CN106959581A - Photosensitive resin composition and application thereof - Google Patents

Photosensitive resin composition and application thereof Download PDF

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Publication number
CN106959581A
CN106959581A CN201611234706.XA CN201611234706A CN106959581A CN 106959581 A CN106959581 A CN 106959581A CN 201611234706 A CN201611234706 A CN 201611234706A CN 106959581 A CN106959581 A CN 106959581A
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carbon number
alkyl
represent
phenyl
group
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许承昌
谢栢源
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Chi Mei Corp
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Chi Mei Corp
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a photosensitive resin composition, and a color filter and a liquid crystal display assembly manufactured by using the photosensitive resin composition. The photosensitive resin composition comprises a pigment (A), a dye (B), an alkali-soluble resin (C), a compound (D) having an ethylenically unsaturated group, a photoinitiator (E), and a thermal acid generator (F). The color filter prepared by the photosensitive resin composition has good thermal solvent film thickness change rate.

Description

Photosensitive resin composition and its application
Technical field
The present invention is a kind of relevant photosensitive resin composition, and using the photosensitive resin composition to manufacture colored filter Mating plate and LCD assembly.Especially it is to provide a kind of photosensitive resin composition, obtained by the photosensitive resin composition Colored filter has good hot solvent Thickness Variation rate.
Background technology
At present, colored filter has been widely used in colour liquid crystal display device, colour facsimile apparatus, colour camera etc. The field of office equipment.As the market demand increasingly expands, the manufacturing technology of colored filter also tends to variation, has opened at present The manufacture methods such as decoration method, print process, galvanoplastic and dispersion method are sent out, wherein using dispersion method as prevailing technology.
The technique of dispersion method is that first coloring pigment is scattered in photoresist, then the photoresist is coated on into glass On glass substrate, through steps such as overexposure, imagings, you can specific pattern is made.Repeated three operations, you can red (R) is made, The pattern of green (G) and blue (B) pixel shader layer, afterwards optionally can be in application protection on the pattern of pixel shader layer Film.
For the photoresist in dispersion method technique such as Japanese Unexamined Patent Publication 6-95211 publications and Unexamined Patent 8-183819 Number publication is announced, the copolymer being for example polymerized using (methyl) acrylic acid by monomer component, and it is as photonasty tree The alkali soluble resin of fat.
However, in the manufacturing process of colored filter, multiple heat treatment step need to be undergone, such as red (R), green (G) And the pixel dyed layer pattern such as blue (B) formed after rear roasting (post-bake) step and nesa coating (ito film) formation Step etc., the step such as this typically need to all be operated at a high temperature of more than 200 DEG C, if but it is above-mentioned known to photoresist in 180 Heated 1 hour or so at DEG C, be then easy to produce the pigment agglutination particle (particle diameter of general pigment agglutination particle in its pixel shader layer Between 1 μm to 10 μm), and the heat resistance of pixel shader layer is not also good.
A kind of photosensitive resin composition is relate in the problem of to improve above-mentioned, Japanese Unexamined Patent Publication 2001-075273, it is wrapped Unsaturated monomer containing carboxylic acid group polymerize with the monomer containing glycidyl obtained by polymer, and using above-mentioned polymer make For the alkali soluble resin of photoresist.However, utilizing the coloured silk obtained by the foregoing photosensitive resin composition for knowing technology Colo(u)r filter, still with hot solvent Thickness Variation rate it is not good the problem of.
Therefore, how to overcome the problem of hot solvent Thickness Variation rate is not good to reach the requirement of current industry, be the present invention Make great efforts the target of research in art.
The content of the invention
The present invention contains the photosensitive resin composition of special hot acid propellant using providing, and obtains the change of hot solvent thickness The good photosensitive resin composition for colour filter of rate.
