CN106970503A - Photosensitive composite - Google Patents

Photosensitive composite Download PDF

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Publication number
CN106970503A
CN106970503A CN201611245667.3A CN201611245667A CN106970503A CN 106970503 A CN106970503 A CN 106970503A CN 201611245667 A CN201611245667 A CN 201611245667A CN 106970503 A CN106970503 A CN 106970503A
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China
Prior art keywords
epoxide
methyl
double
group
anthracene
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Granted
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CN201611245667.3A
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Chinese (zh)
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CN106970503B (en
Inventor
千坂博树
引田二郎
木下哲郎
盐田大
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention relates to photosensitive composite.The problem of the present invention is to provide the solidfied material for being exposed the photosensitive composite that also can well solidify, the manufacture method of the solidfied material of the photosensitive composite and the photosensitive composite even with LED.The present invention solution be：In the photosensitive composite comprising (A) photopolymerizable compound and (B) Photoepolymerizationinitiater initiater, (B) Photoepolymerizationinitiater initiater is set to contain the compound of following formula (1) expression, and cooperation (C) sensitizer in photosensitive composite.In formula (1), R1For hydrogen atom, nitro or monovalent organic group, R2And R3Can respectively have the chain-like alkyl of substituent, can have the cyclic organic group or hydrogen atom of substituent, R2With R3It can be mutually bonded to form ring, R4For monovalent organic group, R5For hydrogen atom, the alkyl of the carbon number 1~11 can with substituent or the aryl can with substituent, n is 0~4 integer, and m is 0 or 1.

Description

Photosensitive composite
Technical field
The present invention relates to photosensitive composite, the manufacture method of the solidfied material of the photosensitive composite and the photonasty group The solidfied material of compound.
Background technology
The display devices such as liquid crystal display are formed as following structures：It is being formed with 2 of mutually opposing paired electrode The structure of liquid crystal layer is accompanied between substrate.Moreover, being formed with the inside of the substrate of a side including red (R), green (G), indigo plant The colour filter (color filter) of the pixel regions of a variety of colors such as color (B).In the colour filter, black square is conventionally formed with Battle array, to divide each pixel regions such as red, green, blueness.
In addition, the panel for display device also possesses transparent insulating film etc. sometimes.
Colour filter, transparent insulating film are usually manufactured using photosensitive composite by photoetching process.For example, colour filter according to Following manner is manufactured：First, the photosensitive composite of painting black and dry it on substrate, be then exposed, Development, forms black matrix".Then, for the photosensitive composite of a variety of colors such as red, green, blueness, each repeat Row coating, it is dry, exposed and developed, form the pixel region of a variety of colors in specific position.
Moreover, for the photosensitive composite for manufacturing liquid crystal display etc., from the manufacture of reduction display device The viewpoints such as cost, raising productivity ratio consider, it is desirable to high sensitive.In this case, as photosensitive composite can be made The good Photoepolymerizationinitiater initiater of susceptibility, propose the oxime ester compound with cycloalkyl in patent document 1.In patent document In embodiment described in 1, the compound that following chemical formula (a) and (b) are represented is specifically disclosed.
Prior art literature
Patent document
Patent document 1：Chinese publication publication the 101508744th
The content of the invention
Invent problem to be solved
The certain susceptibility of photosensitive composite comprising the oxime ester compound described in patent document 1 is good.
But, the photosensitive composite comprising the oxime ester compound described in patent document 1 is exposed using LED When, differ and surely solidify well.
From the viewpoint of the energy, reduction carrying capacity of environment is saved, LED is just constantly being sent out as the application of the light source for exposure Exhibition.
The present invention makes in view of the above problems, it is therefore intended that offer is exposed even with LED also can be good The photosensitive composite, the manufacture method of the solidfied material of the photosensitive composite and the photosensitive composite that solidify well is consolidated Compound.
Means for solving the problems
Inventors herein have recognized that, by making the sense comprising (A) photopolymerizable compound and (B) Photoepolymerizationinitiater initiater (B) Photoepolymerizationinitiater initiater in photosensitiveness composition contains the oxime ester compound for the specific structure for replacing fluorenyl with 9,9- bis-, and And coordinate (C) sensitizer in photosensitive composite, above-mentioned problem is can solve the problem that, so as to complete the present invention.Specifically, originally Invention provides following scheme.
The 1st aspect of the present invention is related to photosensitive composite, and it draws comprising (A) photopolymerizable compound, (B) photopolymerization Agent and (C) sensitizer are sent out, wherein,
(B) Photoepolymerizationinitiater initiater includes the compound that following formula (1) is represented.
(R1For hydrogen atom, nitro or monovalent organic group, R2And R3Can respectively have the chain-like alkyl of substituent, can have The cyclic organic group or hydrogen atom of substituted base, R2With R3It can be mutually bonded and form ring, R4For monovalent organic group, R5 For hydrogen atom, can have substituent carbon number 1~11 alkyl or can have substituent aryl, n for 0~4 it is whole Number, m is 0 or 1.)
The 2nd aspect of the present invention is related to the manufacture method of solidfied material, and it is to the photosensitive composition involved by first method Thing is exposed and solidifies it.
The 3rd aspect of the present invention is related to the solidfied material of the photosensitive composite involved by first method.
The effect of invention
According to the present invention, it is possible to provide be exposed the photosensitive composite that can also solidify well, the sense even with LED The manufacture method of the solidfied material of photosensitiveness composition and the solidfied material of the photosensitive composite.
Embodiment
《Photosensitive composite》
The photosensitive composite of the present invention includes (A) photopolymerizable compound, (B) Photoepolymerizationinitiater initiater and (C) sensitization Agent.(B) Photoepolymerizationinitiater initiater includes the oxime ester compound for the specific structure for replacing fluorenyl with 9,9- bis-.Photosensitive composite can So that comprising (D) colouring agent, (E) alkali soluble resins can also be included.Hereinafter, to the composition contained by photosensitive composite and sense The preparation method of photosensitiveness composition is illustrated successively.
＜ (A) photopolymerizable compounds ＞
(below, it is also known as (A) as (A) photopolymerizable compound included in photosensitive composite of the present invention Composition.), it is not particularly limited, previously known photopolymerizable compound can be used.Wherein, it is preferably unsaturated with ethylenic They, can also be combined by the resin or monomer of group.By by the resin with ethylenic unsaturated group with having The combination of monomers of ethylenic unsaturated group, it is possible to increase the curability of photosensitive composite, makes pattern formation become easy.This In invention, the more preferably monomer with ethylenic unsaturated group.
[resin with ethylenic unsaturated group]
As the resin with ethylenic unsaturated group, (methyl) acrylic acid, fumaric acid, maleic acid, rich horse can be enumerated Sour mono-methyl, monomethyl ester, (methyl) acrylic acid 2- hydroxy methacrylates, ethylene glycol single methyl ether (methyl) acrylate, second Glycol list ethylether (methyl) acrylate, glycerine (methyl) acrylate, (methyl) acrylamide, acrylonitrile, metering system Nitrile, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid 2- ethyl hexyls Ester, (methyl) benzyl acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol Two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, (first of propane diols two Base) acrylate, trimethylolpropane tris (methyl) acrylate, tetra methylol propane four (methyl) acrylate, Ji Wusi Alcohol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta Tetrol six (methyl) acrylate, 1,6-HD two (methyl) acrylate, Cardo- epoxy diacrylates (Cardo Epoxy diacrylate) etc. the oligomeric species that are polymerized；Make (methyl) acrylic acid and polyester prepolyer (the polyester pre-polymerization Thing is obtained by the way that polyalcohols and monoacid or polyacid are condensed) polyester (methyl) acrylate obtained from reaction； Make polyalcohol and have after the compound reaction of 2 NCOs, make polyurethane (first obtained from (methyl) propylene acid reaction Base) acrylate；Make bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresols It is Novolac types epoxy resin, Resol types epoxy resin, tris-phenol type epoxy resin, many ethylene oxidic esters of polycarboxylic acid, many The asphalt mixtures modified by epoxy resin such as first many ethylene oxidic esters of alcohol, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxy benzene-type epoxy resin Fat and epoxy (methyl) acrylate etc. obtained from (methyl) propylene acid reaction.In addition, preferably making polyacid Acid anhydride and resin obtained from the reaction of epoxy (methyl) acrylate.It should be noted that in this specification, " (methyl) third Alkene-" refers to " propylene-or metering system-".
In addition, as the resin with ethylenic unsaturated group, preferably using：By making epoxide with containing The reactant of the carboxylic acid compound of unsaturated group, further with multi-anhydride reaction obtained from resin.
Wherein, the compound that preferably following formulas (a1) represent.The compound that the formula (a1) is represented is from the light of its own It is preferred from the aspect of curability is high.
In above-mentioned formula (a1), X represents the group that following formulas (a2) are represented.
In above-mentioned formula (a2), R1aHydrogen atom, the alkyl or halogen atom of carbon number 1~6 are represented independently of one another, R2aHydrogen atom or methyl are represented independently of one another, and W represents the group that singly-bound or following structural formula (a3) are represented.Need explanation It is that in formula (a2) and structural formula (a3), " * " represents the end of the chemical bond of divalent group.
In above-mentioned formula (a1), Y represents to remove residue obtained from anhydride group (- CO-O-CO-) from dicarboxylic anhydride.Make For the example of dicarboxylic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic acid can be enumerated Acid anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, chlorendic anhydride (chlorendic Anhydride), methyl tetrahydrophthalic anhydride, glutaric anhydride etc..
In addition, in above-mentioned formula (a1), Z represents to remove residue obtained from 2 anhydride groups from tetracarboxylic dianhydride.As The example of tetracarboxylic dianhydride, can enumerate pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, diphenyl Ether tetracarboxylic acid dianhydride etc..In addition, in above-mentioned formula (a1), a represents 0~20 integer.
For the acid number of the resin with ethylenic unsaturated group, in terms of resin solid state component, preferably 10~ 150mgKOH/g, more preferably 70~110mgKOH/g.By making acid number be more than 10mgKOH/g, it can obtain relative to development The sufficient dissolubility of liquid, thus preferably.In addition, by making acid number be below 150mgKOH/g, sufficient curability is can obtain, Superficiality can be made good, thus preferably.
In addition, the matter average molecular weight of the resin with ethylenic unsaturated group is preferably 1000~40000, more preferably 2000~30000.By making matter average molecular weight be more than 1000, good heat resistance, film-strength are can obtain, thus preferably.Separately Outside, by making matter average molecular weight be less than 40000, good developability is can obtain, thus preferably.
[monomer with ethylenic unsaturated group]
Monomer with ethylenic unsaturated group includes monofunctional monomer and polyfunctional monomer.Hereinafter, to simple function Monomer and polyfunctional monomer are illustrated successively.
As monofunctional monomer, (methyl) acrylamide, methylol (methyl) acrylamide, methoxy can be enumerated (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, butoxymethoxy Methyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- hydroxymethyls (methyl) acrylamide, (methyl) propylene Acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- acrylamides- 2- methyl propane sulfonic acids, tert-butyl acrylamide sulfonate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene Acid butyl ester, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (first Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 2- phenoxy group -2- hydroxy propyl esters, neighbour Phthalic acid 2- (methyl) acryloyl group epoxide -2- hydroxy propyl esters, glycerine list (methyl) acrylate, (methyl) acrylic acid tetrahydrochysene Furfuryl group ester, (methyl) acrylate ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2- trifluoros Ethyl ester, (methyl) acrylic acid 2,2,3,3- tetrafluoros propyl ester, (methyl) acrylate half ester of phthalic acid derivatives etc..These lists Functional monomer can be used alone, and two or more also can be combined and uses.
As polyfunctional monomer, can enumerate ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, fourth two Alcohol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, the alkylene oxide of carbon number 1~5 are modified neopentyl glycol Diacrylate (especially epoxy pronane modification neopentylglycol diacrylate), 1,6-HD two (methyl) acrylate, Trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythritol triacrylate, pentaerythrite Tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, pentaerythrite two (methyl) acrylic acid Ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, 2,2- double (4- (methyl) acryloxy diethoxy phenyl) propane, 2,2- Double (4- (methyl) acryloyl-oxies Quito ethoxyl phenenyl) propane, (methyl) acrylic acid 2- hydroxyls -3- (methyl) acryloyl group oxygen Base propyl ester, ethylene glycol diglycidyl base ether two (methyl) acrylate, (methyl) third of diethylene glycol diglycidyl glyceryl ether two Olefin(e) acid ester, phthalic acid 2-glycidyl base ester two (methyl) acrylate, glycerol tri-acrylate, glycerine poly epihydric alcohol Poly- (methyl) acrylate of base ether, carbamate (methyl) acrylate (that is, toluene di-isocyanate(TDI)), trimethyl -1,6- Reactant, the di-2-ethylhexylphosphine oxide (methyl) of hexamethylene diisocyanate and hexamethylene diisocyanate and (methyl) acrylic acid 2- hydroxy methacrylates Many officials such as acrylamide, (methyl) acrylamide methylene ether, the condensation product of polyalcohol and N- methylols (methyl) acrylamide Energy monomer, 1,3,5- triacryl hexahydro -1,3,5- triazines (triacrylformal) etc..These polyfunctional monomers can be independent Use, two or more also can be combined and uses.
Relative to the mass parts of total 100 of the composition in addition to solvent described later in photosensitive composite, as (A) into The content of the photopolymerizable compound divided is preferably 10~99.9 mass parts, more preferably 80~99.5 mass parts, further more Preferably 90~99 mass parts.By making the content of (A) composition relative to the mass of total 100 of the composition in addition to aftermentioned solvent Part is more than 10 mass parts, so that easily excellent using photosensitive composite formation heat resistance, chemical proofing and mechanical strength Different film.
In the present invention, (A) composition preferably comprises polyfunctional monomer, and polyfunctional monomer is more preferably 2 functions or 3 function lists Body, more preferably 2 functional monomers.(A) ratio of the polyfunctional monomer in composition is preferably more than 50 mass %, more preferably For more than 85 mass %, more preferably 90~100 mass %.
＜ (B) Photoepolymerizationinitiater initiaters ＞
(below, also known as photosensitive composite contains (B) Photoepolymerizationinitiater initiater of the compound represented comprising following formula (1) For (B) composition.).Comprising following formula (1) represent compound as the photosensitive composite of (B) Photoepolymerizationinitiater initiater sensitivity Degree is very excellent.Therefore, feelings of the compound comprising formula (1) expression as the photosensitive composite of Photoepolymerizationinitiater initiater are being used Under condition, also photosensitive composite can be made to solidify well even if by LED exposure.
In addition, by using the compound, the photosensitive composite that susceptibility is excellent, energy that are represented comprising following formula (1) Pattern when enough suppressing pattern formation is peeled off, and can suppress occur (the Japanese that rises and falls when forming line pattern (line pattern)： Ga つ I) (described rise and fall produces at the edge of pattern).
In addition, in the case where using the photosensitive composite formation pattern without colouring agent, according to Photoepolymerizationinitiater initiater Species, sometimes due to using photosensitive composite formation pattern implement after dry (post bake) and damage pattern The transparency.But, using photosensitive composite of the compound comprising following formula (1) expression as (B) Photoepolymerizationinitiater initiater In the case of, it is not easy to occurring the transparent pattern caused by heating reduces.
