双-卤代甲基-s-三氮杂苯化合物的具体例为：2-(萘并-1-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(4-甲氧基-萘并-1-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(4-乙氧基-萘并-1-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(4-丁氧基-萘并-1-取代基)-4,6-双-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-双-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-双-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-双-三氯甲基-s-三氮杂苯、2-(2-甲氧基-萘并-1-取代基)-4,6-双-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-双-三氯甲基-s-三氮杂苯、2-(6-甲氧基-萘并-2-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(5-甲氧基-萘并-1-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(4,7-二甲氧基-萘并-1-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(6-乙氧基-萘并-2-取代基)-4,6-双-三氯甲基-s-三氮杂苯、2-(4,5-二甲氧基-萘并-1-取代基)-4,6-双-三氯甲基-s-三氮杂苯等。
前述的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为： 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-双(三氯甲基)-6-[3-溴-4-[N,N-双(乙氧基羰基甲基)胺基]苯基]-1,3,5-三氮杂苯等。
前述的三氮杂苯系化合物以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-双(三氯甲基)-6-对-甲氧基苯乙烯基-s-三氮杂苯等为较佳。上述的三氮杂苯系化合物可单独一种或混合复数种使用，端视实际需要而定。
上述的苯乙烷酮类化合物的具体例为：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-丁酮等。前述的苯乙烷酮类化合物以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-丁酮等为较佳。上述的苯乙烷酮类化合物可单独一种或混合复数种使用，端视实际需要而定。
上述的二咪唑类化合物的具体例为：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’-四苯基二咪唑等。前述的二咪唑类化合物以2,2’-双(2,4-二氯苯基)-4,4’,5,5’-四苯基二咪唑为较佳。上述的二咪唑类化合物可单独一种或混合复数种使用，端视实际需要而定。
上述的二苯甲酮类化合物的具体例为：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)二苯甲酮等。前述的二苯甲酮类化合物以4,4’-双(二乙胺)二苯甲酮为较佳。上述的二苯甲酮类化合物可单独一种或混合复数种使用，端视实际需要而定。
上述的α-二酮类化合物的具体例为：苯偶酰、乙酰基等。上述的酮醇类化合物的具体例为：二苯乙醇酮。上述的酮醇醚类化合物的具体例为：二苯乙醇酮甲醚、二苯乙醇酮乙醚、二苯乙醇酮异丙醚等。上述的酰膦氧化物类化合物的具体例为：2,4,6-三甲基苯酰二苯基膦氧化物、双-(2,6-二甲氧基苯 酰)-2,4,4-三甲基苯基膦氧化物等。上述的醌类化合物的具体例为：蒽醌、1,4-萘醌等。上述的含卤素类化合物的具体例为：苯酰甲基氯、三溴甲基苯砜、三(三氯甲基)-s-三氮杂苯等。上述的过氧化物的具体例为：二-第三丁基过氧化物等。上述的α-二酮类化合物、酮醇类化合物、酮醇醚类化合物、酰膦氧化物类化合物、醌类化合物、含卤素类化合物、过氧化物等可单独一种或混合复数种使用，端视实际需要而定。
基于所述碱可溶性树脂(A)的使用量为100重量份，所述光起始剂(C)的使用量为2至200重量份。
有机溶剂(D)
本发明的有机溶剂(D)是指可将碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)、光起始剂(C)以及下述的邻萘醌二叠氮磺酸酯(E)、无机粒子(F)以及有机酸(G)溶解，但又不与上述的成分产生反应的有机溶剂。所述有机溶剂较佳具有适当的挥发性。
有机溶剂(D)可包含但不限于乙二醇甲醚、乙二醇乙醚、二甘醇甲醚、二甘醇乙醚、二甘醇正丙醚、二甘醇正丁醚、三甘醇甲醚、三甘醇乙醚、丙二醇甲醚、丙二醇乙醚、一缩二丙二醇甲醚、一缩二丙二醇乙醚、一缩二丙二醇正丙醚、一缩二丙二醇正丁醚、二缩三丙二醇甲醚(tripropylene glycol monomethyl ether)或二缩三丙二醇乙醚(tripropylene glycol monoethyl ether)等的(聚)亚烷基二醇单烷醚类溶剂；乙二醇单甲醚醋酸酯、乙二醇单乙醚醋酸酯、丙二醇单甲醚醋酸酯或丙二醇单乙醚醋酸酯等的(聚)亚烷基二醇单烷醚醋酸酯类溶剂；二甘醇二甲醚、二甘醇甲乙醚、二甘醇二乙醚或四氢呋喃等的其他醚类溶剂；甲乙烷酮、环己酮、2-庚酮或3-庚酮等的酮类溶剂；2-羟基丙酸甲酯或2-羟基丙酸乙酯等的乳酸烷酯类溶剂；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、乙氧基乙酸乙酯、羟基乙酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、乙酸正戊酯、乙酸异戊酯、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、乙酰乙酸甲酯、乙酰乙酸乙 酯或2-氧基丁酸乙酯等的其他酯类溶剂；甲苯或二甲苯等的芳香族碳氢化合物溶剂；氮-甲基吡咯烷酮、氮,氮-二甲基甲酰胺或氮,氮-二甲基乙酰胺等的羧酸酰胺溶剂。所述有机溶剂(D)可单独一种使用或混合复数种使用。