Therefore, the present invention provides a kind of photosensitive resin composition, and it is included：
Pigment (A)；
Dyestuff (B)；
Alkali soluble resin (C)；
Compound (D) with ethene unsaturated group；
Light initiator (E)；
Hot acid propellant (F) with structure shown in formula (I)；And
Solvent (G)；
R1f(SO3R2f)aFormula (I)
In formula (I), R1fAnd R2fArbitrary substituent is represented independently of one another；And
A represents more than 1 integer.
The present invention also provides a kind of manufacture method of colored filter, and it is to use foregoing photosensitive resin composition shape Into a pixel layer.
The present invention also provides a kind of colored filter, and it is as obtained by foregoing method.
The present invention also provides a kind of LCD assembly, includes foregoing colorized optical filtering.
Embodiment
The present invention provides a kind of photosensitive resin composition, and it is included：
Pigment (A)；
Dyestuff (B)；
Alkali soluble resin (C)；
Compound (D) with ethene unsaturated group；
Light initiator (E)；
Hot acid propellant (F) with structure shown in formula (I)；And
Solvent (G)；
R1f(SO3R2f)aFormula (I)
In formula (I), R1fAnd R2fArbitrary substituent is represented independently of one another；And
A represents more than 1 integer.
Can be inorganic pigment, organic pigment or combinations of the above according to the pigment (A) of the present invention.
The inorganic pigment can be the metallic compounds such as metal oxide, the wrong salt of metal, its can be selected from iron, cobalt, aluminium, cadmium, The wrong salt of the oxide of metal, the composite oxides of aforementioned metal and the metal such as lead, copper, titanium, magnesium, chromium, sub- lead, antimony.
The organic pigment can be selected from C.1. pigment yellow 1,3,11,12,13,14,15,16,17,20,24,31,53,55, 60、61、65、71、73、74、81、83、93、95、97、98、99、100、101、104、106、108、109、110、113、114、 116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、167、 168、175；C.I. pigment orange l, 5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73； C.I. paratonere l, 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：l、48：2、48：3、48：4、49：l、49：2、50：1、52：l、53：l、57、57：l、57：2、58：2、 58：4、60：l、63：l、63：2、64：l、81：l、83、88、90：l、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、193、194、202、206、207、208、209、215、216、220、224、226、242、 243、245、254、255、264、265；C.I. pigment violet l, 14,19,23,29,32,33,36,37,38,39,40,50；C.I. Alizarol saphirol l, 2,15,15：1、15：2、15：3、15：4、15：5、15：6、16、21、22、60、61、64、66；C.I. pigment Green 7, 36、37、42、58；C.I. pigment brown 23,25,28；And C.I. pigment blacks l, 7.Above-mentioned organic pigment can be individually a kind of or mixed Close a variety of use.
The averaged particles footpath of the pigment (A) is preferably 10nm to 200nm；More preferably 20nm to 150nm；Most preferably 30nm is extremely 130nm。
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, and the usage amount of the pigment (A) is 30 parts by weight To 300 parts by weight；Preferably 40 parts by weight are to 250 parts by weight；More preferably 50 parts by weight are to 200 parts by weight.
If necessary, the pigment (A) also can optionally use dispersant, for example：Cation system, anion system, nonionic The interfacial agents such as system, both sexes, polysiloxane series, fluorine system.
Foregoing interfacial agent can be including but not limited to PEO lauryl ether, PEO stearoyl The polyethylene oxide alkyl ethers class of the oily ether of ether, PEO etc.；PEO octyl group phenylate, PEO nonyl phenylate Deng PEO alkylbenzene ethers interfacial agent；Polyethylene glycol dilaurate, polyglycol distearate etc. Polyethylene glycol di class interfacial agent；Sorbitan fatty acid ester class interfacial agent；Polyesters circle of aliphatic acid modification Face activating agent；The polyurethane class interfacial agent of tertiary amine modification；SHIN-ETSU HANTOTAI's chemical industry manufacture, model KP business Product, Toray Dow Corning Silicon manufactures, model SF-8427 commodity, the oil chemical industry manufacture of common prosperity society, Model Polyflow commodity, get Ke Mu companies (Tochem Products Co., Ltd.s) manufacture, model F-Top business Product, big Japanese ink chemical industry manufacture, model Megafac product, Sumitomo 3M manufactures, model Fluorad product, Asahi Glass is manufactured, model Asahi Guard and Surflon commodity.Interfacial agent can be individually a kind of or mixes a variety of make With.