If especially photosensitive composite includes opacifier as (D) colouring agent described later, due to the shadow of opacifier Ring and make it that the bottom of the coated film of photosensitive composite is difficult to solidify, and therefore, produces undercut portions in the pattern of formation sometimes (undercut)。
If producing undercut portions in the pattern using the photosensitive composite formation comprising opacifier, for example, using this When the pattern of sample makes display device as black matrix", exist causes display due to remaining in the bubble of undercut portions part The problem of image quality of device is reduced.But, not only contain (D) colouring agent as opacifier in photosensitive composite but also contain In the case of (B) Photoepolymerizationinitiater initiater for having the compound represented comprising following formula (1), it can suppress using such photosensitive Property composition formation pattern in produce undercut portions.
For using photosensitive composite formation various patterns, expect its have will not be because of moisture etc. from strippable substrate Such excellent water resistance.If using the photonasty of (B) Photoepolymerizationinitiater initiater containing the compound represented comprising following formula (1) Composition, then be not easy to, from strippable substrate, easily form the pattern of excellent water resistance in the case of contacting with water.
In addition, in the pattern using photosensitive composite formation, sometimes included in the forming process of pattern because triggering Agent, the aggegation of resin and the foreign matter generated.But, if using (B) photopolymerization containing the compound represented comprising following formula (1) The photosensitive composite of initiator, then easily form the poor pattern of foreign matter.
(R1For hydrogen atom, nitro or monovalent organic group, R2And R3Can respectively have the chain-like alkyl of substituent, can have The cyclic organic group or hydrogen atom of substituted base, R2With R3It can be mutually bonded and form ring, R4For monovalent organic group, R5 For hydrogen atom, can have substituent carbon number 1~11 alkyl or can have substituent aryl, n for 0~4 it is whole Number, m is 0 or 1.)
In formula (1), R1For hydrogen atom, nitro or monovalent organic group.R1Be bonded in fluorenes ring in formula (1) with- (CO)mThe different hexa-atomic aromatic rings of hexa-atomic aromatic rings that-shown group is bonded.In formula (1), R1Relative to the bonding of fluorenes ring Position is not particularly limited.The compound that formula (1) is represented has the R of more than 11When, the chemical combination represented from the formula that is readily synthesized (1) Consider in terms of thing, it is preferable that the R of more than 11In 1 R1It is bonded to 2 in fluorenes ring.R1For it is multiple when, multiple R1Can With it is identical can also be different.
R1During for organic group, R1It is not particularly limited in the range of without prejudice to the object of the invention, can be from various organic groups Suitably selected in group.It is used as R1Preference during for organic group, can enumerate alkyl, alkoxy, cycloalkyl, cycloalkyloxy, full With aliphatic acyl radical, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, the phenyl can with substituent, can have substituent Phenoxy group, the benzoyl can with substituent, the phenyloxycarbonyl can with substituent, the benzoyl can with substituent Epoxide, can have substituent phenylalkyl, can have substituent naphthyl, can have substituent naphthoxy, can have take Dai Ji naphthoyl, can have substituent naphthoxycarbonyl, can have substituent naphthoyl epoxide, can have substitution The naphthylalkyl of base, can have substituent heterocyclic radical (heterocyclyl), can have substituent Heterocyclylcarbonyl, by 1 Individual or 2 organic group substitutions amino, morpholine -1- bases and piperazine -1- bases etc..
R1During for alkyl, the carbon number of alkyl is preferably 1~20, and more preferably 1~6.In addition, R1, can be with during for alkyl For straight chain, or side chain.It is used as R1Concrete example during for alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, positive fourth It is base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, different pungent Base, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..In addition, R1During for alkyl, alkyl can be in carbochain In include ehter bond (- O-).As in carbochain with ehter bond alkyl example, can enumerate methoxy ethyl, ethoxyethyl group, Methoxyethoxyethyl, ethoxyethoxyethyl, propyl group epoxide ethoxyethyl group and methoxy-propyl etc..
R1During for alkoxy, the carbon number of alkoxy is preferably 1~20, and more preferably 1~6.In addition, R1For alkoxy When, can be straight chain, or side chain.It is used as R1Concrete example during for alkoxy, can enumerate methoxyl group, ethyoxyl, positive third Base epoxide, isopropyl epoxide, normal-butyl epoxide, isobutyl group epoxide, sec-butyl epoxide, tert-butyl group epoxide, n-pentyl epoxide, isoamyl Base epoxide, sec-amyl epoxide, tertiary pentyl epoxide, n-hexyl epoxide, n-heptyl epoxide, n-octyl epoxide, iso-octyl epoxide, Zhong Xin Base epoxide, t-octyl epoxide, n-nonyl epoxide, isononyl epoxide, positive decyl epoxide and isodecyl epoxide etc..In addition, R1For alkane During epoxide, alkoxy can include ehter bond (- O-) in carbochain.As the example of the alkoxy with ehter bond in carbochain, it can lift Go out methoxy ethoxy, ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propyl group epoxide second Epoxide ethyoxyl and methoxy-propyl epoxide etc..
R1During for cycloalkyl or cycloalkyloxy, the carbon number of cycloalkyl or cycloalkyloxy is preferably 3~10, more preferably 3~6.It is used as R1Concrete example during for cycloalkyl, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring pungent Base etc..It is used as R1Concrete example during for cycloalkyloxy, can enumerate cyclopropyl epoxide, cyclobutyl epoxide, cyclopentyloxy, cyclohexyl Epoxide, suberyl epoxide and cyclooctyl epoxide etc..
R1During for representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy, representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyl The carbon number of base epoxide is preferably 2~21, and more preferably 2~7.It is used as R1Concrete example during for representative examples of saturated aliphatic acyl group, can Enumerate acetyl group, propiono, positive bytyry, 2- methylpropionyls, positive valeryl, 2,2- Dimethylpropanoyls, positive caproyl, just Heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, positive ten Four alkanoyls, n-pentadecane acyl group and hexadecane acyl group etc..It is used as R1Concrete example during for representative examples of saturated aliphatic acyloxy, Acetyl group epoxide, propiono epoxide, positive bytyry epoxide, 2- methylpropionyls epoxide, positive valeryl epoxide, 2,2- bis- can be enumerated Methylpropionyl epoxide, positive caproyl epoxide, positive heptanoyl group epoxide, positive caprylyl epoxide, positive pelargonyl group epoxide, positive capryl oxygen Base, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, positive 15 Alkanoyl epoxide and hexadecane acyloxy etc..
R1During for alkoxy carbonyl, the carbon number of alkoxy carbonyl is preferably 2~20, and more preferably 2~7.It is used as R1For Concrete example during alkoxy carbonyl, can enumerate methoxycarbonyl, ethoxy carbonyl, n-propyl Epoxide carbonyl, isopropyl epoxide carbonyl Base, normal-butyl Epoxide carbonyl, isobutyl group Epoxide carbonyl, sec-butyl Epoxide carbonyl, t-butyloxycarbonyl, n-pentyl epoxide carbonyl Base, isopentyl Epoxide carbonyl, sec-amyl Epoxide carbonyl, t-amyloxycarbonyl group, n-hexyl Epoxide carbonyl, n-heptyl epoxide carbonyl Base, n-octyl Epoxide carbonyl, iso-octyl Epoxide carbonyl, secondary octyl Epoxide carbonyl, t-octyl Epoxide carbonyl, n-nonyl epoxide carbonyl Base, isononyl Epoxide carbonyl, positive decyl Epoxide carbonyl and isodecyl Epoxide carbonyl etc..
R1During for phenylalkyl, the carbon number of phenylalkyl is preferably 7~20, and more preferably 7~10.In addition, R1For naphthalene During base alkyl, the carbon number of naphthylalkyl is preferably 11~20, and more preferably 11~14.It is used as R1Tool during for phenylalkyl Style, can enumerate benzyl, 2- phenylethyls, 3- phenyl propyls and 4- phenyl butyls.It is used as R1It is specific during for naphthylalkyl Example, can enumerate Alpha-Naphthyl methyl, betanaphthyl methyl, 2- (Alpha-Naphthyl) ethyls and 2- (betanaphthyl) ethyl.R1For phenylalkyl or During naphthylalkyl, R1Can further have substituent on phenyl or naphthyl.
R1During for heterocyclic radical, heterocyclic radical is five yuan or single six-membered rings comprising more than 1 N, S, O, or is the list Ring is each other or the monocyclic heterocyclic radical condensed with phenyl ring.When heterocyclic radical is fused rings, number of rings is less than 3.Heterocyclic radical can Think aromatic group (heteroaryl), or non-aromatic group.As the heterocycle for constituting the heterocyclic radical, furan can be enumerated Mutter, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, rattle away Piperazine, benzofuran, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, BTA, benzoxazole, benzothiazole, Carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperidines, piperazine, morpholine, piperidines, oxinane and Tetrahydrofuran etc..R1During for heterocyclic radical, heterocyclic radical can further have substituent.
R1During for Heterocyclylcarbonyl, the heterocyclic radical and R included in Heterocyclylcarbonyl1It is same for the situation of heterocyclic radical.
R1For replaced by 1 or 2 organic groups amino when, on the preference of organic group, carbon atom can be enumerated The alkyl of number 1~20, the cycloalkyl of carbon number 3~10, the representative examples of saturated aliphatic acyl group of carbon number 2~21, there can be substitution The phenyl of base, can have substituent benzoyl, can have substituent carbon number 7~20 phenylalkyl, can have The naphthyl of substituent, can have substituent naphthoyl, can have substituent carbon number 11~20 naphthylalkyl and Heterocyclic radical etc..The concrete example and R of these preferred organic groups1Equally.It is used as the amino replaced by 1 or 2 organic groups Concrete example, methylamino, ethylamino, diethylamino, n-propyl amino, diη-propyl amino, isopropyl ammonia can be enumerated Base, n-butylamino, di-n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino, n-nonyl Amino, positive decyl amino, phenyl amino, naphthyl-amino, acetyl-amino, propanoylamino, positive bytyry amino, positive valeryl Amino, positive caproyl amino, positive heptanoyl group amino, positive octanoylamino, positive decanoylamino, benzoyl-amido, α-naphthalene first Acyl amino and β-naphthoyl amino etc..
It is used as R1In the substituent of the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, carbon can be enumerated former Alkyl, the alkoxy of carbon number 1~6, the representative examples of saturated aliphatic acyl group of carbon number 2~7, the carbon number 2~7 of subnumber 1~6 Alkoxy carbonyl, the representative examples of saturated aliphatic acyloxy of carbon number 2~7, the monoalkyl of alkyl with carbon number 1~6 Dialkyl amido, morpholine -1- bases, piperazine -1- bases, halogen, nitro and the cyano group of amino, alkyl with carbon number 1~6 Deng.R1In the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, the number of the substituent is in this hair of without prejudice to Do not limited in the range of improving eyesight, preferably 1~4.R1In the phenyl, naphthyl and the heterocyclic radical that include there are multiple substituents When, multiple substituents can be the same or different.
In the group being illustrated above, R is used as1, it is nitro or R6During the group that-CO- is represented, there is susceptibility raising Tendency, be preferred.R6It is not particularly limited, can be selected from various organic groups in the range of without prejudice to the object of the invention Select.On being adapted as R6Group example, can enumerate carbon number 1~20 alkyl, can have substituent phenyl, can Naphthyl with substituent and the heterocyclic radical can with substituent.In these groups, R is used as6, particularly preferred 2- methylbenzenes Base, thiophene -2- bases and Alpha-Naphthyl.
In addition, R1During for hydrogen atom, there is hyalinosis and obtain good tendency, be preferred.It should be noted that R1For Hydrogen atom and R4For formula described later (R4-2) represent group when, there is hyalinosis and obtain better tendency.
In formula (1), R2And R3Respectively can have substituent chain-like alkyl, can have substituent cyclic organic group, Or hydrogen atom.R2With R3It can be mutually bonded and form ring.In these groups, R is used as2And R3, it is preferably can have substituent Chain-like alkyl.R2And R3For that can have during the chain-like alkyl of substituent, chain-like alkyl can be that straight chained alkyl can also be side chain Alkyl.
R2And R3During for chain-like alkyl without substituent, the carbon number of chain-like alkyl is preferably 1~20, more preferably For 1~10, particularly preferably 1~6.It is used as R2And R3Concrete example during for chain-like alkyl, can enumerate methyl, ethyl, n-propyl, Isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, N-octyl, iso-octyl, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..In addition, R2And R3For alkyl When, alkyl can include ehter bond (- O-) in carbochain.As the example of the alkyl with ehter bond in carbochain, methoxyl group can be enumerated Ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxyethoxyethyl, propyl group epoxide ethoxyethyl group and methoxyl group Propyl group etc..
R2And R3During for chain-like alkyl with substituent, the carbon number of chain-like alkyl is preferably 1~20, and more preferably 1 ~10, particularly preferably 1~6.In this case, not including the carbon number of substituent in the carbon number of chain-like alkyl.Have The chain-like alkyl of substituent is preferably straight-chain.
The substituent that alkyl can have is not particularly limited in the range of without prejudice to the object of the invention.It is used as substituent Preference, cyano group, halogen atom, cyclic organic group and alkoxy carbonyl can be enumerated.As halogen atom, fluorine can be enumerated Atom, chlorine atom, bromine atoms, iodine atom.Wherein, preferably fluorine atom, chlorine atom, bromine atoms.As cyclic organic group, it can lift Go out cycloalkyl, aromatic hydrocarbyl, heterocyclic radical.As the concrete example of cycloalkyl, with R1Preference during for cycloalkyl is same.As The concrete example of aromatic hydrocarbyl, can enumerate phenyl, naphthyl, xenyl, anthryl and phenanthryl etc..As the concrete example of heterocyclic radical, with R1Preference during for heterocyclic radical is same.R1During for alkoxy carbonyl, the alkoxy included in alkoxy carbonyl can be straight chain Shape, or branched, preferably straight-chain.The carbon number of the alkoxy included in alkoxy carbonyl is preferably 1~10, More preferably 1~6.
When chain-like alkyl has substituent, the number of substituent is not particularly limited.It is preferred that substituent number according to The carbon number of chain-like alkyl and change.Typically, the number of substituent is 1~20, preferably 1~10, more preferably 1~6.
R2And R3During for cyclic organic group, cyclic organic group can be ester ring type group, or aromatic series base Group.As cyclic organic group, aliphatic cyclic alkyl, aromatic hydrocarbyl, heterocyclic radical can be enumerated.R2And R3For ring-type organic group During group, substituent and R that cyclic organic group can have2And R3It is same for the situation of chain-like alkyl.
R2And R3During for aromatic hydrocarbyl, it is preferable that aromatic hydrocarbyl is phenyl, or it is that multiple phenyl ring enter via carbon-carbon bond Group formed by line unit conjunction, or the group formed by the fusion of multiple phenyl ring.Aromatic hydrocarbyl is phenyl or is multiple phenyl ring Formed by being bonded or being condensed during group, the number of rings of the phenyl ring included in aromatic hydrocarbyl is not particularly limited, and preferably 3 Hereinafter, more preferably less than 2, particularly preferably 1.As the preferred concrete example of aromatic hydrocarbyl, can enumerate phenyl, naphthyl, Xenyl, anthryl and phenanthryl etc..