基于所述碱可溶性树脂(A)为100重量份，所述有机溶剂(D)的使用量为500至5000重量份，较佳为600重量份至4500重量份，更佳为700重量份至4000重量份。
邻萘醌二叠氮磺酸酯(E)
本发明的感光性树脂组成物更包括邻萘醌二叠氮磺酸酯(E)。邻萘醌二叠氮磺酸酯(E)没有特别的限制，可选用一般所使用的。所述邻萘醌二叠氮磺酸酯(E)可为完全酯化或部份酯化的酯化物。较佳地，所述邻萘醌二叠氮磺酸酯(E)是由邻萘醌二叠氮磺酸或其盐类与羟基化合物反应所制得。更佳地，所述邻萘醌二叠氮磺酸酯(E)是由邻萘醌二叠氮磺酸或其盐类与多元羟基化合物反应所制得。
前述的邻萘醌二叠氮磺酸可包括但不限于邻萘醌二叠氮-4-磺酸、邻萘醌二叠氮-5-磺酸、邻萘醌二叠氮-6-磺酸等。上述的邻萘醌二叠氮磺酸的盐类可包括但不限于邻萘醌二叠氮磺酸卤盐。
前述的羟基化合物可单独或混合使用，且所述羟基化合物可包括但不限于：
(1)羟基二苯甲酮类化合物：
羟基二苯甲酮类化合物的具体例可包括但不限于2,3,4-三羟基二苯甲酮、2,4,4'-三羟基二苯甲酮、2,4,6-三羟基二苯甲酮、2,3,4,4'-四羟基二苯甲酮、2,4,2',4'-四羟基二苯甲酮、2,4,6,3',4'-五羟基二苯甲酮、2,3,4,2',4'-五羟基二苯甲酮、2,3,4,2',5'-五羟基二苯甲酮、2,4,5,3',5'-五羟基二苯甲酮、2,3,4,3',4',5'-六羟基二苯甲酮等。
(2)羟基芳基类化合物，可包括但不限于下式(E-1)所示的羟基芳基类化合物：
Figure PCTCN2015092013-appb-000155
在式(E-1)中，Q1至Q3表示氢原子或C1至C6的烷基；Q4至Q9表示氢原子、卤素原子、C1至C6的烷基、C1至C6的烷氧基(alkoxy)、C1至C6的脂烯基(alkenyl)，或环烷基(cycloalkyl)；Q10及Q11表示氢原子、卤素原子及C1至C6的烷基；g、h及i表示1至3的整数；j表示0或1。
上式(E-1)所示的羟基芳基类化合物的具体例可包括但不限于三(4-羟基苯基)甲烷、双(4-羟基-3,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基苯基)-3-甲氧基-4-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-3-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-2-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-4-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-2-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-3-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-4-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-3,4-二羟基苯基甲烷、双(3-环己基-6-羟基苯基)-3-羟基苯基甲烷、双(3-环己基-6-羟基苯基)-4-羟基苯基甲烷、双(3-环己基-6-羟基苯基)-2-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-2-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-4-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-3,4-二羟基苯基甲烷、1-[1-(4-羟基苯基)异丙基]-4-[1,1-双(4-羟基苯基)乙基]苯、1-[1-(3-甲基-4-羟基苯基)异丙基]-4-[1,1-双(3-甲基-4-羟基苯基)乙基]苯等。
(3)(羟基苯基)烃类化合物，可包括但不限于下式(E-2)所示的(羟基苯基)烃类化合物：
Figure PCTCN2015092013-appb-000156
在式(E-2)中，Q12及Q13表示氢原子或C1至C6的烷基，而c及d表示1至3的整数。
上式(E-2)所示的(羟基苯基)烃类化合物的具体例可包括但不限于2-(2,3,4-三羟基苯基)-2-(2',3',4'-三羟基苯基)丙烷、2-(2,4-二羟基苯基)-2-(2',4'-二羟基苯基)丙烷、2-(4-羟基苯基)-2-(4'-羟基苯基)丙烷、双(2,3,4-三羟基苯基)甲烷、双(2,4-二羟基苯基)甲烷等。
(4)其他芳香族羟基类化合物：
其他芳香族羟基类化合物的具体例可包括但不限于苯酚、对-甲氧基苯酚、二甲基苯酚、对苯二酚、双酚A、萘酚、邻苯二酚、1,2,3-苯三酚甲醚、1,2,3-苯三酚-1,3-二甲基醚、3,4,5-三羟基苯甲酸、部份酯化或部份醚化的3,4,5-三羟基苯甲酸、4,4'-[1-[4[-1-(4-羟基苯基)-1-甲基乙基]苯基]亚乙基]双酚等。
较佳地，上述的羟基化合物是选自于由4,4'-[1-[4[-1-(4-羟基苯基)-1-甲基乙基]苯基]亚乙基]双酚、2,3,4-三羟基二苯甲酮、2,3,4,4'-四羟基二苯甲酮、2-(2,3,4-三羟基苯基)-2-(2',3',4'-三羟基苯基)丙烷以及上述的任意组合所组成的一族群。
前述的邻萘醌二叠氮磺酸或其盐类，与前述的羟基化合物的反应通常在二氧杂环己烷(dioxane)、氮-吡咯烷酮(N-pyrrolidone)、乙酰胺(acetamide)等有机溶剂中进行，同时在三乙醇胺、碱金属碳酸盐或碱金属碳酸氢盐等碱性缩合剂存在下进行较有利。
较佳地，前述的邻萘醌二叠氮磺酸酯(E)的酯化度在50％以上，即以前述的羟基化合物中的羟基总量为100摩尔百分比(mol％)计，所述羟基化合物中有50mol％以上的羟基与邻萘醌二叠氮磺酸或其盐类进行酯化反应。更佳地，所述醌二叠氮系化合物(B)的酯化度在60％以上。
基于所述碱可溶性树脂(A)为100重量份，所述邻萘醌二叠氮磺酸酯(E)的使用量为0.2至15重量份，较佳为0.3重量份至10重量份，更佳为0.4重 量份至6重量份。当感光性树脂组成物使用了邻萘醌二叠氮磺酸酯(E)时，则感光性树脂组成物所制得的保护膜/间隙体的解析度较佳。
无机粒子(F)
本发明的感光性树脂组成物还包括无机粒子(F)。所述无机粒子(F)是以第四族元素的氧化物为主成分。