Used according to dyestuff (B) pigment (A) that can arrange in pairs or groups of the present invention, the technical staff in the technical field of the invention is optional The dyestuff (B) of special spectrum is selected, in the concrete example of the present invention, the dyestuff (B) is azo dyes, azo metal complex dye Material, anthraquinone dye, bipseudoindoxyl dye, thioindigo color, phthalocyanine dye, diphenylmethane dyes, kiton colors, xanthene dye, thiophene Piperazine dyestuff, the dye of positive ion, cyanine dyes, nitro dye, quinoline dye, naphthoquinone dyestuff, oxazine dye etc..
In the preferred embodiment of the present invention, the dyestuff (B) is C.I. solvent reds 2, C.I. solvent red 24s, C.I. solvent reds 27th, C.I. solvent red 49s, C.I. solvent reds 52, C.I. solvent reds 57, C.I. solvent red 8s 9, C.I. solvent reds 111, C.I. solvents Red 114, C.I. solvent reds 119, C.I. solvent reds 124, C.I. solvent of red 135, C.I. solvent reds 136, C.I. solvent reds 137, C.I. solvent red 138, C.I. solvent reds 139, C.I. solvent reds 143, C.I. solvent reds 144, C.I. solvent reds 145, C.I. are molten Agent red 146, C.I. solvent reds 147, C.I. solvent reds 148, C.I. solvent reds 149, C.I. solvent reds 150, C.I. solvent reds 151st, C.I. solvent reds 152, C.I. solvent reds 155, C.I. solvent reds 156, C.I. solvent reds 162, C.I. solvent reds 168, C.I. solvent red 169, C.I. solvent reds 170, C.I. solvent reds 171, C.I. solvent reds 172, C.I. solvent reds 177, C.I. are molten Agent red 178, C.I. solvent reds 179, C.I. solvent reds 181, C.I. solvent reds 190, C.I. solvent reds 191, C.I. solvent reds 194th, C.I. solvent reds 199, C.I. solvent reds 200, C.I. solvent reds 201, C.I. solvent reds 299, C.I. directly red 2, C.I. Directly red 81, C.I. azogeramines, C.I. azogeramines 4, C.I. acid reds 27, C.I. acid reds 52, C.I. acid red 87s, C.I. Acid red 88, C.I. acid reds 289, C.I. alkali red 1:1s, C.I. medium reds 3, C.I. ice dyeings red 21, C.I. vat reds 1, C.I. Vat red 2, C.I. vat reds 15, C.I. vat reds 23, C.I. vat reds 41, C.I. vat reds 47, C.I. Red-1 200s, C.I. Dispersion red 11, C.I. Red-1 200s 5, C.I. disperse reds 22, C.I. disperse red 60s, C.I. disperse reds 92, C.I. Red-1 200s 46, C.I. disperse red 191, C.I. disperse reds 283, C.I. disperse reds 288, C.I. active reds 12.Above-mentioned dyestuff can be according to required property Matter is used alone or as a mixture.
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, the usage amount of the dyestuff (B) for 5 parts by weight extremely 50 parts by weight；Preferably 10 parts by weight are to 45 parts by weight；More preferably 15 parts by weight are to 40 parts by weight.