R2And R3During for aliphatic cyclic alkyl, aliphatic cyclic alkyl can be that monocyclic can also be polycycle.Fat The carbon number of race's cyclic hydrocarbon group is not particularly limited, preferably 3~20, more preferably 3~10.It is used as the cyclic hydrocarbon of monocyclic The example of base, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, isobornyl, three Cyclononyl, tricyclodecyl, tetracyclododecyl group (tetracyclododecyl) and adamantyl etc..
R2And R3During for heterocyclic radical, heterocyclic radical is five yuan or single six-membered rings comprising more than 1 N, S, O, or is described It is monocyclic each other or the monocyclic heterocyclic radical condensed with phenyl ring.When heterocyclic radical is fused rings, number of rings is less than 3.Heterocyclic radical It can be aromatic group (heteroaryl), or non-aromatic group.As the heterocycle for constituting the heterocyclic radical, it can enumerate Furans, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, BTA, benzoxazole, benzo thiophene Azoles, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperidines, piperazine, morpholine, piperidines, tetrahydrochysene pyrrole Mutter and tetrahydrofuran etc..
R2With R3It can be mutually bonded and form ring.Include R2With R3The group of the ring formed preferably cycloalkylidene (cycloalkylidene group)。R2With R3When being bonded and forming cycloalkylidene, the ring for constituting cycloalkylidene is preferably five yuan Ring~hexatomic ring, more preferably five-membered ring.
R2With R3When group formed by bonding is cycloalkylidene, cycloalkylidene can be condensed with more than 1 other rings. As the example for the ring that can be condensed with cycloalkylidene, phenyl ring, naphthalene nucleus, cyclobutane ring, pentamethylene ring, cyclohexane ring, ring can be enumerated Heptane ring, cyclooctane ring, furan nucleus, thiphene ring, pyrrole ring, pyridine ring, pyrazine ring and pyrimidine ring etc..
The R being illustrated above2And R3In, as the example of preferred group, formula-A can be enumerated1-A2The group of expression. In formula, A1For straight-chain alkyl-sub, A2For alkoxy, cyano group, halogen atom, haloalkyl, cyclic organic group or alkoxy carbonyl Base.
It is used as A1The carbon number of straight-chain alkyl-sub be preferably 1~10, more preferably 1~6.A2During for alkoxy, alcoxyl Base can be straight-chain, or branched, preferably straight-chain.The carbon number of alkoxy is preferably 1~10, more preferably For 1~6.A2During for halogen atom, preferably fluorine atom, chlorine atom, bromine atoms, iodine atom, more preferably fluorine atom, chlorine are former Son, bromine atoms.A2During for haloalkyl, the halogen atom included in haloalkyl be preferably fluorine atom, chlorine atom, bromine atoms, Iodine atom, more preferably fluorine atom, chlorine atom, bromine atoms.Haloalkyl can be straight-chain, or branched, preferably For straight-chain.A2During for cyclic organic group, the example and R of cyclic organic group2And R3The ring-type having as substituent has Machine group is same.A2During for alkoxy carbonyl, the example and R of alkoxy carbonyl2And R3The alkoxy carbonyl having as substituent Base is same.
It is used as R2And R3Preferred concrete example, ethyl, n-propyl, normal-butyl, n-hexyl, n-heptyl and just pungent can be enumerated The alkyl such as base；2- methoxy ethyls, 3- methoxyl groups n-propyl, 4- methoxyl groups normal-butyl, 5- methoxyl groups n-pentyl, 6- methoxyl groups are just Hexyl, 7- methoxyl groups n-heptyl, 8- methoxyl groups n-octyl, 2- ethoxyethyl groups, 3- ethyoxyls n-propyl, the positive fourth of 4- ethyoxyls The alkoxyalkyls such as base, 5- ethyoxyls n-pentyl, 6- ethyoxyls n-hexyl, 7- ethyoxyls n-heptyl and 8- ethyoxyl n-octyls； 2- cyano ethyls, 3- cyano group n-propyl, 4- cyano group normal-butyl, 5- cyano group n-pentyl, 6- cyano group n-hexyl, 7- cyano group n-heptyl, And the cyanoalkyl such as 8- cyano group n-octyls；2- phenylethyls, 3- phenyl n-propyl, 4- phenyl normal-butyl, 5- phenyl n-pentyl, 6- The phenylalkyls such as phenyl n-hexyl, 7- phenyl n-heptyl and 8- phenyl n-octyls；2- cyclohexyl-ethyls, 3- cyclohexyl n-propyl, 4- cyclohexyl normal-butyl, 5- cyclohexyl n-pentyl, 6- cyclohexyl n-hexyl, 7- cyclohexyl n-heptyl, 8- cyclohexyl n-octyl, 2- Cyclopentyl ethyl, 3- cyclopenta n-propyl, 4- cyclopenta normal-butyl, 5- cyclopenta n-pentyl, 6- cyclopenta n-hexyl, 7- rings penta The cycloalkyl-alkyl such as base n-heptyl and 8- cyclopenta n-octyls；2- dion es, 3- methoxycarbonyls n-propyl, 4- Methoxycarbonyl normal-butyl, 5- methoxycarbonyls n-pentyl, 6- methoxycarbonyls n-hexyl, 7- methoxycarbonyls n-heptyl, 8- Methoxycarbonyl n-octyl, 2- ethoxycarbonylethyl groups, 3- ethoxy carbonyls n-propyl, 4- ethoxy carbonyls normal-butyl, 5- second The alkane such as Epoxide carbonyl n-pentyl, 6- ethoxy carbonyls n-hexyl, 7- ethoxy carbonyls n-heptyl and 8- ethoxy carbonyl n-octyls Epoxide carbonyl alkyl；2- chloroethyls, 3- chlorine n-propyl, 4- chloro-n-butyls, 5- chlorine n-pentyl, 6- chlorine n-hexyl, 7- chlorine n-heptyl, 8- chlorine n-octyl, 2- bromoethyls, 3- bromines n-propyl, 4- bromines normal-butyl, 5- bromines n-pentyl, 6- bromines n-hexyl, 7- bromines n-heptyl, 8- The haloalkyls such as bromine n-octyl, 3,3,3- trifluoro propyls and the fluorine n-pentyls of 3,3,4,4,5,5,5- seven.
It is used as R2And R3, it is above-mentioned in preferred group be ethyl, n-propyl, normal-butyl, n-pentyl, 2- methoxy ethyls, 2- Cyano ethyl, 2- phenylethyls, 2- cyclohexyl-ethyls, 2- dion es, 2- chloroethyls, 2- bromoethyls, 3,3,3- tri- Fluoropropyl and the fluorine n-pentyls of 3,3,4,4,5,5,5- seven.
It is used as R4Preferred organic group example, with R1Similarly, alkyl, alkoxy, cycloalkyl, cycloalkanes can be enumerated Epoxide, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, can have substituent phenyl, can have take Dai Ji phenoxy group, the benzoyl can with substituent, the phenyloxycarbonyl can with substituent, the benzene can with substituent Formoxyl epoxide, can have substituent phenylalkyl, can have substituent naphthyl, can have substituent naphthoxy, can Naphthoyl with substituent, can have substituent naphthoxycarbonyl, can have substituent naphthoyl epoxide, can have The naphthylalkyl of substituted base, the heterocyclic radical can with substituent, there can be the Heterocyclylcarbonyl of substituent, be had by 1 or 2 Amino, morpholine -1- bases and piperazine -1- bases of machine substituent group etc..The concrete example of these groups is with being directed to R1And explanation is specific Example is same.In addition, being used as R4, also preferably cycloalkyl-alkyl, can on aromatic rings the phenoxyalkyl with substituent, can be There is the phenylsulfartyl alkyl of substituent on aromatic rings.Substituent that phenoxyalkyl and phenylsulfartyl alkyl can have with R1In the substituent that can have of the phenyl that includes it is same.
In organic group, R is used as4, preferably alkyl, cycloalkyl, can have substituent phenyl or cycloalkyl-alkyl, There can be the phenylsulfartyl alkyl of substituent on aromatic rings.It is more excellent as the alkyl of alkyl, preferably carbon number 1~20 Elect the alkyl of the alkyl of carbon number 1~8, particularly preferably carbon number 1~4, most preferably methyl as.There can be substituent Phenyl in, preferably aminomethyl phenyl, more preferably 2- aminomethyl phenyls.The carbon number of the cycloalkyl included in cycloalkyl-alkyl is preferred For 5~10, more preferably 5~8, particularly preferably 5 or 6.The carbon number of the alkylidene included in cycloalkyl-alkyl is preferably 1 ~8, more preferably 1~4, particularly preferably 2.In cycloalkyl-alkyl, preferred cyclopentyl ethyl.There can be substitution on aromatic rings The carbon number of the alkylidene included in the phenylsulfartyl alkyl of base is preferably 1~8, more preferably 1~4, particularly preferably 2. Can be on aromatic rings in the phenylsulfartyl alkyl with substituent, preferably 2- (4- chlorophenyl sulfanyls) ethyl.
In addition, being used as R4, it is also preferably-A3-CO-O-A4The group of expression.A3For divalent organic group, preferably divalence Alkyl, more preferably alkylidene.A4For monovalent organic group, preferably monovalent hydrocarbon.
A3During for alkylidene, alkylidene can be straight-chain, or branched, preferably straight-chain.A3For alkylidene When, the carbon number of alkylidene is preferably 1~10, more preferably 1~6, particularly preferably 1~4.
It is used as A4Preference, the alkyl, the aralkyl of carbon number 7~20 and carbon that can enumerate carbon number 1~10 be former The aromatic hydrocarbyl of subnumber 6~20.It is used as A4Preferred concrete example, methyl, ethyl, n-propyl, isopropyl, positive fourth can be enumerated Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, Alpha-Naphthyl methyl and β-naphthalene Ylmethyl etc..
It is used as-A3-CO-O-A4The preferred concrete example of the group of expression, can enumerate 2- dion es, 2- ethoxies Base carbonylethyl, 2- n-propyl Epoxide carbonyls ethyl, 2- normal-butyl Epoxide carbonyls ethyl, 2- n-pentyl Epoxide carbonyls ethyl, 2- N-hexyl Epoxide carbonyl ethyl, 2- benzyloxycarbonyls ethyl, 2- phenyloxycarbonyls ethyl, 3- methoxycarbonyls n-propyl, 3- Ethoxy carbonyl n-propyl, 3- n-propyl Epoxide carbonyls n-propyl, 3- normal-butyl Epoxide carbonyls n-propyl, 3- n-pentyl epoxide carbonyls Base n-propyl, 3- n-hexyl Epoxide carbonyls n-propyl, 3- benzyloxycarbonyls n-propyl and 3- phenyloxycarbonyl n-propyls etc..
Above to R4It is illustrated, is used as R4, the group that preferably following formula (R4-1) or (R4-2) are represented.
(in formula (R4-1) and (R4-2), R7And R8Respectively organic group, p is 0~4 integer, R7And R8It is present in benzene During adjacent position on ring, R7With R8Can be mutually bonded and form ring, q be 1~8 integer, r be 1~5 integer, s be 0~ (r+3) integer, R9For organic group.)
R is used as in formula (R4-1)7And R8Organic group example and R1Equally.It is used as R7, preferably alkyl or benzene Base.R7During for alkyl, its carbon number is preferably 1~10, more preferably 1~5, particularly preferably 1~3, most preferably 1.That is, R7Most preferably methyl.R7With R8When being bonded and forming ring, the ring can be aromatic ring, or aliphatic ring.It is used as R7 With R8The preference of the group of formula (R4-1) expression of ring is formd, naphthalene -1- bases, 1,2,3,4- naphthane -5- bases etc. can be enumerated. In above-mentioned formula (R4-1), p is 0~4 integer, preferably 0 or 1, more preferably 0.
In above-mentioned formula (R4-2), R9For organic group.As organic group, it can enumerate with being directed to R1And the organic group illustrated The same group of group.In organic group, preferred alkyl.Alkyl can be straight-chain, or branched.The carbon atom of alkyl Number is preferably 1~10, more preferably 1~5, particularly preferably 1~3.It is used as R9, preferably enumerate methyl, ethyl, propyl group, different Propyl group, butyl etc., wherein, more preferably methyl.
In above-mentioned formula (R4-2), r is 1~5 integer, preferably 1~3 integer, more preferably 1 or 2.Above-mentioned formula (R4- 2) in, s is 0~(r+3), preferably 0~3 integer, more preferably 0~2 integer, particularly preferably 0.Above-mentioned formula (R4-2) In, q is 1~8 integer, preferably 1~5 integer, more preferably 1~3 integer, particularly preferably 1 or 2.
In formula (1), R5For hydrogen atom, the alkyl of the carbon number 1~11 can with substituent or there can be substituent Aryl.It is used as R5The substituent that can have during for alkyl, preferably enumerates phenyl, naphthyl etc..In addition, being used as R1During for aryl The substituent that can have, preferably enumerates alkyl, alkoxy, halogen atom of carbon number 1~5 etc..
In formula (1), R is used as5, preferably enumerate hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, phenyl, Benzyl, aminomethyl phenyl, naphthyl etc., wherein, more preferably methyl or phenyl.
Relative to the mass parts of gross mass 100 of the composition in addition to solvent in photosensitive composite, (B) composition is used as The content of Photoepolymerizationinitiater initiater is preferably 0.001~30 mass parts, more preferably 0.1~20 mass parts, more preferably 0.5 ~10 mass parts, particularly preferably 1~5 mass parts.
In addition, relative to the summation of (A) composition He (B) composition, the content as the Photoepolymerizationinitiater initiater of (B) composition is preferred For 0.05~50 mass %, more preferably more preferably 0.1~30 mass %, 0.5~20 mass %.
The content for the compound that following formula (1) is represented is for example relative to (B) composition generally 1~100 mass % scope , preferably more than 50 mass %, more preferably 70~100 mass %.
(B) compound that formula (1) in composition is represented can be used alone, it is possible to use two or more, during using two or more, It is preferred that following (i)~(iii)：
(i)R1For the compound and R of hydrogen atom1For the combination of the compound of nitro；
(ii)R4For the compound and R of formula (R4-1)4For the combination of the compound of formula (R4-2)；
(iii)R4For formula (R4-1) or the compound and R of formula (R4-2)4For the compound of the alkyl of carbon number 1~4.
Wherein, from the viewpoint of the characteristics such as the transmitance for improving susceptibility and solidfied material, the combination of preferably above-mentioned (i), More preferably meet above-mentioned (ii) or (iii), the combination with (i).
Based on above-mentioned (i)~match ratio (mass ratio) of each compound of the combination of (iii) is according to spies such as target susceptibility degree Property and suitably adjust, for example, it is preferable to for 1：99~99：1, more preferably 10：90~90：10, more preferably 30：70 ~70：30.
The manufacture method for the compound that formula (1) is represented is not particularly limited.Formula (1) represent compound preferably by including The method of following processes is manufactured, and the process is：The oximido (=N-OH) included in the compound that following formula (2) is represented turns Turn to=N-O-COR5The oxime ester base of expression.R5With the R in formula (1)5Equally.
(R1、R2、R3、R4, m and n and formula (1) it is same.N is 0~4 integer, and m is 0 or 1.)
Therefore, the synthesis for the compound that the compound that above-mentioned formula (2) represents is represented as formula (1) is useful with intermediate 's.