在本发明的一具体例中，其中所述无机粒子(F)的粒径大小为1nm至100nm。所述粒径的测量方法可为现有的测量方法，例如通过动态光散射粒子所量测，其粒径较佳为1nm至50nm；更佳为5nm至15nm。当粒径小于1nm时，所制得的薄膜容易发生二次凝集，并可能产生白化；当粒径大于100nm时，则可能影响所形成薄膜表面的均匀性。
在本发明的具体例中，可供作为无机粒子(F)的氧化物粒子较佳为氧化钛、氧化锆、氧化铪以及这些金属氧化物和氧化硅以及氧化锡的复合粒子，所得的薄膜产物的折射率增加，其中更佳为氧化钛或氧化锆，即所述无机粒子(F)中第四族元素为钛或锆物是优选的。
另一方面，氧化钛的结晶形式同时存在锐钛矿型(Anatase)和金红石型(Rutile)，较佳为金红石型，其具有高折射率及优异的耐光性。
再者，由于氧化钛具有光催化活性，故难以作为光学应用，故较佳是以氧化硅覆盖粒子表面。
根据本发明的无机粒子(F)可为粉末形式或是将氧化物颗粒分散于分散介质中的分散溶胶形式。所述分散介质例如甲醇、甲基乙基酮、甲基异丁基酮、环己酮、N-甲基-2-吡咯烷酮、丙二醇单甲基醚、乙氧基乙醇。
在本发明的一具体例中，市售氧化钛粒子为日本C.I.Kasei制，NanoTek TiO2(分散剂为甲基异丁基酮，锐钛矿型)；韩国NanoCMS制，Lot No.：S111109(分散剂为乙氧基乙醇，金红石型)；日本日挥触媒化成制，Red Lake series(分散剂为甲醇，锐钛矿型)；Tayca制造，TS series(分散剂为甲基乙基酮，金红石型)。市售氧化锆粒子为日本Osaka Cement Co.制造，HXU-120JC(分散剂为甲基乙基酮)或Mikuni Color Ltd.制，平均粒径13.00nm。
基于所述碱可溶性树脂(A)为100重量份，所述无机粒子(F)的使用量为40至300重量份，较佳为50重量份至250重量份，更佳为60重量份至200 重量份。当感光性树脂组成物使用了无机粒子(F)时，则感光性树脂组成物所制得的保护膜/间隙体的折射率较佳。
有机酸(G)
本发明的感光性树脂组成物还包括有机酸(G)，其中所述有机酸(G)的分子量为1000以下。
在本发明的具体例中，所述分子量为1000以下的有机酸包含但不限于脂肪族羧酸、脂环族羧酸或芳香族羧酸。
作为上述脂肪族羧酸，例如可列举：甲酸(formic acid)、乙酸(acetic acid)、丙酸(propionic acid)、丁酸(butyric acid)、戊酸(valeric acid)、新戊酸(pivalic acid)、己酸(caproic acid)、二乙基乙酸(diethyl acetic acid)、庚酸(heptanoic acid)、辛酸(octanoic acid)、2-呋喃甲酸(2-Furoic acid)等单羧酸；草酸(oxalic acid)、丙二酸(malonic acid)、丁二酸(succinic acid)、戊二酸(glutaric acid)、己二酸(adipic acid)、庚二酸(pimelic acid)、辛二酸(suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、十三烷二酸(brassylic acid)、甲基丙二酸(methylmalonic acid)、乙基丙二酸(ethyl malonate acid)、二甲基丙二酸(dimethyl malonic acid)、甲基丁二酸(methyl succinic acid)、四甲基丁二酸(tetramethyl succinic acid)、亚甲基丁二酸(itaconic acid)、甲基顺丁烯二酸(citraconic acid)、顺丁烯二酸(maleic acid)、反丁烯二酸(fumaric acid)、甲基反丁烯二酸(methyl fumaric acid)等二羧酸；1,2,3-丙三甲酸(1,2,3-propanetricarboxylic acid)、乌头酸(aconitic acid)、降莰三酸(camphoronic acid)等三羧酸。
作为上述脂环族羧酸，例如可列举：胆酸(cholic acid)、去氧胆酸(deoxycholic acid)、石胆酸(lithocholate)等具有类固醇结构的羧酸衍生物、金刚烷羧酸衍生物(adamantane carboxylic acid derivatives)、金刚烷二羧酸(adamantane dicarboxylic acid)、环己基甲酸(cyclohexyl carboxylic acid)、环己基二甲酸(Cyclohexyl dicarboxylic acid)等。
作为上述芳香族羧酸，可列举羧基直接键结于苯基的芳香族羧酸、或羧基经由碳链键结于苯基的羧酸，作为其具体例，可列举：苯甲酸(benzoic acid)、甲苯甲酸(toluic acid)、小茴香酸(cumin acid)、2,3-二甲基苯甲酸(2,3-dimethylbenzoic acid)、3,5-二甲基苯甲酸(3,5-dimethylbenzoic acid)等芳香 族单羧酸；邻苯二甲酸(phthalic acid)、间苯二甲酸(isophthalic acid)、对苯二甲酸(terephthalic acid)等芳香族二羧酸；偏苯三甲酸(trimellitic acid)、1,3,5-苯三甲酸(1,3,5-benzene tricarboxylic acid)、1,2,3,5-苯四甲酸(1,2,3,5-pyromellitic acid)、均苯四甲酸(pyromellitic acid)等3元以上的芳香族多羧酸；及苯基乙酸(phenyl acetic acid)、氢阿托酸(Hydratropic acid)、氢桂皮酸(hydrocinnamic acid)、杏仁酸(mandelic acid)、苯基丁二酸(phenyl succinic acid)、阿托酸(atropic acid)、桂皮酸(cinnaimic acid)、亚桂皮乙酸(cinnamylideneacetic acid)、香豆酸(coumaric acid)、伞形酸(umbellic acid)等其他芳香族羧酸。前述有机酸可单独或合并使用。针对涂膜的透明性提高、碱溶解性、对溶剂的溶解性、防止形成像素的部分以外的区域的残渣观点而言，所述有机酸较佳为丙二酸、己二酸、亚甲基丁二酸、甲基顺丁烯二酸、2-呋喃甲酸、反丁烯二酸、甲基反丁烯二酸。
基于所述碱可溶性树脂(A)为100重量份，所述有机酸(G)的使用量为1至10重量份，较佳为1.5重量份至9重量份，更佳为2重量份至8重量份。当感光性树脂组成物使用了有机酸(G)时，则所制得的保护膜/间隙体的解析度较佳。
添加剂(H)