One first alkali soluble resin (C-1), first alkali-soluble are included according to the alkali soluble resin (C) of the present invention Resin (C-1) is that as obtained by a mixture carries out polymerisation, and the mixture has at least two epoxy radicals comprising one Epoxide (c-1-1) and a compound (c-1- with least one carboxylic acid group and at least one ethene unsaturated group 2).In addition, said mixture is more selectively included compound carboxylic acid anhydride (c-1-3) and/or the chemical combination containing epoxy radicals Thing (c-1-4).
There is the epoxide (c-1-1) of at least two epoxy radicals can have such as following formula (II-1) or following formula (II-2) for this Shown structure.Here, " epoxide (c-1-1) can have the structure as shown in following formula (II-1) or following formula (II-2) " Narration also cover compound with structure as shown in following formula (II-1) and with the structure as shown in following formula (II-2) Compound simultaneously exist and be used as epoxide (c-1-1) situation.Specifically, it is foregoing that there are at least two epoxy radicals Epoxide (c-1-1) be, for example, with structure as shown in following formula (II-1)：
In formula (II-1), R1c、R2c、R3cAnd R4cIt is respectively identical or different, and represent hydrogen atom, halogen atom, carbon The aralkyl that the aromatic radical or carbon number that alkoxy that alkyl that number is 1 to 5, carbon number are 1 to 5, carbon number are 6 to 12 are 6 to 12.
The epoxide (c-1-1) with least two epoxy radicals of previously described formula (II-1) may include by bisphenol fluorene type Compound (bisphenol fluorene) and the bis-phenol containing epoxy radicals obtained by halogenated epoxy propane (epihalohydrin) reaction Fluorenes type compound, but it is not limited to this.
As the concrete example of above-mentioned bisphenol fluorene type compound, it can enumerate but be not limited to：Double (4- hydroxy phenyls) fluorenes of 9,9- [9, 9-bis (4-hydroxy phenyl) fluorene], double (the 4- hydroxy-3-methyls phenyl) fluorenes [9,9-bis (4- of 9,9- Hydroxy-3-methylphenyl) fluorene], double (4- hydroxyl -3- chlorphenyls) fluorenes [9,9-bis (4-hydroxy- of 9,9- 3-chlorophenyl) fluorene], double (4- hydroxyl -3- bromophenyls) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Bromophenyl) fluorene], double (4- hydroxyl -3- fluorophenyls) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Fluorophenyl) fluorene], double (the 4- hydroxy 3-methoxybenzenes base) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- Methoxyphenyl) fluorene], double (4- hydroxyl -3,5- 3,5-dimethylphenyls) fluorenes of 9,9- [9,9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene], double (4- hydroxyl -3,5- dichlorophenyls) fluorenes of 9,9- [9,9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene], double (4- hydroxyl -3,5- dibromo phenyls) fluorenes of 9,9- [9,9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene] etc. compound.
Above-mentioned halogenated epoxy propane (epihalohydrin) may include but be not limited to epichlorohydrin Or bromo- 1,2 epoxy prapanes of 3- (epibromohydrin) etc. (epichlorohydrin).
The above-mentioned bisphenol fluorene type compound containing epoxy radicals as obtained by bisphenol fluorene type compound and halogenated epoxy propane are reacted Including but not limited to：(1) commodity manufactured by Nippon Steel chemical (Nippon Steel Chemical Co., Ltd)：For example ESF-300 etc.；(2) commodity manufactured by Osaka gas (Osaka Gas Co., Ltd)：Such as PG-100, EG-210；(3) Commodity manufactured by short message science and technology (S.M.S Technology Co., Ltd)：Such as SMS-F9PhPG, SMS-F9CrG, SMS- F914PG etc..
Secondly, the epoxide (c-1-1) should with least two epoxy radicals can also have as shown in following formula (II-2) Structure：
In formula (II-2), R5cTo R18cIt is respectively identical or different, and each can independently represent hydrogen atom, halogen atom, The aromatic radical that the alkyl or carbon number that carbon number is 1 to 8 are 6 to 15；And g represents 0 to 10 integer.