Oximido (=N-OH) is converted into=N-O-COR5The method of the oxime ester base of expression is not particularly limited.Typically, The hydroxyl and offer-COR made in oximido can be provided5The method that the acylating agent of the acyl group of expression is reacted., can as acylating agent Enumerate (R5CO)2Acid anhydrides that O is represented, R5The carboxylic acid halides that COHal (Hal is halogen atom) is represented.
, for example can be according to following synthesis paths (scheme) 1 when m is 0 for the compound that formula (1) is represented Synthesis.In synthesis path 1, the fluorene derivative represented using following formula (1-1) is used as raw material.R1For nitro or monovalent organic group When, formula (1-1) represent fluorene derivative can by using known method to 9 by R2And R3Imported in substituted fluorene derivative Substituent R1And obtain.For 9 by R2And R3For substituted fluorene derivative, such as R2And R3During for alkyl, such as day can be passed through Described in this Unexamined Patent 06-234668 publications like that, it is in the presence of an alkali metal hydroxide, organic in aprotic polar In solvent, fluorenes is set to be obtained with alkylation reactions.In addition, by adding haloalkyl so in the organic solvent solution to fluorenes Alkylating agent, phase transfer catalyst as the aqueous solution of alkali metal hydroxide and tetrabutylammonium iodide, potassium tert-butoxide and Reaction is alkylated, 9,9- alkyl substituted fluorenes are can obtain.
Using friedel-crafts (Friedel-Crafts) acylation reaction, the fluorene derivative represented to formula (1-1) Middle importing-CO-R4The acyl group of expression, can obtain the fluorene derivative of formula (1-3) expression.For importing-CO-R4The acyl group of expression Acylating agent can be halo carbonyl compounds, or acid anhydrides.As acylating agent, the halo carbonyl that preferably formula (1-2) is represented Based compound.In formula (1-2), Hal is halogen atom.In fluorenes ring import acyl group position can by suitably change Fred- Gram carry out the condition of Ford reaction or implement protection and the method being deprotected for the position beyond the position that is acylated and carry out Selection.
Then ,-the CO-R in the fluorene derivative obtained formula (1-3) represented4The group of expression is converted into-C (=N- OH)-R4The group of expression, obtains the oxime compound of formula (1-4) expression.By-CO-R4The group of expression be converted into-C (=N-OH)- R4The method of the group of expression is not particularly limited, the oximate carried out preferably by hydroxylamine.Make formula (1-4) oxime compound, The acid anhydrides ((R represented with following formula (1-5)5CO)2O) or following formulas (1-6) represent carboxylic acid halides (R5COHal, Hal are that halogen is former Son.) reacted, it can obtain the compound of following formula (1-7) expression.
It should be noted that in formula (1-1), (1-2), (1-3), (1-4), (1-5), (1-6) and (1-7), R1、R2、R3、 R4And R5It is same with formula (1).
In addition, in synthesis path 1, formula (1-2), formula (1-3) and formula (1-4) it is various in the R that includes4Can be with identical With difference.That is, the R in formula (1-2), formula (1-3) and formula (1-4)4Can be in the building-up process shown as synthesis path 1 By chemical modification.As the example of chemical modification, esterification, etherificate, acylation, amidatioon, halogenation, organic group can be enumerated to ammonia Substitution of hydrogen atom in base etc..R4Acceptable chemical modification is not limited to these.
The ＞ of ＜ synthesis paths 1
For the compound that formula (1) is represented, when m is 1, for example, it can be synthesized according to following synthesis paths 2.Synthesize road In footpath 2, the fluorene derivative represented using following formula (2-1) is used as raw material.Formula (2-1) represent fluorene derivative can by using with Importing-CO- in the same method of synthesis path 1, the compound represented using Friedel-Crafts reaction to formula (1-1) CH2-R4The acyl group of expression and obtain.It is used as acylating agent, preferably formula (1-8)：Hal-CO-CH2-R4The acid halide of expression.Connect , be present in R in the compound that formula (2-1) is represented4Methylene between carbonyl carries out oximate, obtains following formula (2-3) The ketoxime compounds of expression.By methylene carry out oximate method be not particularly limited, preferably in the presence of hydrochloric acid with it is following (RONO, R are the alkyl of carbon number 1~6 to the nitrous acid ester that formula (2-2) is represented.) method reacted.Then, under making The ketoxime compounds for stating formula (2-3) expression, the acid anhydrides ((R represented with following formula (2-4)5CO)2O) or following formulas (2-5) represent Carboxylic acid halides (R5COHal, Hal are halogen atom.) reacted, it can obtain the compound of following formula (2-6) expression.Need explanation , in following formula (2-1), (2-3), (2-4), (2-5) and (2-6), R1、R2、R3、R4And R5It is same with formula (1).
When m is 1, there is following tendency：The photosensitive composition using the compound represented containing formula (1) can further be reduced The generation of foreign matter in pattern formed by thing.
In addition, in synthesis path 2, formula (1-8), formula (2-1) and formula (2-3) it is various in the R that includes4Can be with identical With difference.That is, the R in formula (1-8), formula (2-1) and formula (2-3)4Can be in the building-up process shown as synthesis path 2 By chemical modification.As the example of chemical modification, esterification, etherificate, acylation, amidatioon, halogenation, organic group can be enumerated to ammonia Substitution of hydrogen atom in base etc..R4Acceptable chemical modification is not limited to these.
The ＞ of ＜ synthesis paths 2
The preferred concrete example of the compound represented as formula (1), can enumerate following 1~compound of compound 41.
＜ (C) sensitizers ＞
Photosensitive composite not only containing above-mentioned (B) Photoepolymerizationinitiater initiater but also contains (C) sensitizer.By making sense Photosensitiveness composition not only contains (B) Photoepolymerizationinitiater initiater of the compound represented comprising above-mentioned formula (1) but also containing (C) sensitization Agent, so as to also photosensitive composite can be made to solidify well even with LED exposure.
It is thought that because the compound that formula (1) is represented is particularly easy to be sensitized agent sensitization.
As (C) sensitizer, can be not particularly limited using in the past in photosensitive composite for making photopolymerization The purpose of initiator sensitization and the compound that uses.
It is used as (C) sensitizer, it is however preferred to have selected from by alkoxy, substituted carbonyl epoxide (carbonyloxy) and oxo Base (=O) composition group in more than a kind of group as substituent compound.As the compound with the substituent, Preferably fused polycyclic aromatic hydrocarbon compound or fused polycyclic aromatic heterocyclic compounds.
Fused polycyclic aromatic hydrocarbon compound or fused polycyclic aromatic heterocyclic compounds, which can also have, removes alcoxyl Substituent beyond base, substituted carbonyl epoxide and oxo base (=O).As the example of the substituent, carbon number 1 can be enumerated ~20 alkyl, the haloalkyl of carbon number 1~20, the alkoxyalkyl of carbon number 2~20, carbon number 2~20 Aliphatic acyl radical, the aromatic acyl (aroyl) of carbon number 7~11, cyano group, nitro, nitroso, halogen atom, hydroxyl, And sulfydryl etc..
Alkoxy can be straight-chain, or branched.The carbon number of alkoxy is not particularly limited, and is preferably 1~20, more preferably 1~12, particularly preferably 1~6.
As the preference of alkoxy, methoxyl group, ethyoxyl, n-propyl epoxide, isopropyl epoxide, normal-butyl oxygen can be enumerated Base, isobutyl group epoxide, tert-butyl group epoxide, n-pentyl epoxide, n-hexyl epoxide, n-heptyl epoxide, n-octyl epoxide, 2- ethyl hexyls Base, n-nonyl epoxide and positive decyl epoxide etc..
Substituted carbonyl epoxide is the group that-O-CO-A is represented.For A, if (C) sensitizer have it is desired quick Change is acted on, and is not particularly limited, can is various organic groups.It is used as A, the preferably alkyl of carbon number 1~20, carbon Aryl, the alkoxy of carbon number 1~20, the aryloxy of carbon number 6~10 of atomicity 6~10.
Aryl or aryloxy can have one or more substituents.For the species of substituent, as long as without prejudice to sheet The purpose of invention is not particularly limited.When aryl or aryloxy have multiple substituents, multiple substituents can be with identical Can be different.
As the preference of substituent, the alkyl, the alkoxy of carbon number 1~6, carbon that can enumerate carbon number 1~6 are former The aryl of subnumber 6~10, the aryloxy of carbon number 6~10, the aliphatic acyl radical of carbon number 2~7, carbon number 7~ 11 aromatic acyl (aroyl), cyano group, nitro, nitroso, halogen atom, hydroxyl and sulfydryl etc..
When A is alkyl or alkoxy, these groups can be straight-chain, or branched.
As the preference of alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, N-pentyl, n-hexyl, n-heptyl, n-octyl and 2- ethylhexyls etc..
As the preference of aryl, phenyl, o-tolyl, a tolyl, p-methylphenyl, Alpha-Naphthyl, betanaphthyl can be enumerated Deng.
As the preference of alkoxy, methoxyl group, ethyoxyl, n-propyl epoxide, isopropyl epoxide, normal-butyl oxygen can be enumerated Base, isobutyl group epoxide, tert-butyl group epoxide, n-pentyl epoxide, n-hexyl epoxide, n-heptyl epoxide, n-octyl epoxide and 2- ethyls Hexyl epoxide etc..
More than a kind of group being selected from the group being made up of alkoxy, substituted carbonyl epoxide and oxo base (=O) takes In the fused polycyclic aromatic hydrocarbon compound or fused polycyclic aromatic heterocyclic compounds in generation, the number of rings of fused rings is constituted It is not particularly limited, as long as desired sensibilization can be obtained.Number of rings is preferably more than 2, and more preferably more than 3, it is special You Xuanwei 3~6, most preferably 3 or 4.
It should be noted that it is not necessarily aromatic rings to form the monocyclic of fused polycycle, as long as fused polycyclic aromatic series Hydrocarbon compound or fused polycyclic aromatic heterocyclic compounds have armaticity.
It is used as the fusion included in fused polycyclic aromatic hydrocarbon compound or fused polycyclic aromatic heterocyclic compounds Polycyclic preference, can enumerate acenaphthylene ring, phenanthrene ring, anthracene nucleus, naphthonaphthalene (naphthacene) ring, xanthene ring and thioxanthene ring.This In a little rings, preferably anthracene nucleus, naphtho- naphthalene nucleus and thioxanthene ring.
As it is comprising anthracene nucleus, be suitable as (C) sensitizer compound concrete example, the double (acetyl group of 9,10- can be enumerated Epoxide) anthracene, double (propiono epoxide) anthracenes of 9,10-, double (the n-propyl carbonyl epoxide) anthracenes of 9,10-, double (the Isopropylcarbonyl oxygen of 9,10- Base) anthracene, double (n-butylcarbonyl epoxide) anthracenes of 9,10-, double (butylcarbonyl epoxide) anthracenes of 9,10-, the double (n-pentylcarbonyls of 9,10- Epoxide) anthracene, double (n-hexylcarbonyl epoxide) anthracenes of 9,10-, double (the n-heptyl carbonyl epoxide) anthracenes of 9,10-, double (the 2- ethyl hexyls of 9,10- Acyloxy) anthracene, double (the n-octyl carbonyl epoxide) anthracenes of 9,10-, double (the n-nonyl carbonyl epoxide) anthracenes of 9,10-, 9,10- double (positive last of the ten Heavenly stems Base carbonyl epoxide) anthracene, double (benzoyl epoxide) anthracenes of 9,10-, double (the 4- methyl benzoyls epoxide) anthracenes of 9,10-, 9,10- are double Double (acetyl group epoxide) anthracenes of (2- naphthoyls epoxide) anthracene, 2- methyl -9,10-, double (propiono epoxide) anthracenes of 2- methyl -9,10-, Double (the n-propyl carbonyl epoxide) anthracenes of 2- methyl -9,10-, 2- methyl -9,10- double (Isopropylcarbonyl epoxide) anthracene, 2- methyl -9, Double (n-butylcarbonyl epoxide) anthracenes of 10-, double (butylcarbonyl epoxide) anthracenes of 2- methyl -9,10-, 2- methyl -9,10- double (positive penta Base carbonyl epoxide) anthracene, double (n-hexylcarbonyl epoxide) anthracenes of 2- methyl -9,10-, 2- methyl -9,10- be double (benzoyl epoxide) Double (the 4- methyl benzoyls epoxide) anthracenes of anthracene, 2- methyl -9,10-, 2- methyl -9,10- double (2- naphthoyls epoxide) anthracene, 1- first Double (acetyl group epoxide) anthracenes of base -9,10-, double (propiono epoxide) anthracenes of 1- methyl -9,10-, double (the n-propyl carbonyls of 1- methyl -9,10- Base epoxide) anthracene, double (Isopropylcarbonyl epoxide) anthracenes of 1- methyl -9,10-, double (n-butylcarbonyl epoxide) anthracenes of 1- methyl -9,10-, Double (butylcarbonyl epoxide) anthracenes of 1- methyl -9,10-, 1- methyl -9,10- double (n-pentylcarbonyl epoxide) anthracene, 1- methyl -9, Double (n-hexylcarbonyl epoxide) anthracenes of 10-, double (benzoyl epoxide) anthracenes of 1- methyl -9,10-, double (the 4- methyl of 1- methyl -9,10- Benzoyl epoxide) anthracene, double (the 2- naphthoyls epoxide) anthracenes of 1- methyl -9,10-, 2- ethyls -9,10- be double (acetyl group epoxide) Double (propiono epoxide) anthracenes of anthracene, 2- ethyls -9,10-, 2- ethyls -9,10- double (n-propyl carbonyl epoxide) anthracene, 2- ethyls -9,10- Double (n-butylcarbonyl epoxide) anthracenes of double (butylcarbonyl epoxide) anthracenes, 2- ethyls -9,10-, double (the isobutyl group carbonyls of 2- ethyls -9,10- Base epoxide) anthracene, double (n-pentylcarbonyl epoxide) anthracenes of 2- ethyls -9,10-, double (n-hexylcarbonyl epoxide) anthracenes of 2- ethyls -9,10-, Double (benzoyl epoxide) anthracenes of 2- ethyls -9,10-, 2- ethyls -9,10- double (4- ethylamino benzonitrile acyl groups epoxide) anthracene, 2- ethyl -9, Double (the 2- naphthoyls epoxide) anthracenes of 10-, double (acetyl group epoxide) anthracenes of 1- ethyls -9,10-, double (the propiono oxygen of 1- ethyls -9,10- Base) anthracene, double (the n-propyl carbonyl epoxide) anthracenes of 1- ethyls -9,10-, 1- ethyls -9,10- double (Isopropylcarbonyl epoxide) anthracene, 1- second Double (n-butylcarbonyl epoxide) anthracenes of base -9,10-, double (butylcarbonyl epoxide) anthracenes of 1- ethyls -9,10-, 1- ethyls -9,10- are double Double (n-hexylcarbonyl epoxide) anthracenes of (n-pentylcarbonyl epoxide) anthracene, 1- ethyls -9,10-, double (the benzoyl oxygen of 1- ethyls -9,10- Base) anthracene, double (the 4- ethylamino benzonitrile acyl groups epoxide) anthracenes of 1- ethyls -9,10-, double (the 2- naphthoyls epoxide) anthracenes of 1- ethyls -9,10-, Double (the n-propyl carbonyl epoxide) anthracenes of the 1- tert-butyl groups -9,10-, the 1- tert-butyl groups -9,10- double (Isopropylcarbonyl epoxide) anthracene, the tertiary fourths of 1- Double (n-butylcarbonyl epoxide) anthracenes of base -9,10-, the 1- tert-butyl groups -9,10- double (butylcarbonyl epoxide) anthracene, the 1- tert-butyl group -9, Double (n-pentylcarbonyl epoxide) anthracenes of 10-, double (n-hexylcarbonyl epoxide) anthracenes of the 1- tert-butyl groups -9,10-, the 1- tert-butyl groups -9,10- are double Double (the 4- tert-butyl-benzoyls epoxide) anthracenes of (benzoyl epoxide) anthracene, the 1- tert-butyl groups -9,10-, the double (2- of the 1- tert-butyl groups -9,10- Naphthoyl epoxide) anthracene, double (the n-propyl carbonyl epoxide) anthracenes of the 2- tert-butyl groups -9,10-, double (the isopropyl carbonyls of the 2- tert-butyl groups -9,10- Base epoxide) anthracene, double (n-butylcarbonyl epoxide) anthracenes of the 2- tert-butyl groups -9,10-, the 2- tert-butyl groups -9,10- be double (butylcarbonyl epoxide) Double (n-pentylcarbonyl epoxide) anthracenes of anthracene, the 2- tert-butyl groups -9,10-, the 2- tert-butyl groups -9,10- double (n-hexylcarbonyl epoxide) anthracene, uncles 2- Double (benzoyl epoxide) anthracenes of butyl -9,10-, the 2- tert-butyl groups -9,10- double (4- tert-butyl-benzoyls epoxide) anthracene, the tertiary fourths of 2- Double (the 2- naphthoyls epoxide) anthracenes of base -9,10-, double (the n-propyl carbonyl epoxide) anthracenes of 2- amyl groups -9,10-, 2- amyl groups -9,10- are double Double (n-butylcarbonyl epoxide) anthracenes of (Isopropylcarbonyl epoxide) anthracene, 2- amyl groups -9,10-, the double (butylcarbonyls of 2- amyl groups -9,10- Epoxide) anthracene, double (n-pentylcarbonyl epoxide) anthracenes of 2- amyl groups -9,10-, 2- amyl groups -9,10- double (n-hexylcarbonyl epoxide) anthracene, 2- Double (benzoyl epoxide) anthracenes of amyl group -9,10-, double (the 4- tert-butyl-benzoyls epoxide) anthracenes of 2- amyl groups -9,10- and 2- amyl groups - Double (2- naphthoyls epoxide) anthracenes of 9,10- etc..