在不影响本发明功效的前提下，本发明的感光性树脂组成物可选择性地包含添加剂(H)。所述添加剂(H)可包含填充剂、前述碱可溶性树脂(A)以外的聚合物、密着促进剂、抗氧化剂、紫外线吸收剂或防凝集剂。
前述填充剂的具体例可包含但不限于玻璃或铝等。
前述聚合物的具体例可包含但不限于聚乙烯醇、聚乙二醇单烷基醚、聚氟丙烯酸烷酯或上述聚合物的任意组合。
前述密着促进剂的具体例可包含但不限于乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧乙氧基)硅烷、氮-(2-胺基乙基)-3-胺基丙基甲基二甲氧基硅烷、氮-(2-胺基乙基)-3-胺基丙基三甲氧基硅烷、3-胺基丙基三乙氧基硅烷、3-环氧丙醇丙基三甲氧基硅烷、3-环氧丙醇丙基甲基二甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-甲基丙烯氧基丙基三甲氧基硅烷、3-硫醇基丙基三甲 氧基硅烷或上述化合物的任意组合。
前述抗氧化剂的具体例可包含但不限于2,2-硫代双(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚或上述化合物的任意组合。
前述紫外线吸收剂的具体例可包含但不限于2-(3-第三丁基-5-甲基-2-羟基苯基)-5-氯苯基叠氮、烷氧基苯酮(alkoxy phenone)或上述化合物的任意组合。
前述防凝集剂的具体例可包含但不限于聚丙烯酸钠(sodium polyacrylate)等。
基于所述碱可溶性树脂(A)为100重量份，所述添加剂(H)的使用量为0.01至5重量份，较佳为0.05重量份至5重量份，更佳为0.1重量份至5重量份。
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)、含乙烯性不饱和基的化合物(B)、光起始剂(C)以及溶剂(D)放置于搅拌器中搅拌，使其均匀混合成溶液状态，必要时亦可添加邻萘醌二叠氮磺酸酯(E)、无机粒子(F)、有机酸(G)以及添加剂(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)及含乙烯性不饱和基的化合物(B)分散于一部分的有机溶剂(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)、含乙烯性不饱和基的化合物(B)、光起始剂(C)、有机溶剂(D)、邻萘醌二叠氮磺酸酯(E)、无机粒子(F)、有机酸(G)以及添加剂(H)。
保护膜与间隙体的形成
本发明提供一种保护膜与一种间隙体，其是使用上述的感光性树脂组成物所形成。以下详细说明其制备方法。
本发明的保护膜的形成方法是先将由红色、绿色及蓝色着色层组成的像素层形成在透明基板上，再将前述的透明感光性树脂组成物涂布在前述形成红、绿、蓝等像素着色层的基板上后，进行曝光、显影以及后烤等步骤，藉此去除其中的溶剂，以形成彩色滤光层保护膜。
本发明的间隙体的形成方法是先在已形成有保护膜及像素层的透明基板上，形成透明导电膜，再将前述的透明感光性树脂组成物涂布在前述透明导电膜上，接着，进行曝光、显影以及后烤等步骤，藉此去除其中的溶剂，以形成间隙体。
换言之，若欲形成保护膜，是将感光性树脂组成物涂布于基板上的像素层上；而若欲形成间隙体，则是将感光性树脂组成物涂布于基板上的透明导电膜上。
上述的涂布方法可例如为喷洒(spray)法、辊式(roller)涂布法、旋转涂布(spin coating)法、杆式(bar)涂布法或喷墨印刷(ink jet)法等。上述的涂布方法可采用旋转涂布机(spin coater)、非旋转式涂布机(spin loess coating machine)以及狭缝式涂布机(slit-die coating machine)等进行涂布为较佳。
上述预烤(pre-bake)的条件，依各成分的种类，配合比率而异，通常预烤乃在70℃至90℃温度下进行1分钟至15分钟。预烤后，预烤涂膜的厚度为0.15μm至8.5μm，然以0.15μm至6.5μm为较佳，又以0.15μm至4.5μm为更佳。可以理解的是，上述预烤涂膜的厚度是指去除溶剂后的厚度。
上述预烤涂膜形成后，再以热板或烘箱等加热装置进行加热处理。加热处理的温度通常为150至250℃，其中，使用热板的加热时间为5分钟至30分钟，使用烘箱的加热时间为30分钟至90分钟。
当上述硬化性树脂组成物使用光起始剂时，倘若有需要，可在将硬化性树脂组成物涂布在基板表面上，并以预烤方式去除溶剂而形成预烤涂膜后，对所述预烤涂膜进行曝光处理。
上述的曝光处理所使用的光线可例如可见光、紫外线、远紫外线、电子束(electron beam)、X射线等，然以波长为190nm至450nm的含有紫外线的光为较佳。
上述的曝光处理的曝光量以100J/m2至20,000J/m2为宜，然以150J/m2至10,000J/m2为较佳。
在上述曝光处理后，可选择性利用热板或烘箱等加热装置进行加热处理。加热处理的温度通常为150至250℃，其中，使用热板的加热时间为5分钟至30分钟，使用烘箱的加热时间为30分钟至90分钟。
本发明的保护膜及间隙体并不限定于形成于像素层或透明导电膜上，而 可以形成于基板上或基板上的各种元件上。
彩色滤光片的制备方法
具体而言，本发明的彩色滤光片的制造方法例如是：在形成红、绿、蓝等像素着色层及保护膜后，在温度介于220℃至250℃的间的真空环境下，在保护膜层的表面上进行溅镀，而形成ITO保护膜，必要时，对ITO保护膜进行蚀刻，并进行布线，然后在ITO保护膜表面上涂布配向膜，便能制造出包含将本发明的感光性树脂组成物硬化而成的硬化物的彩色滤光片。
液晶显示装置的制造方法
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。但是，可使用任何一种液晶化合物及液晶组成物。
此外，在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。
以下将列举实施例详细说明本发明，但本发明并不局限于这些实施例所揭示的内容。
实施例
碱可溶性树脂(A-1)的合成例
以下说明碱可溶性树脂(A-1)的的合成例A-1-1至合成例A-1-6：
合成例A-1-1
在一容积1000毫升的四颈锥瓶上设置氮气入口、搅拌器、加热器、冷凝管及温度计，导入氮气后，添加10重量份的丙烯酸、30重量份的丙烯酸环 氧丙酯、20重量份的甲基丙烯酸2-羟基乙酯、35重量份的苯乙烯、5重量份的1,3-丁二烯、2.4重量份的2,2’-偶氮双-2-甲基丁腈以及240重量份的二乙二醇二甲醚溶剂。接着，缓慢搅拌上述成份使溶液升温至85℃，并于此温度下聚合5小时。然后，将溶剂脱挥后，可得一碱可溶性树脂(A-1-1)。