The epoxide (c-1-1) with least two epoxy radicals of previously described formula (II-2) is, for example, by alkali metal In the presence of hydroxide, the compound with following formula (II-2-1) structure is set to be reacted and be obtained with halogenated epoxy propane.
In formula (II-2-1), R5cTo R18cAnd g definition be respectively with the R in formula (II-2)5cTo R18cAnd g Definition is identical, does not repeat separately herein.
Furthermore, the epoxide (c-1-1) with least two epoxy radicals of previously described formula (II-2) is, for example, to be urged in acid In the presence of agent, carried out after condensation reaction, formed using the compound with following formula (II-2-2) structure and phenol (phenol) class Compound with formula (II-2-1) structure.Then, de-hydrogen halide is carried out by adding excessive halogenated epoxy propane (dehydrohalogenation) epoxide (c- with least two epoxy radicals as shown in formula (II-2), is obtained 1-1)。
In above formula (II-2-2), R19cWith R20cRespectively identical or different hydrogen atom, halogen atom, carbon number are 1 to 8 Alkyl or carbon number be 6 to 15 aromatic radical；T1And T2Respectively identical or different halogen atom, carbon number are 1 to 6 alkyl Or the alkoxy that carbon number is 1 to 6.It is preferred that foregoing halogen atom can be chlorine or bromine, foregoing alkyl can be methyl, ethyl Or tributyl, foregoing alkoxy can be methoxy or ethoxy.
As the concrete example of above-mentioned phenols, can enumerate but be not limited to as：Phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), the phenol of n- third (n-propylphenol), isobutyl phenol (isobutylphenol), t- fourth phenol (t- Butylphenol), octyl phenol (octylphenol), nonyl phenol (nonylphenol), stubble phenol (xylenol), methyl butyl benzene Phenol (methylbutylphenol), two tributyl phenols (di-t-butylphenol), phenol ethylene (vinylphenol), third Alkene phenol (propenylphenol), acetylene phenol (ethinylphenol), the phenol of ring penta (cyclopentylphenol), ring Hexyl phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc..Above-mentioned phenols typically can individually or Mixing is a variety of to be used.
Usage amount based on the above-mentioned compound with formula (II-2-2) structure is 1 mole, and the usage amount of phenols is rubbed for 0.5 You are to 20 moles, wherein with 2 moles to 15 moles preferably.
As the concrete example of above-mentioned acid catalyst, can enumerate but be not limited to as：Hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid (p- Toluenesulfonic acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous chlorination Aluminium (anhydrous aluminium chloride), zinc chloride (zinc chloride) etc., wherein with p-methyl benzenesulfonic acid, sulphur Acid or hydrochloric acid are preferable.Above-mentioned acid catalyst individually or can be mixed and a variety of used.
Though in addition, the usage amount of above-mentioned acid catalyst is without particular limitation, there is formula (II-2-2) structure based on above-mentioned The usage amount of compound be 100 percentage by weights (wt%), the usage amount of acid catalyst is preferably 0.1wt% to 30wt%.
Above-mentioned condensation reaction can be solvent-free or carry out in the presence of an organic.Secondly, the tool of above-mentioned organic solvent Style can enumerate but be not limited to as：Toluene (toluene), dimethylbenzene (xylene) or methyl iso-butyl ketone (MIBK) (methyl Isobutyl ketone) etc..Above-mentioned organic solvent individually or can be mixed and a variety of used.
It is 100wt% based on compound and the usage amount summation of phenols with formula (II-2-2) structure, it is above-mentioned organic molten The usage amount of agent be 50wt% to 300wt%, wherein preferable with 100wt% to 250wt%.In addition, the behaviour of above-mentioned condensation reaction Make temperature for 40 DEG C to 180 DEG C, and the operating time of condensation reaction is 1 hour to 8 hours.