In addition, the anthracene compound being substituted with halogen atoms is it is also preferred that be used as (C) sensitizer.As halogen atom, it can enumerate Fluorine atom, chlorine atom, bromine atoms or iodine atom.
On preferably as (C) sensitizer, the concrete example of anthracene compound that is substituted with halogen atoms, 2- can be enumerated chloro- Double (acetyl group epoxide) anthracenes of 9,10-, double (propiono epoxide) anthracenes of the chloro- 9,10- of 2-, the chloro- 9,10- of 2- are double (n-propyl carbonyl epoxide) Double (Isopropylcarbonyl epoxide) anthracenes of the chloro- 9,10- of anthracene, 2-, double (n-butylcarbonyl epoxide) anthracenes of the chloro- 9,10- of 2-, the chloro- 9,10- of 2- are double Double (n-pentylcarbonyl epoxide) anthracenes of (butylcarbonyl epoxide) anthracene, the chloro- 9,10- of 2-, double (the n-hexylcarbonyl oxygen of the chloro- 9,10- of 2- Base) anthracene, double (benzoyl epoxide) anthracenes of 2- chloro- 9,10-, the chloro- 9,10- of 2- double (4- methyl benzoyls epoxide) anthracene, 2- chloro- 9, Double (the 2- naphthoyls epoxide) anthracenes of 10-, double (acetyl group epoxide) anthracenes of the chloro- 9,10- of 1-, the chloro- 9,10- of 1- are double (propiono epoxide) Double (the n-propyl carbonyl epoxide) anthracenes of the chloro- 9,10- of anthracene, 1-, double (Isopropylcarbonyl epoxide) anthracenes of the chloro- 9,10- of 1-, the chloro- 9,10- of 1- are double Double (butylcarbonyl epoxide) anthracenes of (n-butylcarbonyl epoxide) anthracene, the chloro- 9,10- of 1-, double (the n-pentylcarbonyl oxygen of the chloro- 9,10- of 1- Base) anthracene, double (n-hexylcarbonyl epoxide) anthracenes of 1- chloro- 9,10-, the chloro- 9,10- of 1- double (benzoyl epoxide) anthracene, the chloro- 9,10- of 1- Double (the 2- naphthoyls epoxide) anthracenes of double (4- methyl benzoyls epoxide) anthracenes, the chloro- 9,10- of 1-, double (the acetyl group oxygen of the fluoro- 9,10- of 2- Base) anthracene, double (propiono epoxide) anthracenes of 2- fluoro- 9,10-, double (the n-propyl carbonyl epoxide) anthracenes of the fluoro- 9,10- of 2-, the fluoro- 9,10- of 2- be double Double (n-butylcarbonyl epoxide) anthracenes of (Isopropylcarbonyl epoxide) anthracene, the fluoro- 9,10- of 2-, double (the butylcarbonyl oxygen of the fluoro- 9,10- of 2- Base) anthracene, double (n-pentylcarbonyl epoxide) anthracenes of 2- fluoro- 9,10-, the fluoro- 9,10- of 2- double (n-hexylcarbonyl epoxide) anthracene, 2- fluoro- 9, Double (benzoyl epoxide) anthracenes of 10-, double (the 4- methyl benzoyls epoxide) anthracenes of the fluoro- 9,10- of 2-, double (the 2- naphthalene first of the fluoro- 9,10- of 2- Acyloxy) anthracene, double (acetyl group epoxide) anthracenes of 1- fluoro- 9,10-, the fluoro- 9,10- of 1- double (propiono epoxide) anthracene, the fluoro- 9,10- of 1- Double (Isopropylcarbonyl epoxide) anthracenes of double (n-propyl carbonyl epoxide) anthracenes, the fluoro- 9,10- of 1-, double (the n-butylcarbonyl oxygen of the fluoro- 9,10- of 1- Base) anthracene, double (butylcarbonyl epoxide) anthracenes of 1- fluoro- 9,10-, the fluoro- 9,10- of 1- double (n-pentylcarbonyl epoxide) anthracene, 1- fluoro- 9, Double (n-hexylcarbonyl epoxide) anthracenes of 10-, double (benzoyl epoxide) anthracenes of the fluoro- 9,10- of 1-, double (the 4- methylbenzene first of the fluoro- 9,10- of 1- Acyloxy) anthracene, double (the 2- naphthoyls epoxide) anthracenes of 1- fluoro- 9,10-, the bromo- 9,10- of 2- double (acetyl group epoxide) anthracene, 2- bromo- 9, Double (propiono epoxide) anthracenes of 10-, double (the n-propyl carbonyl epoxide) anthracenes of the bromo- 9,10- of 2-, double (the Isopropylcarbonyl oxygen of the bromo- 9,10- of 2- Base) anthracene, double (n-butylcarbonyl epoxide) anthracenes of 2- bromo- 9,10-, the bromo- 9,10- of 2- double (butylcarbonyl epoxide) anthracene, 2- bromo- 9, Double (n-pentylcarbonyl epoxide) anthracenes of 10-, double (n-hexylcarbonyl epoxide) anthracenes of the bromo- 9,10- of 2-, the double (benzoyls of the bromo- 9,10- of 2- Epoxide) anthracene, double (the 4- methyl benzoyls epoxide) anthracenes of 2- bromo- 9,10-, the bromo- 9,10- of 2- double (2- naphthoyls epoxide) anthracene, 1- Double (acetyl group epoxide) anthracenes of bromo- 9,10-, double (propiono epoxide) anthracenes of the bromo- 9,10- of 1-, double (the n-propyl ketonic oxygens of the bromo- 9,10- of 1- Base) anthracene, double (Isopropylcarbonyl epoxide) anthracenes of 1- bromo- 9,10-, the bromo- 9,10- of 1- double (n-butylcarbonyl epoxide) anthracene, 1- bromo- 9, Double (butylcarbonyl epoxide) anthracenes of 10-, double (n-pentylcarbonyl epoxide) anthracenes of the bromo- 9,10- of 1-, double (the n-hexyl carbonyls of the bromo- 9,10- of 1- Base epoxide) anthracene, double (benzoyl epoxide) anthracenes of 1- bromo- 9,10-, double (the 4- methyl benzoyls epoxide) anthracenes of the bromo- 9,10- of 1- and Double (2- naphthoyls epoxide) anthracenes of the bromo- 9,10- of 1- etc..
In addition, the anthracene compound replaced by alkoxy is it is also preferred that be used as (C) sensitizer.
On preferably as (C) sensitizer, the concrete example of anthracene compound that is replaced by alkoxy, 9,10- bis- can be enumerated Double (n-propyl epoxide) anthracenes of methoxyl group anthracene, 9,10- diethoxies anthracene, 9,10-, double (normal-butyl epoxide) anthracenes of 9,10-, 9,10- are double Double (the isopentyl epoxide epoxide) anthracenes of (n-pentyl epoxide) anthracene, 9,10-, double (n-hexyl epoxide) anthracenes of 9,10-, the double (n-heptyls of 9,10- Epoxide) anthracene, double (n-octyl epoxide) anthracenes of 9,10-, 9,10- double (2- ethylhexyls epoxide) anthracene, 9- methoxyl groups anthracene, 9- ethyoxyls Anthracene, 9- (n-propyl epoxide) anthracene, 9- (normal-butyl epoxide) anthracene, 9- (n-pentyl epoxide) anthracene, 9- (isopentyl epoxide epoxide) anthracene, 9- (n-hexyl epoxide) anthracene, 9- (n-heptyl epoxide) anthracene, 9- (n-octyl epoxide) anthracene, 9- (2- ethylhexyls epoxide) anthracene, 2- methyl- 9,10- dimethoxys anthracene, 2- methyl -9,10- diethoxies anthracene, 2- methyl -9,10- double (n-propyl epoxide) anthracene, 2- methyl -9, Double (normal-butyl epoxide) anthracenes of 10-, double (n-pentyl epoxide) anthracenes of 2- methyl -9,10-, double (the isopentyl epoxide oxygen of 2- methyl -9,10- Base) anthracene, double (n-hexyl epoxide) anthracenes of 2- methyl -9,10-, 2- methyl -9,10- double (n-heptyl epoxide) anthracene, 2- methyl -9,10- Double (n-octyl epoxide) anthracenes, 2- methyl -9,10- double (2- ethylhexyls epoxide) anthracene, 2- ethyl -9,10- dimethoxys anthracene, 2- second Double (n-propyl epoxide) anthracenes of base -9,10- diethoxies anthracene, 2- ethyls -9,10-, double (normal-butyl epoxide) anthracenes of 2- ethyls -9,10-, Double (n-pentyl epoxide) anthracenes of 2- ethyls -9,10-, double (the isopentyl epoxide epoxide) anthracenes of 2- ethyls -9,10-, 2- ethyls -9,10- are double Double (n-heptyl epoxide) anthracenes of (n-hexyl epoxide) anthracene, 2- ethyls -9,10-, 2- ethyls -9,10- double (n-octyl epoxide) anthracene, 2- second Base -9,10- double (2- ethylhexyls epoxide) anthracene, 2- methyl -9- methoxyl groups anthracene, 2- methyl -9- ethyoxyls anthracene, 2- methyl -9- are (just Propyl group epoxide) anthracene, 2- methyl -9- (normal-butyl epoxide) anthracene, 2- methyl -9- (n-pentyl epoxide) anthracene, 2- methyl -9- (isopentyl Epoxide epoxide) anthracene, 2- methyl -9- (n-hexyl epoxide) anthracene, 2- methyl -9- (n-heptyl epoxide) anthracene, 2- methyl -9- (n-octyls Epoxide) anthracene, 2- methyl -9- (2- ethylhexyls epoxide) anthracene, 2- ethyl -9- methoxyl groups anthracene, 2- ethyl -9- ethyoxyls anthracene, 2- second Base -9- (n-propyl epoxide) anthracene, 2- ethyls -9- (normal-butyl epoxide) anthracene, 2- ethyls -9- (n-pentyl epoxide) anthracene, 2- ethyls -9- (isopentyl epoxide epoxide) anthracene, 2- ethyls -9- (n-hexyl epoxide) anthracene, 2- ethyls -9- (n-heptyl epoxide) anthracene, 2- ethyls -9- (n-octyl epoxide) anthracene, 2- ethyls -9- (2- ethylhexyls epoxide) anthracene, the chloro- 9,10- dimethoxys anthracenes of 2-, the chloro- 9,10- bis- of 2- Double (n-propyl epoxide) anthracenes of the chloro- 9,10- of ethyoxyl anthracene, 2-, double (normal-butyl epoxide) anthracenes of the chloro- 9,10- of 2-, the chloro- 9,10- of 2- are double Double (the isopentyl epoxide epoxide) anthracenes of (n-pentyl epoxide) anthracene, the chloro- 9,10- of 2-, the chloro- 9,10- of 2- double (n-hexyl epoxide) anthracene, 2- Double (n-heptyl epoxide) anthracenes of chloro- 9,10-, double (n-octyl epoxide) anthracenes of the chloro- 9,10- of 2-, double (the 2- ethylhexyl oxygen of the chloro- 9,10- of 2- Base) anthracene, the bromo- 9,10- dimethoxys anthracenes of 2-, the bromo- 9,10- diethoxies anthracenes of 2-, 2- bromo- 9,10- double (n-propyl epoxide) anthracene, 2- Double (normal-butyl epoxide) anthracenes of bromo- 9,10-, double (n-pentyl epoxide) anthracenes of the bromo- 9,10- of 2-, double (the isopentyl epoxide oxygen of the bromo- 9,10- of 2- Base) anthracene, double (n-hexyl epoxide) anthracenes of 2- bromo- 9,10-, double (n-heptyl epoxide) anthracenes of the bromo- 9,10- of 2-, the bromo- 9,10- of 2- be double (just pungent Base epoxide) anthracene, 2- bromo- 9,10- double (2- ethylhexyls epoxide) anthracene, the chloro- 9- methoxyl groups anthracenes of 2-, the chloro- 9- ethyoxyls anthracenes of 2-, 2- Chloro- 9- (n-propyl epoxide) anthracene, the chloro- 9- of 2- (normal-butyl epoxide) anthracene, the chloro- 9- of 2- (n-pentyl epoxide) anthracene, the chloro- 9- (isoamyls of 2- Base epoxide epoxide) anthracene, the chloro- 9- of 2- (n-hexyl epoxide) anthracene, the chloro- 9- of 2- (n-heptyl epoxide) anthracene, the chloro- 9- of 2- (n-octyl epoxide) The chloro- 9- of anthracene, 2- (2- ethylhexyls epoxide) anthracene, the bromo- 9- methoxyl groups anthracenes of 2-, the bromo- 9- ethyoxyls anthracenes of 2-, 2- bromo- 9- (n-propyl oxygen Base) anthracene, the bromo- 9- of 2- (normal-butyl epoxide) anthracene, the bromo- 9- of 2- (n-pentyl epoxide) anthracene, 2- ethyls -9- (isopentyl epoxide epoxide) The bromo- 9- of anthracene, 2- (n-hexyl epoxide) anthracene, the bromo- 9- of 2- (n-heptyl epoxide) anthracene, the bromo- 9- of 2- (n-octyl epoxide) anthracenes and 2- are bromo- 9- (2- ethylhexyls epoxide) anthracene etc..