合成例A-1-2至合成例A-1-6
合成例A-1-2至合成例A-1-6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：改变碱可溶性树脂的成分种类及其使用量、反应时间以及反应温度(如表1所示)。
表1中的简称所对应的化合物如下所示。
Figure PCTCN2015092013-appb-000157
表1
Figure PCTCN2015092013-appb-000158
具有不饱和基的树脂(A-2)的合成例
以下说明具有不饱和基的树脂(A-2)的合成例A-2-1至合成例A-2-3：
合成例A-2-1
将100重量份的芴环氧化合物(型号ESF-300，新日铁化学制；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，及130重量份的丙二醇甲醚醋酸酯以连续式添加方式加入至500mL的四口烧瓶中，且入料速度控制在25重量份/分钟，所述反应过程的温度维持在100℃～110℃，反应15小时，即可获得一固成分浓度为50wt％的淡黄色透明混合液。
接着，将100重量份的上述所得的淡黄色透明混合液溶于25重量份的乙二醇乙醚醋酸酯中，并同时添加6重量份的四氢邻苯二甲酸酐及13重量份的二苯甲酮四甲酸二酐，并加热至110℃～115℃，反应2小时，即可得一酸价为98.0mgKOH/g的具有不饱和基的树脂(以下简称为A-2-1)。
合成例A-2-2
将100重量份的芴环氧化合物(型号ESF-300，新日铁化学制；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，及130重量份的丙二醇甲醚醋酸酯以连续式添加方式加入置500mL的四口烧瓶中，且入料速度控制在25重量份/分钟，该反应过成的温度维持在100℃～110℃，反应15小时，即可获得一固成分浓度为50wt％的淡黄色透明混合液。
接着，将100重量份的上述所得的淡黄色透明混合液溶在25重量份的乙二醇乙醚醋酸酯中，并添加13重量份的二苯甲酮四甲酸二酐，在90℃～95℃下反应2小时，接着，添加6重量份的四氢邻苯二甲酸酐，并于90℃～95℃下反应4小时，即可得一酸价为99.0mgKOH/g的具有不饱和基的树脂(以下简称为A-2-2)。
合成例A-2-3
将400重量份的环氧化合物[型号NC-3000，日本化药(株)制；环氧当量288]、102重量份的丙烯酸、0.3重量份的甲氧基酚(methoxyphenol)、5重量份的三苯基膦，及264重量份的丙二醇甲醚醋酸酯置于反应瓶中，该反应过成的温度维持在95℃，反应9小时，即可获得一酸价为2.2mgKOH/g的中间产物。接着，加入151重量份的四氢邻苯二甲酸酐(tetrahydrophthalic anhydride)，在95℃下反应4小时，即可得一酸价为102mgKOH/g，且重量平均分子量为3,200的具有不饱和基的树脂(以下简称为A-2-3)。
聚硅氧烷聚合物(A-3)的合成例
以下说明聚硅氧烷聚合物(A-3)的合成例A-3-1至合成例A-3-4：
合成例A-3-1
在一容积500毫升的三颈烧瓶中，加入0.23摩尔的二甲基二甲氧基硅烷(以下简称为DMDMS)、0.7摩尔的苯基三甲氧基硅烷(以下简称为PTMS)、0.07摩尔的3-环氧丙氧基丙基三甲氧基硅烷(以下简称为TMS-GLY)及200克的二丙酮醇(以下简称为DAA)，并于室温下一边搅拌一边于30分钟内添加草酸水溶液(0.35克的草酸溶解于75克的水中)。接着，将烧瓶浸渍于30℃的油浴中，搅拌30分钟后，将上述的反应溶液加热至105℃，持续搅拌以进行聚缩合反应。反应6小时后，利用蒸馏方式去除溶液中的溶剂，即可得到聚硅氧烷聚合物(A-3-1)。
合成例A-3-2至合成例A-3-4
合成例A-3-2至合成例A-3-4的聚硅氧烷聚合物是以与合成例A-3-1相同的步骤来制备，并且其不同处在于：改变聚硅氧烷聚合物中原料的种类与使用量及聚合条件(如表2所示)。
表2中的简称所对应的化合物如下所示。
Figure PCTCN2015092013-appb-000159
表2
Figure PCTCN2015092013-appb-000160
感光性树脂组成物的实施例
以下说明感光性树脂组成物的实施例1至实施例15以及比较例1至比较例7：
实施例1
将100重量份合成例A-1-1的碱可溶性树脂(以下简称为A-1-1)、20重量份的四季戊四醇九(甲基)丙烯酸酯(以下简称为B-1-1)、30重量份的p-枯基异丙苯基苯基(甲基)丙烯酸酯(以下简称为B-2-1)、1重量份由式(1-1)所表示的化合物(以下简称为C-1-1)、0.2重量份的4,4'-[1-[4[-1-(4-羟基苯基)-1-甲基乙基]苯基]亚乙基]双酚与邻萘醌二叠氮-5-磺酸所形成的邻萘醌二叠氮磺酸酯(以下简称为E-1)加入500重量份的丙二醇甲醚醋酸酯(以下简称为D-1)中，并且以摇动式搅拌器(shaking type stirrer)搅拌均匀后，即可制造得实施例1的感光性树脂组成物。将所制得的感光性树脂组成物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)，其中表3中标号所对应的化合物如下所示。将所制得的感光性树脂组成物以后述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7
比较例1至比较例7的感光性树脂组成物是以与实施例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)。将所制得的感光性树脂组成物以后述各评价方式进行评价，其结果如表4所示。
表3及表4中的简称所对应的化合物如下所示。
Figure PCTCN2015092013-appb-000161
Figure PCTCN2015092013-appb-000162
Figure PCTCN2015092013-appb-000163
评价方式
(a)高速涂布性
将上述感光性树脂组成物以丝网印刷机(东远精技制，AT-45PA)在100mm x 100mm的矩形玻璃基板上涂布一80mm x 80mm的涂膜。观察涂膜表面，其评价标准如下：
◎：涂布后表面呈现平坦状，无不规则纹路出现
○：涂布后表面呈现平坦状，但有少数不规则纹路出现
△：涂布后表面呈现平坦状，但有严重不规则纹路出现
╳：涂布后表面呈现不平坦状，且有严重不规则纹路出现
(b)显影时密着性
将上述预烤涂膜介于所指定的光罩图案间，利用能量100mJ/cm2的紫外光(曝光机型号AG500-4N；M&R Nano Technology制)照射，以进行曝光制程。之后，将曝光后的涂膜浸于0.05％KOH水溶液中45秒，除去未曝光的部分后，显影出100个直径为15μm的圆柱。以纯水洗净后，再以显微镜(例如Eclipse 50i，Nikon制)观察可显影的圆柱数量。
◎：圆柱出现破损数量＜5
○：5≤圆柱出现破损数量＜10
△：10≤圆柱出现破损数量＜15
╳：15≤圆柱出现破损数量＜20
(c)硬度
将感光性树脂组成物以旋转涂布的方式，涂布在100mm×100mm的玻璃基板上，先进行减压干燥，压力100mmHg、时间30秒钟，然后再进行预烤，温度80℃、时间3分钟后，以紫外光(曝光机Canon PLA-501F)300mJ/cm2的光量照射，再浸渍于23℃的显影液2分钟，以纯水洗净，再以200℃后烤80分钟，即可在玻璃基板上形成一膜厚2.0μm的感光性树脂层，以铅笔硬度计(Mitsubishi/P-247)分析上述感光性树脂层。
使用500克的砝码重进行测量，且使用铅笔分别在薄膜的60度、120度、180度、240度、300度及360度的六个角度以0.5mm/s的移动速率各划1公分长，当六条线中有两条以上(包含两条)画出刻痕，即判不合格。
◎：≥4H；
○：3H；
△：2H；
╳：＜2H。
(d)折射率
在25℃的恒温室中，使用PC-2010棱镜耦合型(Metricon公司制)来测定于硅基板上所形成薄膜的折射率。另外，光源为633nm的激光。
◎：折射率≥1.65
○：1.65＞折射率≥1.60
△：1.60＞折射率≥1.55
╳：折射率＜1.55
(e)解析度
将所制得的感光性树脂组成物，在玻璃基板上以旋转涂布方式涂布，在100℃下预烤2分钟，可得到约1μm的预烤涂膜。将所述预烤涂膜介于线与间距(line and space)的光罩(日本Filcon制)，利用50mJ/cm2的紫外光(曝光机型号AG500-4N；M&R Nano Technology制)进行照射后，再以0.84％氢氧化钾水溶液，在23℃下予以显影1分钟，将基板上未曝光部份的涂膜除去，然后以纯水洗净，其形成的线条幅度的最小值定为解析度。
：最小图案线幅≤10μm
：10μm<最小图案线幅≤15μm
：15μm<最小图案线幅≤20μm
╳：20μm<最小图案线幅
表3
Figure PCTCN2015092013-appb-000164
Figure PCTCN2015092013-appb-000165
表3(续)
Figure PCTCN2015092013-appb-000166
Figure PCTCN2015092013-appb-000167
表4
Figure PCTCN2015092013-appb-000168
Figure PCTCN2015092013-appb-000169
评价结果
由表3及表4得知，与包括含乙烯性不饱和基的第一化合物(B-1)的感光性树脂组成物(实施例1至实施例15)相比，不包括含乙烯性不饱和基的第一化合物(B-1)的感光性树脂组成物(比较例1至比较例4)的高速涂布性及硬度不 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4至比较例7)所形成的膜于高温及显影时密着性与解析度不佳。
综上所述，本发明的感光性树脂组成物由于包括碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)以及特定结构的光起始剂(C)、邻萘醌二叠氮磺酸酯(E)、无机粒子(F)以及有机酸(G)，因此，可形成具备高速涂布性、在显影时密着性、硬度、折射率与解析度均佳的感光性树脂组成物。
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 (24)

  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)；
    含乙烯性不饱和基的化合物(B)；
    光起始剂(C)；
    溶剂(D)；
    其中，所述含乙烯性不饱和基的化合物(B)包括具有式(II)结构的含乙烯性不饱和基的第一化合物(B-1)，
    Figure PCTCN2015092013-appb-100001
    其中，A5表示氢原子或甲基；
    A6表示氢原子、丙烯酰基或甲基丙烯酰基；及
    r表示3至4；
    所述光起始剂(C)包括由式(1)表示的光起始剂(C-1)
    Figure PCTCN2015092013-appb-100002
    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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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COR16、NO2或式(2)所表示的基团、
    Figure PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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 PCTCN2015092013-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，该碱可溶性树脂(A)包括碱可溶性树脂(A-1)，其中所述碱可溶性树脂(A-1)是由不饱和羧酸或不饱和羧酸酐化合物(a1)及其他不饱和化合物(a2)所共聚合而得。
  3. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述碱可溶性树脂(A)包括具有不饱和基的树脂(A-2)，其中所述具有不饱和基的树脂(A-2)是由一混合物聚合而得，并且所述混合物包括具有至少二个环氧基的环氧化合物(a-1-1)与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(a-1-2)。
  4. 根据权利要求3所述的感光性树脂组成物，其特征在于，所述具有至少二个环氧基的环氧化合物(a-1-1)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 PCTCN2015092013-appb-100017