In the anthracene compound being illustrated above, examined from the easiness of manufacture and as the viewpoint of the performance of (C) sensitizer Consider, double (propiono epoxide) anthracenes of double (acetyl group epoxide) anthracenes of preferably 9,10-, 9,10-, double (the n-propyl carbonyl epoxide) anthracenes of 9,10-, Double (Isopropylcarbonyl epoxide) anthracenes of 9,10-, double (n-butylcarbonyl epoxide) anthracenes of 9,10-, 9,10- are double (butylcarbonyl epoxide) Double (the positive caproyl epoxide) anthracenes of anthracene, 9,10-, double (the positive heptanoyl group epoxide) anthracenes of 9,10-, 9,10- double (positive caprylyl epoxide) anthracene, 9, Double (the 2- ethyl hexyls acyloxy) anthracenes of 10-, 9,10- double (positive pelargonyl group epoxide) anthracene, 9,10- diethoxies anthracene, 9,10- dipropyl oxygen Base anthracene and 9,10- dibutoxy anthracenes.
As it is comprising naphtho- naphthalene nucleus, be suitable as (C) sensitizer compound concrete example, can enumerate：
2- methyl -5,11- dioxos -6,12- double (acetyl group epoxide) naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- Double (the n-propyl carbonyl epoxide) naphthonaphthalenes of double (propiono epoxide) naphthonaphthalenes, 2- methyl -5,11- dioxos -6,12-, 2- methyl - Double (Isopropylcarbonyl epoxide) naphthonaphthalenes of 5,11- dioxos -6,12-, double (the normal-butyl carbonyls of 2- methyl -5,11- dioxos -6,12- Base epoxide) naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- double (butylcarbonyl epoxide) naphthonaphthalene, 2- methyl -5,11- two Double (n-pentylcarbonyl epoxide) naphthonaphthalenes of oxo -6,12-, 2- methyl -5,11- dioxos -6,12- are double (n-hexylcarbonyl epoxide) Naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- double (n-heptyl carbonyl epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxo -6, Double (acetyl group epoxide) naphthonaphthalenes of 12-, double (propiono epoxide) naphthonaphthalenes of 2- ethyl -5,11- dioxos -6,12-, 2- ethyls - Double (the n-propyl carbonyl epoxide) naphthonaphthalenes of 5,11- dioxos -6,12-, double (the isopropyl carbonyls of 2- ethyl -5,11- dioxos -6,12- Base epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- double (n-butylcarbonyl epoxide) naphthonaphthalene, 2- methyl -5,11- two Double (butylcarbonyl epoxide) naphthonaphthalenes of oxo -6,12-, 2- ethyl -5,11- dioxos -6,12- are double (n-pentylcarbonyl epoxide) Naphthonaphthalene, -6,12- pairs of (n-hexylcarbonyl epoxide) naphthonaphthalenes of 2- ethyl -5,11- dioxos and 2- ethyl -5,11- dioxos - The naphtho- naphthalene compound that double (n-heptyl carbonyl epoxide) naphthonaphthalenes of 6,12- etc. replace through alkyl carbonyl epoxide；
2- methyl -5,11- dioxos -6,12- double (benzoyl epoxide) naphthonaphthalene, 2- methyl -5,11- dioxo -6, Double (the toluoyl base epoxide) naphthonaphthalenes of double (the toluoyl base epoxide) naphthonaphthalenes of 12-, 2- methyl -5,11- dioxos -6,12-, Double (the toluoyl base epoxide) naphthonaphthalenes of 2- methyl -5,11- dioxos -6,12-, 2- methyl -5,11- dioxos -6,12- are double (α-naphthoyl epoxide) naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- double (β-naphthoyl epoxide) naphthonaphthalene, 2- second Double (benzoyl epoxide) naphthonaphthalenes of base -5,11- dioxos -6,12-, double (the adjacent toluene of 2- ethyl -5,11- dioxos -6,12- Acyloxy) naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- double (toluoyl base epoxide) naphthonaphthalene, 2- ethyls -5,11- Double (the toluoyl base epoxide) naphthonaphthalenes of dioxo -6,12-, the double (α-naphthoyl oxygen of 2- ethyl -5,11- dioxos -6,12- Base) naphthonaphthalene and double (β-naphthoyl epoxide) naphthonaphthalenes of 2- ethyl -5,11- dioxos -6,12- etc. take through aroyl epoxide The naphtho- naphthalene compound in generation；
Double (methoxycarbonyl epoxide) naphthonaphthalenes of 2- methyl -5,11- dioxos -6,12-, 2- methyl -5,11- dioxos - Double (ethoxy carbonyl epoxide) naphthonaphthalenes of 6,12-, 2- methyl -5,11- dioxos -6,12- are double (n-propyl Epoxide carbonyl epoxide) Naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- double (isopropyloxycarbonyl group epoxide) naphthonaphthalene, 2- methyl -5,11- dioxies Double (the normal-butyl Epoxide carbonyl epoxide) naphthonaphthalenes of generation -6,12-, double (the isobutyl group epoxide carbonyls of 2- methyl -5,11- dioxos -6,12- Base epoxide) naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- double (n-pentyl Epoxide carbonyl epoxide) naphthonaphthalene, 2- methyl -5, Double (the n-hexyl Epoxide carbonyl epoxide) naphthonaphthalenes of 11- dioxos -6,12-, the double (n-heptyls of 2- methyl -5,11- dioxos -6,12- Epoxide carbonyl epoxide) naphthonaphthalene, 2- methyl -5,11- dioxos -6,12- double (n-octyl Epoxide carbonyl epoxide) naphthonaphthalene, 2- second Double (methoxycarbonyl epoxide) naphthonaphthalenes of base -5,11- dioxos -6,12-, the double (ethoxies of 2- ethyl -5,11- dioxos -6,12- Base carbonyl epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- double (n-propyl Epoxide carbonyl epoxide) naphthonaphthalene, 2- second Double (isopropyloxycarbonyl group epoxide) naphthonaphthalenes of base -5,11- dioxos -6,12-, 2- ethyl -5,11- dioxos -6,12- are double Double (the isobutyl group Epoxide carbonyl epoxide) naphtho-s of (normal-butyl Epoxide carbonyl epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- Naphthalene, 2- ethyl -5,11- dioxos -6,12- double (n-pentyl Epoxide carbonyl epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxo -6, Double (the n-hexyl Epoxide carbonyl epoxide) naphthonaphthalenes of 12-, double (the n-heptyl Epoxide carbonyl oxygen of 2- ethyl -5,11- dioxos -6,12- Base) naphthonaphthalene and double (the n-octyl Epoxide carbonyl epoxide) naphthonaphthalenes of 2- ethyl -5,11- dioxos -6,12- etc. be through alkoxy carbonyl The naphtho- naphthalene compound of base epoxide substitution；And,
Double (phenyloxycarbonyl epoxide) naphthonaphthalenes of 2- methyl -5,11- dioxos -6,12-, 2- methyl -5,11- dioxos - Double (the o-tolyl Epoxide carbonyl epoxide) naphthonaphthalenes of 6,12-, double (the tolyl epoxide carbonyl of 2- methyl -5,11- dioxos -6,12- Base epoxide) naphthonaphthalene, double (the p-methylphenyl Epoxide carbonyl epoxide) naphthonaphthalenes of 2- methyl -5,11- dioxos -6,12-, 2- methyl - Double (the Alpha-Naphthyl Epoxide carbonyl epoxide) naphthonaphthalenes of 5,11- dioxos -6,12-, the double (β-naphthalene of 2- methyl -5,11- dioxos -6,12- Base Epoxide carbonyl epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- double (phenyloxycarbonyl epoxide) naphthonaphthalene, 2- second Double (the o-tolyl Epoxide carbonyl epoxide) naphthonaphthalenes of base -5,11- dioxos -6,12-, 2- ethyl -5,11- dioxos -6,12- are double (a tolyl Epoxide carbonyl epoxide) naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- are double (p-methylphenyl Epoxide carbonyl epoxide) Double (the Alpha-Naphthyl Epoxide carbonyl epoxide) naphthonaphthalenes of naphthonaphthalene, 2- ethyl -5,11- dioxos -6,12- and 2- ethyls -5,11- two The naphthonaphthalene chemical combination that double (betanaphthyl Epoxide carbonyl epoxide) naphthonaphthalenes of oxo -6,12- etc. replace through aroyl Epoxide carbonyl epoxide Thing.
In the above-mentioned compound comprising naphtho- naphthalene nucleus, preferably 5,11- dioxos -6,12- are double (methoxycarbonyl epoxide) Double (ethoxy carbonyl epoxide) naphthonaphthalenes of naphthonaphthalene, 5,11- dioxos -6,12-, double (the isopropyl oxygen of 5,11- dioxos -6,12- Base carbonyl epoxide) naphthonaphthalene, double (the isobutyl group Epoxide carbonyl epoxide) naphthonaphthalenes of 5,11- dioxos -6,12-, 5,11- dioxos - Double (n-butylcarbonyl epoxide) naphthonaphthalenes of 6,12-, 5,11- dioxos -6,12- double (n-pentylcarbonyl epoxide) naphthonaphthalene, 5,11- Double (the positive heptanoyl group epoxide) naphthonaphthalenes of dioxo -6,12-.
From with from the viewpoint of the compatibility of (A) photopolymerizable compound, the double (isopropyls of preferably 5,11- dioxos -6,12- Base Epoxide carbonyl epoxide) naphthonaphthalene, 5,11- dioxos -6,12- double (isobutyl group Epoxide carbonyl epoxide) naphthonaphthalene, 5,11- dioxies Double (the positive bytyry epoxide) naphthonaphthalenes of generation -6,12-, 5,11- dioxos -6,12- double (positive valeryl epoxide) naphthonaphthalene, 5,11- Double (heptanoyl group epoxide) naphthonaphthalenes of dioxo -6,12-.
As it is comprising thioxanthene ring, be suitable as (C) sensitizer compound concrete example, thioxanthene-9-one, 2- can be enumerated Methyl -9H- thioxanthene-9-ones, 2- isopropyl -9H- thioxanthene-9-ones, 1,4- dimethyl thioxanthene-9-one and acetic acid 3- methyl -9- oxygen Generation -9H- thioxanthene -2- base esters etc..
Relative to the mass parts of total 100 of (B) composition in photosensitive composite, contain as the sensitizer of (C) composition Amount is preferably 0.01~1000 mass parts, more preferably more preferably 0.1~150 mass parts, 0.3~100 mass parts.
It should be noted that making total 100 mass parts of the content relative to (B) composition as the sensitizer of (C) composition During for 0.01~3 mass parts, coloring caused by the absorption because of (C) composition can be reduced, accordingly, it is capable to access transparent or bright The good solidfied material of degree.
＜ (D) colouring agents ＞
Photosensitive composite can further include (D) colouring agent.Photosensitive composite is by comprising being used as (D) composition Colouring agent, so as to the purposes for the colour filter for being preferred for for example being formed liquid crystal display.Moreover, it relates to photonasty Composition comprising opacifier by being used as colouring agent, so as to the black for being preferred for for example being formed in the colour filter of display device The purposes of matrix.
As (D) colouring agent included in photosensitive composite, it is not particularly limited, for example, it is preferable to use Colour Index (C.I.；The Society of Dyers and Colourists companies issue) in be classified as pigment (Pigment) change Compound, the specifically as described below compound numbered with Colour Index (C.I.).
As the example of the yellow uitramarine preferably used, (following, also " the C.I. face of C.I. pigment yellows 1 can be enumerated Material is yellow ", only record numbering.), 3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74, 81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、 125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、 168th, 175,180 and 185.
As the example of the orange pigment preferably used, (following, also " the C.I. face of C.I. pigment oranges 1 can be enumerated Material orange ", only records numbering.)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、 71 and 73.
As the example of the violet pigment preferably used, C.I. pigment violet 1s (following, also " C.I. face can be enumerated Material is purple ", only record numbering.), 19,23,29,30,32,36,37,38,39,40 and 50.
As the example of the red pigment preferably used, (following, also " the C.I. face of C.I. paratoneres 1 can be enumerated Material is red ", only record numbering.)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、 32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、 58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、 113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、 178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、 223rd, 224,226,227,228,240,242,243,245,254,255,264 and 265.
As the example of the blue pigment preferably used, C.I. pigment blue 1s (following, also " C.I. face can be enumerated Material is blue ", only record numbering.)、2、15、15：3、15：4、15：6th, 16,22,60,64 and 66.
As the example of the pigment of form and aspect preferably using, other than the above, C.I. pigment Green 7s, C.I. face can be enumerated Expect the viridine greens such as green 36, C.I. naphthol greens 37, C.I. pigment browns 23, C.I. pigment brown 25s, C.I. pigment browns 26, C.I. pigment The black pigments such as brown 28 grade browns, C.I. pigment blacks 1, C.I. pigment blacks 7.
In addition, when making colouring agent for opacifier, as opacifier, preferably using black pigment.As black pigment, it can lift Go out metal oxide, composite oxides, metal sulfide, the gold of black carbon black, titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc. Belong to the various pigment such as sulfate or metal carbonate (whether organic matter or inorganic matter).Wherein, preferably using has The carbon black of high light-proofness.
As carbon black, channel black (channel black), furnace black (furnace black), hot tearing charcoal can be used Carbon black known to black (thermal black), lampblack (lamp black) etc., preferably uses the excellent channel black of light-proofness. In addition, it is possible to use through resin-coated carbon black.
For through resin-coated carbon black, because its electric conductivity is lower than without resin-coated carbon black, therefore, in conduct The black matrix"s of liquid crystal display cells as liquid crystal display can manufacture reliability high in use, the leakage of electric current is few Low power consumption display.
In addition, the tone in order to adjust carbon black, can suitably add above-mentioned organic pigment as auxiliary pigment.
In order that above-mentioned colouring agent is dispersed in photosensitive composite, dispersant can be further used.It is used as this The dispersant of sample, preferably uses polyethyleneimine amine system, carbamate resins system, the macromolecule dispersing agent of acrylic resin. Especially, when using carbon black as colouring agent, the dispersant of acrylic resin is preferably used as dispersant.
In addition, inorganic pigment and organic pigment can be used individually, or also and two or more can be used, be used in combination When, relative to the mass parts of total amount 100 of inorganic pigment and organic pigment, organic face is preferably used with the scope of 10~80 mass parts Material, more preferably uses organic pigment with the scope of 20~40 mass parts.
It is suitable true according to the purposes of photosensitive composite for the usage amount of the colouring agent in photosensitive composite It is fixed, as one, relative to the mass parts of gross mass 100 of the composition in addition to solvent in photosensitive composite, preferably For 5~70 mass parts, more preferably 25~60 mass parts.By make colouring agent usage amount be above range, so as to Target pattern formation black matrix", each dyed layer, are preferred.