    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 PCTCN2015092013-appb-100018
    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。
  5. 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)包括具有酸酐基或环氧基的聚硅氧烷聚合物(A-3)，且所述聚硅氧烷聚合物(A-3)是由至少一具有式(9)结构所表示的硅烷单体经加水分解及部份缩合而得：
    Si(U1)w(OU2)4-w     式(9)
    w表示1至3的整数，且当w表示2或3时，复数个U1各自为相同或不同；且当4-w表示2或3时，复数个U2各自为相同或不同；
    至少一个U1表示经酸酐基取代的C1至C10的烷基、经环氧基取代的C1至C10的烷基或经环氧基取代的烷氧基，且其余U1表示氢、C1至C10的烷基、C2至C10的烯基或C6至C15的芳香基；及
    U2表示氢、C1至C6的烷基、C1至C6的酰基或C6至C15的芳香基。
  6. 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)的使用量为100重量份，所述含乙烯性不饱和基的第一化合物(B-1)的使用量为20重量份至200重量份。
  7. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述含乙烯性不饱和基的化合物(B)包括由下式(III)所示的含乙烯性不饱和基的第二化合物(B-2)；
    Figure PCTCN2015092013-appb-100019
    其中：
    式(III)中，
    A1和A2各自独立代表氢原子或甲基；及
    l表示0至4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，所述含乙烯性不饱和基的化合物(B)包括下式(IV)所示的含乙烯性不饱和基的第三化合物(B-3)；
    Figure PCTCN2015092013-appb-100020
    式(IV)中，
    A3和A4各自独立代表氢原子或甲基；及
    v表示0至4的整数。
  9. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述含乙烯性不饱和基的化合物(B)包括如下式(V)或如下式(VI)所示的含乙烯性不饱和基的第四化合物(B-4)；
    Figure PCTCN2015092013-appb-100021
    其中：
    式(V)中，B1至B8各自独立代表氢原子或烃基，且B1至B8中至少一个在其端部包括乙烯性不饱和基作为取代基；以及
    式(VI)中，B1至B6各自独立代表氢原子或烃基，且B1至B6中至少一个在其端部包括乙烯性不饱和基作为取代基。
  10. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述含乙烯性不饱和基的化合物(B)包括具有直链状二醇的二丙烯酸酯或二甲基丙烯酸酯的含乙烯性不饱和基的第五化合物(B-5)，且所述直链状二醇的碳数为2至12。
  11. 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分别独立代表氢原子、C1-C20烷基、COR16、NO2或由式(2)所表示的基团、
    Figure PCTCN2015092013-appb-100022
    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 PCTCN2015092013-appb-100023
    但条件为R1及R2、R2及R3、R3及R4、R5及R6、R6及R7或R7及R8中的至少一对是是由式(5)所表示的基团；
    X表示CO或直接键；
    R13表示C1-C20烷基、苯基或萘基；
    当R13表示C1-C20烷基时，其是未经取代或经一或多个以下基团取代：卤素、OR17、SR18、COOR17、CONR19R20或NR19R20、PO(OCkH2k+1)2；
    当R13表示C2-C20烷基时，其是未经间杂或间杂有至少一O、S、CO或NR26；
    当R13是苯基或萘基时，其各为未经取代或经COR16取代或经至少一式(7)表示的基团所取代；
    Figure PCTCN2015092013-appb-100024
    R14表示C1-C20烷基、苯基或C1-C8烷氧基；
    R15表示苯基、萘基、C3-C20杂芳基或C1-C20烷基；
    当R15表示苯基、萘基或C3-C20杂芳基时，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、间杂有一或多个O、S的C2-C20烷基，或者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；
    当R15表示C1-C20烷基时，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所给出含义中的一个；
    R'15具有针对R15所给出含义中的一个；
    R16表示苯基或C1-C20烷基；
    当R16表示苯基时，其是未经取代或经一或多个以下基团取代：OR17、SR18、NR19R20、间杂有一或多个O、S或NR26的C2-C20烷基，或者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；
    当R16表示C1-C20烷基时，其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、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：OCH2CH2(CO)O(C1-C4烷基)、O(C1-C4烷基)、(CO)O(C1-C4烷基)、C3-C20环烷基，其中C3-C10环烷基是未经间杂或间杂有一或多个O；
    当R17表示C2-C20烷基时，其是间杂有一或多个O；
    R18表示经(CO)OR17取代的甲基；
    R19及R20彼此独立为氢、苯基、C1-C20烷基、C1-C8烷酰基或C1-C8烷酰基氧基；