Especially, when using photosensitive composite formation black matrix", the shading in photosensitive composite is preferably adjusted The amount of agent with cause black matrix" every 1 μm of envelope OD values turn into more than 4.If the OD values of every 1 μm of envelope of black matrix" are 4 More than, then in the black matrix" for liquid crystal display, can sufficiently it be displayed contrast.
For colouring agent, it is preferred that using dispersant that it is scattered and dispersion liquid is made with appropriate concentration Afterwards, added in photosensitive composite.
＜ (E) alkali soluble resins ＞
Photosensitive composite of the present invention can also be comprising (E) alkali soluble resins as except being used as (A) optical polymerism Other resins beyond the resin of compound., can be to photonasty by coordinating (E) alkali soluble resins in photosensitive composite Composition assigns alkali-developable.
In this specification, alkali soluble resins refers to：Utilize the resin solution (solvent that resin concentration is 20 mass %：The third two Alcohol monomethyl ether acetate), the resin film that thickness is 1 μm is formed on substrate, and it is water-soluble for 0.05 mass % KOH in concentration When being impregnated 1 minute in liquid, thickness dissolves more than 0.01 μm of resin.
(E) in alkali soluble resins, the characteristic of resin is adjusted in terms of Film making properties are excellent, easily by the selection of monomer In terms of consider, the polymer of the monomer with ethylenic unsaturated double-bond is preferred.As unsaturated double with ethylenic The monomer of key, can enumerate (methyl) acrylic acid；(methyl) acrylate；(methyl) acrylamide；Crotonic acid；Maleic acid, rich horse Acid, citraconic acid, mesaconic acid, itaconic acid, the acid anhydride of these dicarboxylic acids；Allyl acetate, allyl hexanoate, allyl octanoate, bay Allyl propionate, palm allyl propionate, stearic allyl propionate, allyl benzoate, acetoacetic acid allyl ester, allyl lactate and The allyl compound of pi-allyl ethoxy-ethanol etc；Hexyl vinyl ethers, octyl vinyl ether, decave, ethyl Hexyl vinyl ethers, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1- methyl -2,2- Dimethylpropyl vinyl ether, 2- ethylbutyl vinyl ethers, hydroxyethyl vinyl ether, diethylene glycol vinyl ethers, diformazan Base amino-ethyl vinyl ethers, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ethers, vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl -2,4 dichloro benzene The vinyl ethers of base ether, vinyl naphthyl ether and vinyl anthryl ether etc；Vinyl butyrate, vinyl isobutyrate ester, trimethyl Vinyl acetate, diethacetic acid vinyl acetate, vinyl valerate (vinyl valerate), vinyl caproate, vinyl chloroacetate Ester, vinyl dichloroacetate ester, vinyl methoxyacetate ester, butoxy acetic acid vinyl acetate, vinyl phenylacetate ester, acetoacetate second Alkene ester, lactate, beta-phenyl vinyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, four The vinyl esters of chlorobenzoic acid vinyl acetate and naphthoic acid vinyl acetate etc；Styrene, methyl styrene, dimethyl styrene, three Methyl styrene, ethyl styrene, diethyl, isopropyl styrene, butylstyrene, hexyl styrene, cyclohexyl Styrene, decyl styrene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, second Pivaloyloxymethyl styrene, methoxy styrene, 4- methoxyl group -3- methyl styrenes, dimethoxy styrene, chlorostyrene, Dichlorostyrene, trichlorostyrene, tetrachloro styrene, pentachloro- styrene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene The styrene or benzene of the bromo- 4- trifluoromethyl styrenes of ethene, trifluorostyrene, 2- and the fluoro- 3- trifluoromethyl styrenes of 4- etc Ethene derivatives；Ethene, propylene, 1- butylene, 1- amylenes, 1- hexenes, 3-methyl-1-butene, 3- Methyl-1-pentenes, 3- ethyls- 1- amylenes, 4-methyl-1-pentene, 4- methyl isophthalic acids-hexene, 4,4- dimethyl -1- hexenes, 4,4- dimethyl -1- amylenes, 4- second Base -1- hexenes, 3- ethyl -1- hexenes, 1- octenes, 1- decene, 1- dodecylenes, tetradecene, cetene, 1- 18 The alkene of carbene and 1- eicosylenes etc.
(E) alkali soluble resins for the polymer of the monomer with ethylenic unsaturated double-bond is generally comprised from insatiable hunger With the unit of carboxylic acid.As the example of unsaturated carboxylic acid, (methyl) acrylic acid can be enumerated；(methyl) acrylamide；Crotonic acid；Horse Come sour, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, the acid anhydride of these dicarboxylic acids.For be used as alkali soluble resins have alkene It is being included in the polymer of the monomer of keyed unsaturated double-bond, for the amount of the unit of unsaturated carboxylic acid, as long as resin With desired alkali solubility, it is not particularly limited.For the quality of resin, it is used as the tree of alkali soluble resins The amount of unit in fat, from unsaturated carboxylic acid is preferably 5~25 mass %, more preferably 8~16 mass %.
It is being used as the polymer, unsaturated with ethylenic of more than a kind of the monomer in monomer exemplified as above In the polymer of the monomer of double bond, the polymerization of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate Thing is preferred.Hereinafter, the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate is entered Row explanation.
For in the preparation of the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate For (methyl) acrylate used, it is not particularly limited in the range of without prejudice to the object of the invention, can be from known (first Base) suitably select in acrylate.
As the preference of (methyl) acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) of the straight-chains such as (methyl) propyl acrylate, (methyl) amyl acrylate, the tertiary monooctyl ester of (methyl) acrylic acid or branched Alkyl acrylate；(methyl) acrylic acid chloroethene ester, (methyl) acrylic acid 2,2- dimethyl hydroxyls propyl ester, (methyl) acrylic acid 2- Hydroxy methacrylate, trimethylolpropane list (methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid furfuryl group ester；Bag (methyl) acrylate containing the group with epoxy radicals；(methyl) acrylate comprising the group with alicyclic skeleton. (methyl) acrylate comprising the group with epoxy radicals and (methyl) acrylic acid comprising the group with alicyclic skeleton The detailed content of ester is as described later.
In the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate, from using From the viewpoint of the transparent insulating film of photosensitive composite formation is for the adaptation of base material, mechanical strength, preferably comprise From the resin of the unit of (methyl) acrylate comprising the group with epoxy radicals.
(methyl) acrylate comprising the group with epoxy radicals, can be comprising with chain fatty race epoxy radicals (methyl) acrylate of group, or aftermentioned such (methyl) propylene for including the group with ester ring type epoxy radicals Acid esters.
(methyl) acrylate comprising the group with epoxy radicals can also include aromatic group.It is used as composition aromatic series The example of the aromatic rings of group, can enumerate phenyl ring, naphthalene nucleus.As with aromatic group and including the base with epoxy radicals The example of (methyl) acrylate of group, can enumerate (methyl) acrylic acid 4- glycidyloxyphenyls ester, (methyl) propylene Sour 3- glycidyloxyphenyls ester, (methyl) acrylic acid 2- glycidyloxyphenyls ester, (methyl) acrylic acid 4- contractings Water glyceryl phenyl methyl esters, (methyl) acrylic acid 3- glycidyloxyphenyls methyl esters and (methyl) acrylic acid 2- contractings Water glyceryl phenyl methyl esters etc..
When requiring the transparency to the film using photosensitive composite formation, (methyl) third comprising the group with epoxy radicals Olefin(e) acid is preferably free of aromatic group.
As the example of (methyl) acrylate comprising the group with chain fatty race epoxy radicals, it can enumerate (methyl) As acrylic acid epoxy base Arrcostab and (methyl) acrylic acid epoxy base alkyloxyalkyl ester etc., at ester group (- O-CO-) In epoxide (- O-) on be bonded with (methyl) acrylate of chain fatty race epoxy radicals.Such (methyl) acrylate institute The chain fatty race epoxy radicals having can include one or more epoxides (- O-) in chain.The carbon atom of chain fatty race epoxy radicals Number is not particularly limited, preferably 3~20, more preferably 3~15, particularly preferably 3~10.
As the concrete example of (methyl) acrylate comprising the group with chain fatty race epoxy radicals, (first can be enumerated Base) glycidyl acrylate, (methyl) acrylic acid 2- methylglycidyl esters, (methyl) acrylic acid 3,4- epoxy radicals butyl ester, (methyl) acrylic acid epoxy base Arrcostab such as (methyl) acrylic acid 6,7- epoxy radicals heptyl esters；(methyl) acrylic acid 2- glycidyls Epoxide ethyl ester, (methyl) acrylic acid 3- glycidyl epoxides n-propyl, the positive fourth of (methyl) acrylic acid 4- glycidyl epoxides (the first such as ester, the just own ester of (methyl) acrylic acid 5- glycidyls epoxide, the just own ester of (methyl) acrylic acid 6- glycidyls epoxide Base) acrylic acid epoxy base alkyloxyalkyl ester.
Containing from (methyl) acrylate comprising the group with epoxy radicals it is unit, selected from (methyl) third In the polymer of more than a kind of monomer in olefin(e) acid and (methyl) acrylate, from including the group with epoxy radicals The content of the unit of (methyl) acrylate preferably with respect to for the weight of resin be 1~95 mass %, more preferably 40~ 80 mass %.
In addition, in the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate, from Easily formed using photosensitive composite from the aspect of the excellent transparent insulating film of the transparency, containing from comprising with alicyclic ring The resin of the unit of (methyl) acrylate of the group of formula skeleton is also preferred.
In (methyl) acrylate comprising the group with alicyclic skeleton, the group with alicyclic skeleton can be Group with alicyclic type hydrocarbon, or the group with ester ring type epoxy radicals.Constitute the ester ring type base of alicyclic skeleton Group can be monocyclic, or polycyclic.As monocyclic ester ring type group, cyclopenta, cyclohexyl etc. can be enumerated.In addition, making For polycyclic ester ring type group, norborny, isobornyl, three cyclononyls, tricyclodecyl, tetracyclododecyl group etc. can be enumerated.
In (methyl) acrylate comprising the group with alicyclic skeleton, as including the base with alicyclic type hydrocarbon (methyl) acrylate of group, for example, can enumerate the compound of following formula (d1-1)~(d1-8) expressions.Wherein, preferred following formula (d1-3) compound that the compound~(d1-8) represented, more preferably following formula (d1-3) or (d1-4) are represented.
In above-mentioned formula, Rd1Represent hydrogen atom or methyl, Rd2Represent the bivalent aliphatic saturation of singly-bound or carbon number 1~6 Alkyl, Rd3Represent the alkyl of hydrogen atom or carbon number 1~5.It is used as Rd2, the preferably alkylene of singly-bound, straight-chain or branched Base, such as methylene, ethylidene, propylidene, 1,4- butylidenes, ethylethylene residue, 1,5- pentylidene, 1,6- hexylidenes.As Rd3, preferably methyl, ethyl.
In (methyl) acrylate comprising the group with alicyclic skeleton, as comprising with ester ring type epoxy radicals The concrete example of (methyl) acrylate of group, for example, can enumerate the compound of following formula (d2-1)~(d2-16) expressions.Its In, in order that the developability appropriateness of photosensitive composite, the compound that preferably following formula (d2-1)~(d2-6) is represented, more preferably The compound that following formula (d2-1)~(d2-4) is represented.
In above-mentioned formula, Rd4Represent hydrogen atom or methyl, Rd5The bivalent aliphatic saturated hydrocarbyl of carbon number 1~6 is represented, Rd6The bivalent hydrocarbon radical of carbon number 1~10 is represented, n represents 0~10 integer.It is used as Rd5, preferably straight-chain or branched Alkylidene, such as methylene, ethylidene, propylidene, 1,4- butylidenes, ethylethylene residue, 1,5- pentylidene, 1,6- hexylidenes. It is used as Rd6, it is preferably such as methylene, ethylidene, propylidene, Isosorbide-5-Nitrae-butylidene, ethylethylene residue, 1,5- pentylidene, 1,6- sub- Hexyl, phenylene, cyclohexylidene (cyclohexylene group) ,-CH2-Ph-CH2- (Ph represents phenylene).
The polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate be containing from During the resin of the unit of (methyl) acrylate comprising the group with alicyclic skeleton, in resin derive from comprising with The amount of the unit of (methyl) acrylate of the group of alicyclic skeleton is preferably 5~95 mass %, more preferably 10~90 matter Measure %, more preferably 30~70 mass %.
In addition, containing from (methyl) acrylate comprising the group with alicyclic skeleton it is unit, be selected from In the polymer of more than a kind of monomer in (methyl) acrylic acid and (methyl) acrylate, preferably comprise from (methyl) The resin of the unit of acrylic acid and unit from (methyl) acrylate comprising the group with ester ring type epoxy radicals. Using comprising such (E) alkali soluble resins photosensitive composite formation film for base material excellent adhesion.In addition, In the case of using such resin, the autoreactivity of the carboxyl and ester ring type epoxy radicals included in resin can be carried out.Therefore, During using photosensitive composite comprising such resin, carboxyl and fat are carried out by using method heated to film etc. The autoreactivity of ring type epoxy radicals, the mechanical properties of the hardness of film so as to improve formation etc.
Containing the unit from (methyl) acrylic acid and from including the group with ester ring type epoxy radicals In the resin of the unit of (methyl) acrylate, the amount of the unit from (methyl) acrylic acid in resin is preferably 1~95 Quality %, more preferably 10~50 mass %.Containing the unit from (methyl) acrylic acid and from comprising with fat In the resin of the unit of (methyl) acrylate of the group of ring type epoxy radicals, deriving from comprising with ester ring type ring in resin The amount of the unit of (methyl) acrylate of the group of epoxide is preferably 1~95 mass %, more preferably 30~70 mass %.
Containing the unit from (methyl) acrylic acid and from the (first for including the group with ester ring type epoxy radicals Base) acrylate more than a kind of monomer unit, in (methyl) acrylic acid and (methyl) acrylate polymer In, preferably comprise unit, the list from (methyl) acrylate comprising alicyclic type hydrocarbon from (methyl) acrylic acid The resin of unit first and from (methyl) acrylate comprising the group with ester ring type epoxy radicals.
Containing the unit from (methyl) acrylic acid, from (methyl) acrylate comprising alicyclic type hydrocarbon Unit and in the resin of the unit of (methyl) acrylate comprising the group with ester ring type epoxy radicals, in resin The amount of the unit from (methyl) acrylic acid be preferably 1~95 mass %, more preferably 10~50 mass %.Containing next Come from the unit of (methyl) acrylic acid, the unit from (methyl) acrylate comprising alicyclic type hydrocarbon and from bag In the resin of the unit of (methyl) acrylate containing the group with ester ring type epoxy radicals, deriving from resin includes alicyclic ring The amount of the unit of (methyl) acrylate of formula alkyl is preferably 1~95 mass %, more preferably 10~70 mass %.Containing Unit from (methyl) acrylic acid, the unit from (methyl) acrylate comprising alicyclic type hydrocarbon and derive from In the resin of the unit of (methyl) acrylate comprising the group with ester ring type epoxy radicals, deriving from resin includes tool The amount for having the unit of (methyl) acrylate of the group of ester ring type epoxy radicals is preferably 1~95 mass %, more preferably 30~ 80 mass %.