    R19及R20与其所附接的N原子一起形成杂芳香族环系统，所述环系统是未经取代或经式(7)表示的基团取代；
    Figure PCTCN2015092013-appb-100025
    其中如所述式(1)所示的结构的光起始剂(C-1)中存在至少一个式(2)或是式(7)所表示的基团
    Figure PCTCN2015092013-appb-100026
  12. 根据权利要求11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分别独立代表氢原子；
    R1及R2、R3及R4、R5及R6彼此独立地共同为式(5)所表示的基团；
    Figure PCTCN2015092013-appb-100027
    但条件为R1及R2、R3及R4、R5及R6中的至少一对是是由式(5)所表示的基团；
    R2表示COR16、NO2、式(2)所表示的基团或是由式(3)所表示的基团、
    Figure PCTCN2015092013-appb-100028
    R7表示COR16或式(2)所表示的基团；
    Figure PCTCN2015092013-appb-100029
    R9、R11及R12彼此独立代表氢原子；
    R10表示氢原子、OR17、COR16；
    X是CO或直接键；
    R13表示C1-C20烷基或苯基；
    当R13表示C1-C20烷基时，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；
    当R13表示C2-C20烷基时，其是间杂有一或多个O；
    k是整数2；
    R14表示C1-C20烷基或噻吩基；
    R15表示苯基、萘基、噻吩基、O或C1-C20烷基；
    当R15表示苯基或萘基时，其是未经取代或经一或多个OR17或C1-C20烷基取代；
    当R15表示C1-C20烷基时，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、NR19R20或COOR17；
    当R15表示C2-C20烷基时，其是间杂有SO2；
    R16表示苯基、萘基或噻吩基；
    当R16表示苯基或萘基时，其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；
    R17表示氢原子、C1-C8烷酰基或C1-C20烷基；
    当R17表示C1-C20烷基时，其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；
    当R17表示C2-C20烷基时，其是间杂有一或多个O；
    R18表示C3-C20环烷基、C1-C20烷基或苯基；
    当R18表示C3-C20环烷基或C1-C20烷基时，其是未经取代或经一或多个OH、O(CO)-(C2-C4烯基)或(CO)OR17取代；
    当R18表示苯基时，其是未经取代或经一或多个卤素取代；
    R19及R-20彼此独立地为C1-C8烷酰基或C1-C8烷酰基氧基；
    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；
    其中如所述式(1)所示的结构的光起始剂(C-1)中存在至少一个式(2)所表示的基团
    Figure PCTCN2015092013-appb-100030
  13. 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)的使用量为100重量份，所述式(1)表示的光起始剂(C-1)的使用量为2至20重量份。
  14. 根据权利要求1所述的感光性树脂组成物，其特征在于，所述光起始剂(C)，包括其他O-酰基肟类化合物(C-2)。
  15. 根据权利要求14所述的感光性树脂组成物，其特征在于，所述其他O-酰基肟类化合物(C-2)包括由下述结构式(10)所示的光起始剂(C-2-I)：
    Figure PCTCN2015092013-appb-100031
    其中，D4及D5各自独立代表氢原子、具有1至12个碳原子数的环状、直链状或支链状的烷基或芳基，且所述烷基或芳基为未经取代或经取代基取代，所述取代基是选自由卤素原子、具有1至6个碳原子数的烷氧基及芳基所组成的群；
    D6及D7各自独立代表卤素原子、具有1至12个碳原子数的烷基、环戊基、环己基、苯基、芐基、苯甲酰基、具有2至12个碳原子数的烷酰基、具有2至12个碳原子数的烷氧羰基、或苯氧基羰基；以及
    e1及e2是独立代表0至5的整数。
  16. 根据权利要求14所述的感光性树脂组成物，其特征在于，所述其他O-酰基肟类化合物(C-2)包括由下述结构式(11)所示的光起始剂(C-2-II)：
    Figure PCTCN2015092013-appb-100032
    式(11)中，J1表示Ja、Jb-S、Jc-O的官能基，其中Ja、Jb、Jc表示氢原子、烷基、芳香族基；J2表示氢原子、C1-C4烷基或卤素。
  17. 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)的使用量为100重量份，所述含乙烯性不饱和基的化合物(B)的使用量为50至500重量份；所述光起始剂(C)的使用量为2至200重量份；所述溶剂(D)的使用量为500至5000重量份。
  18. 根据权利要求1所述的感光性树脂组成物，其特征在于，还包括邻萘醌二叠氮磺酸酯(E)。
  19. 根据权利要求1所述的感光性树脂组成物，其特征在于，还包括无机粒子(F)，所述无机粒子(F)是以第四族元素的氧化物为主成分。
  20. 根据权利要求1所述的感光性树脂组成物，其特征在于，还包括有机酸(G)，其中所述有机酸(G)的分子量为1000以下。
  21. 一种间隙体，其特征在于，根据权利要求1至20任一项所述的感光性树脂组成物，依序施予预烤处理、曝光处理、显影处理及后烤处理而制得具有一图案的间隙体。
  22. 一种保护膜，其特征在于，根据权利要求1至20任一项所述的感光性树脂组成物，依序施予预烤处理、曝光处理、显影处理及后烤处理而制得具有一图案的保护膜。
  23. 一种液晶显示元件，其特征在于，包括权利要求21所述的间隙体。
  24. 一种液晶显示元件，其特征在于，包括权利要求22所述的保护膜。
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