(E) matter average molecular weight (Mw of alkali soluble resins：Convert using gel permeation chromatography (GPC) and according to polystyrene Obtained from measured value.It is identical in this specification.) it is preferably 2000~200000, more preferably 2000~18000.By making Matter average molecular weight is above range, so that in the presence of the developability after being readily available the film Forming ability of photosensitive composite, exposing Balance tendency.
In the case where photosensitive composite includes (E) alkali soluble resins, solvent is removed relative in photosensitive composite The content of (E) alkali soluble resins in the gross mass of composition in addition, photosensitive composite is preferably 15~95 mass %, more excellent Elect 35~85 mass %, particularly preferably 50~70 mass % as.
＜ other compositions ＞
As needed, various additives can be included in photosensitive composite of the present invention.Specifically, it can enumerate molten Agent, sensitizer, curing accelerator, photocrosslinking agent, dispersing aid, filler, closely sealed accelerator, antioxidant, ultraviolet radiation absorption Agent, deflocculant, thermal polymerization inhibitor, defoamer, surfactant etc..
Photosensitive composite of the present invention can be prepared by each composition of dispersing and dissolving in a solvent, if but above-mentioned (A) composition is liquid, then also can be without using solvent.It is molten as what is used in photosensitive composite in the case of comprising solvent Agent, for example, can enumerate ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol n-propyl ether, ethylene glycol list n-butyl ether, Diethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, three second Glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propane diols list n-propyl ether, Propane diols list n-butyl ether, DPGME, dihydroxypropane single-ethyl ether, DPG list n-propyl ether, dipropyl two (poly-) the alkylene glycol monoalkyl ethers classes such as alcohol list n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethylether；Second two Alcohol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, TC Acetic acid esters, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters etc. (poly-) alkylene glycol monoalkyl ethers acetic acid Esters；Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran； The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone；The lactic acid alkyl such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester Esters；2- hydroxy-2-methyls ethyl propionate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-propionic acid first Ester, 3- ethoxyl ethyl propionates, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, acetic acid 3- Methyl -3- methoxybutyls, propionic acid 3- methyl -3- methoxybutyls, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid N-butyl, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, butyric acid are different Propyl ester, butyric acid N-butyl, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, Other esters such as 2-Oxobutyric acid ethyl ester；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；1-METHYLPYRROLIDONE, N, N- dimethyl methyls Amide-types such as acid amides, DMAC N,N' dimethyl acetamide etc..These solvents can be used alone, and two or more also can be combined and uses.
In above-mentioned solvent, propylene glycol monomethyl ether, ethylene glycol single methyl ether acetic acid esters, propylene glycol monomethyl ether, Propylene glycol monoethyl acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, acetic acid 3- methoxyl groups Butyl ester is preferred, because they not only show excellent dissolubility, Er Qieneng to above-mentioned (A) composition and (B) composition So that the favorable dispersibility of above-mentioned (D) composition；Particularly preferably using propylene glycol monomethyl ether, acetic acid 3- methoxyl group fourths Ester.The usage amount of solvent is suitably determined according to the purposes of photosensitive composite, as one, can be enumerated relative to photosensitive Property composition in the composition in addition to solvent the mass parts of gross mass 100 for 50~900 mass parts or so.
As the thermal polymerization inhibitor used in photosensitive composite of the present invention, for example, quinhydrones, quinhydrones can be enumerated Single ethylether etc..In addition, respectively, as defoamer, the compound of polysiloxane series, fluorine system etc. can be enumerated；Lived as surface Property agent, can enumerate the compound of anion system, cation system, nonionic etc..
[preparation method of photosensitive composite]
Whole above-mentioned each compositions can be mixed and prepared by photosensitive composite of the present invention by using mixer. It should be noted that in the case where prepared photosensitive composite is without insoluble compositions such as pigment, filter can be used Progress is filtered so that photosensitive composite becomes uniform.
《The manufacture method of solidfied material》
For the photosensitive composite being described above, it can be exposed by using desired light source so that it is solid Change.
Hereinafter, the method for the film to can be used as dielectric film or colour filter using photosensitive composite formation is illustrated.Make The film formed with photosensitive composite can be patterned as needed.
In order that with the photosensitive composite formation film of the present invention, first, utilizing roll coater, inverse formula coating machine (reverse Coater), the contact transfer printing type such as bar coater apparatus for coating, spinner (rotary apparatus for coating), curtain coater Non-contact type apparatus for coating such as (curtain flow coater), is coated with photosensitive composite on substrate.
Then, as needed, the photosensitive composite of coating is made to dry and form coated film.Drying means is not limited especially It is fixed, for example, following methods can be enumerated：(1) utilize heating plate, in 80~120 DEG C, preferably 90~100 DEG C temperature dry 60~ The method of 120 seconds；(2) method for placing a few hours~a couple of days in room temperature；(3) it is put into storage heater, infrared heater Middle dozens of minutes~a few hours and remove method of solvent etc..
Then, the coated film is exposed.Light source is not particularly limited, for example, high-pressure sodium lamp, LED etc. can be enumerated, from From the viewpoint of the saving energy, reduction carrying capacity of environment, preferably LED.As the wavelength used in the exposure carried out using LED, For example, 365~405nm can be enumerated, the wavelength in the UV such as 385nm, 395nm, 405nm regions more specifically can be enumerated.Generally, it is sharp Easily tailed off with the energy-ray amount of LED illumination.But, because the photosensitive composite being described above contains foregoing (B) Photoepolymerizationinitiater initiater and (C) sensitizer, susceptibility are excellent, therefore, even if being exposed using LED as light source, also can Fully solidified, effectively obtain the solidfied material with superperformance.Thus, as a result, liquid crystal display can be improved The productivity ratio of the display device of device panel etc.
In the case of optionally being exposed in position to coated film, the film after exposure is shown using developer solution Shadow, is consequently formed the pattern of desired shape.Developing method is not particularly limited, and can use such as infusion process, spray-on process. Developer solution can suitably be selected according to the composition of photosensitive composite.The alkali of alkali soluble resins etc is included in photosensitive composite In the case of soluble components, as developer solution, the developer solution of the organic systems such as MEA, diethanol amine, triethanolamine can be used, The aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc..
Then, 200~250 DEG C or so are preferable over to being dried after the pattern progress after development.
The pattern being formed as described above can be suitably used for for example in the display device of liquid crystal display or the like The purposes such as the dielectric film or the pixel and black matrix" of composition colour filter that use.Such dielectric film, colour filter, the filter is used The display device of color chips is also one of present invention.
Embodiment
Hereinafter, embodiment is provided to be further elaborated with the present invention, but the scope of the present invention is not by these embodiments Limit.
In embodiment and comparative example, as (A) photopolymerizable compound, the propylene of epoxy pronane modification neopentyl glycol two is used Acid esters.
In embodiment, as (B) Photoepolymerizationinitiater initiater, the compound 1 obtained using in following synthesis examples 2 as (B) -1, The compound 2 obtained using in following synthesis examples 3 is used as (B) -2.
The structure of compound 1 and compound 2 is as follows.
In addition, in comparative example 2, the Photoepolymerizationinitiater initiater (B ') -1 of the compound represented as the formula that is not belonging to (1) uses 1- Hydroxycyclohexan -1- base phenyl ketones.
In embodiment and comparative example, as (C) sensitizer, following (C) -1~(C) -4 is used.
(C)-1：2- isopropyl -9H- thioxanthene-9-ones
(C)-2：Double (the n-heptyl carbonyl epoxide) anthracenes of 9,10-
(C)-3：Double (normal-butyl epoxide) anthracenes of 9,10-
(C)-4：Double (methoxycarbonyl epoxide) naphthonaphthalenes of 5,11- dioxos -6,12-
(synthesis example 1)
(synthesis of 9,9- diη-propyl fluorenes)
6.64g (40mmol) fluorenes is dissolved in 27mL THF.Under nitrogen atmosphere, gently into obtained solution It is 50 mass %'s to add 0.12g (1.1mmol) potassium tert-butoxide, 12.30g (100mmol) 1- N-Propyl Bromides and 27mL concentration Sodium hydrate aqueous solution.Obtained mixture is stirred 3 hours in 80 DEG C and reacted.Added into reacted mixture After 33g ethyl acetate and 33g water, point liquid is organic layer and water layer.After being dehydrated with anhydrous sodium sulfate to obtained organic layer, Solvent is removed from organic layer using rotary evaporator, 8.32g (yield is 83%) 9,9- diη-propyl fluorenes is obtained.
(synthesis example 2)
(synthesis of compound 1)
In the presence of 2.62g aluminium chloride, in 50ml dichloromethane solvents, 4.10g is made under ice-cooling The 9,9- diη-propyls fluorenes of (16.37mmol) and 3.04g (18.00mmol) (2- aminomethyl phenyls) excess acetyl chloride 1 hour.Will Reactant mixture is poured into frozen water, is divided and is taken organic layer.After the organic layer of recovery is dried with anhydrous magnesium sulfate, it is evaporated. Silicagel column purifying is carried out to residue using the eluent of ethyl acetate/hexane=1/2,5.95g (15.55mmol) 2- is obtained (2- aminomethyl phenyls) acetyl group -9,9- diη-propyl fluorenes.In the presence of 2.42g (23.33mmol) isobutyl nitrite, In 25ml solvent dimethylformamides, 5.95g (15.55mmol) 2- (2- aminomethyl phenyls) acetyl group -9 are made under ice-cooling, The concentrated hydrochloric acid of 9- diη-propyls fluorenes and 1.60g (15.55mmol) reacts 3 hours.Reaction solution is evaporated, second is added into residue Acetoacetic ester, is washed with saturated aqueous common salt, after being dried with anhydrous magnesium sulfate, is evaporated, and obtains 4.80g (11.67mmol) Following structures 2- [2- aminomethyl phenyls (oxyimino) acetyl group] -9,9- diη-propyl fluorenes.
2- [2- aminomethyl phenyls (oxyimino) acetyl group] -9,9- diη-propyl fluorenes1H-NMR measurement result is as follows It is described.
1H-NMR (600MHz, CDCl3, ppm)：8.60 (bs, 1H), 8.15 (d, 1H), 8.14 (s, 1H), 7.76-8.00 (m, 2H), 7.26-7.53 (m, 7H), 2.35 (s, 3H), 1.98-2.01 (m, 4H), 0.63-0.67 (m, 10H)
By 4.80g (11.67mmol) 2- [2- aminomethyl phenyls (oxyimino) acetyl group] -9,9- diη-propyls fluorenes, 1.43g (13.42mmol) acetic anhydride, 1.36g (13.42mmol) triethylamine and 45.00ml solvent dimethylformamides is mixed Close, stirred 3 hours in 35 DEG C.It is cooled to after room temperature, ethyl acetate is added into reaction solution, washed with water, uses anhydrous sulphur After sour magnesium is dried, it is evaporated.Silicagel column purifying is carried out to residue using the eluent of ethyl acetate/hexane=2/1, Obtaining 4.76g, (10.50mmol, yield is compound 1 72%).Compound 11H-NMR measurement result is as described below.
1H-NMR (600MHz, CDCl3, ppm)：8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7.33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (m, 4H), 0.63- 0.66 (m, 10H).
(synthesis example 3)
(synthesis of compound 2)
3.04g (18.00mmol) (2- aminomethyl phenyls) chloroacetic chloride is changed to 3.14g (18.00mmol) 3- hexamethylenes Base propionyl chloride, in addition, is operated in the same manner as synthesis example 2, obtains the 2- [cyclohexyl methyls of following structures as intermediate (oxyimino) acetyl group] (10.80mmol, yield is compound 2 75%) by -9,9- diη-propyls fluorenes and 4.96g.
2- [cyclohexyl methyl (oxyimino) acetyl group] -9,9- diη-propyl fluorenes1H-NMR measurement result is as follows It is described.
1H-NMR (600MHz, CDCl3, ppm)：8.80 (bs, 1H), 7.90-7.98 (m, 2H), 7.70-7.80 (m, 2H), 7.30-7.40 (m, 3H), 2.72 (d, 2H), 1.88-2.02 (m, 4H), 1.54-1.80 (m, 6H), 0.95-1.28 (m, 5H), 0.67-0.77 (m, 10H)
Compound 21H-NMR measurement result is as described below.
1H-NMR (600MHz, CDCl3, ppm)：8.08-8.14 (m, 2H), 7.70-7.79 (m, 2H), 7.32-7.40 (m, 3H), 2.78 (d, 2H), 2.28 (s, 3H), 1.88-2.10 (m, 4H), 1.53-1.78 (m, 6H), 1.00-1.30 (m, 5H), 0.60-0.77 (m, 10H).
(embodiment 1~7 and comparative example 1~2)
Respectively, (A) composition, (B) composition and (C) composition of the species described in table 1 below and amount are equably mixed Close, obtain the photosensitive composite of each embodiment and comparative example.
Obtained photosensitive composite is added dropwise on substrate with pipette (spuit), then, commercially available LED is utilized The drop of photosensitive composite is exposed 15 seconds.For the drop after exposure, confirm whether the inside of drop is cured, evaluate each Curability of the photosensitive composite when being exposed using LED.
The cured situation in the inside of drop is determined as zero, the uncured situation of drop is determined as ×.
The evaluation result of curability when being exposed using LED is recorded in table 1.
[table 1]
It was found from the embodiment in table 1, the compound represented containing (A) photopolymerizable compound and comprising formula (1) (B) photosensitive composite of Photoepolymerizationinitiater initiater and (C) sensitizer can well be solidified by LED exposure.In addition, right For embodiment 1~3, coloring has been confirmed in embodiment 1 and 2, but it is unconfirmed to coloring in embodiment 3.Can be true Recognize, though in order to prevent colour and reduce the addition of (C) composition, be also able to maintain that when being exposed using LED well Curability.
On the other hand, it can be seen from comparative example, (B) photopolymerizable compound contained in photosensitive composite is free of formula (1) in the case of the compound represented, although and the compound that is represented in photosensitive composite comprising formula (1) as (B) light Polymerizable compound but without in the case of (C) sensitizer, photosensitive composite fails well to solidify by LED exposure.

Claims (5)

1. photosensitive composite, it includes (A) photopolymerizable compound, (B) Photoepolymerizationinitiater initiater and (C) sensitizer, wherein,
(B) Photoepolymerizationinitiater initiater includes the compound that following formula (1) is represented,
In formula (1), R1For hydrogen atom, nitro or monovalent organic group, R2And R3Respectively can have substituent chain-like alkyl, Can have the cyclic organic group or hydrogen atom of substituent, R2With R3It can be mutually bonded and form ring, R4For any monovalent organic radical Group, R5For hydrogen atom, the alkyl of the carbon number 1~11 can with substituent or the aryl can with substituent, n is 0~4 Integer, m be 0 or 1.
2. photosensitive composite as claimed in claim 1, wherein, (C) sensitizer is as substituent with following radicals Fused polycyclic aromatic hydrocarbon cycle compound or fused polycyclic aromatic heterocyclic compounds, the group are selected from by alcoxyl More than a kind in the group of base, substituted carbonyl epoxide and oxo base composition.
3. the manufacture method of solidfied material, and it is that the photosensitive composite described in claim 1 or 2 is exposed to consolidate it Change.
4. the manufacture method of solidfied material as claimed in claim 3, wherein, the exposure is carried out using LED.
5. the solidfied material of the photosensitive composite described in claim 1 or 2.
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