After above-mentioned condensation reaction is completed, neutralisation treatment or washing process can be carried out.Above-mentioned neutralisation treatment is by after reaction The pH value of solution be adjusted to pH 3 to pH 7, wherein preferable with pH 5 to pH 7.Nertralizer can be used in above-mentioned washing process Carry out, this nertralizer is alkaline matter, and its concrete example can enumerate：NaOH (sodium hydroxide), potassium hydroxide Alkali metal hydroxides such as (potassium hydroxide)；Calcium hydroxide (calcium hydroxide), magnesium hydroxide Alkaline-earth metal hydroxide such as (magnesium hydroxide)；Two stretch second triamine (diethylene triamine), three Stretch second tetramine (triethylene tetramine), aniline (aniline), phenylenediamine (phenylene diamine) etc. organic Amine；And ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate) etc..Above-mentioned washing process can be adopted Carried out with well-known process, for example, in solution after the reaction, adding the aqueous solution containing nertralizer, extraction being repeated.Through After neutralisation treatment or washing process, handled through heating under reduced pressure, unreacted phenols and solvent given into distillation, and concentrated, The compound with formula (II-2-1) structure can be obtained.
As the concrete example of above-mentioned halogenated epoxy propane, can enumerate but be not limited to as：Epichlorohydrin (3- Chloro-1,2-epoxypropane), the bromo- 1,2 epoxy prapanes of 3- (3-bromo-1,2-epoxypropane) or above-mentioned Meaning combination.Before above-mentioned de-hydrogen halide is carried out, it can in advance add or NaOH, hydroxide are added in course of reaction The alkali metal hydroxides such as potassium.The operation temperature of above-mentioned de-hydrogen halide is 20 DEG C to 120 DEG C, and its operating time scope is 1 Hour was to 10 hours.
In the concrete example of the present invention, it also can be used in the alkali metal hydroxide added in above-mentioned de-hydrogen halide The aqueous solution.In this concrete example, above-mentioned alkali metal hydroxide aqueous solution is continuously added in de-hydrogen halide system Meanwhile, can be under decompression or normal pressure, continuous still water outlet and halogenated epoxy propane, by separating and removing water, while can be by halogen Change expoxy propane to be continuously back in reaction system.
Before above-mentioned de-hydrogen halide is carried out, tetramethyl-ammonium chloride (tetramethyl ammonium can be also added Chloride), tetramethylammonium bromide (tetramethyl ammonium bromide), trimethyl benzyl ammonia chloride (trimethyl Benzyl ammonium chloride) etc. quarternary ammonium salt as catalyst, and at 50 DEG C to 150 DEG C, reaction 1 hour is extremely 5 hours, alkali metal hydroxide or its aqueous solution are added, at a temperature of 20 DEG C to 120 DEG C, it is reacted 1 hour to 10 Hour, to carry out de-hydrogen halide.
It is 1 equivalent, above-mentioned halogenated epoxy based on the hydroxyl total yield in the above-mentioned compound with formula (II-2-1) structure The usage amount of propane can for 1 equivalent to 20 equivalents, wherein preferable to 10 equivalents with 2 equivalents.There is formula (II-2-1) based on above-mentioned Hydroxyl total yield in the compound of structure is making for the alkali metal hydroxide that adds in 1 equivalent, above-mentioned de-hydrogen halide Consumption can for 0.8 equivalent to 15 equivalents, wherein preferable to 11 equivalents with 0.9 equivalent.
In addition, in order that above-mentioned de-hydrogen halide is smoothed out, in addition to it can add the alcohols such as methanol, ethanol, also The aprotics such as dimethyl sulfone (dimethyl sulfone), dimethyl sulfoxide (dimethyl sulfoxide) can be added (aprotic) polar solvent etc. is reacted.In the case of using alcohols, the total amount based on above-mentioned halogenated epoxy propane For 100wt%, the usage amount of alcohols can be 2wt% to 20wt%, preferably 4wt% to 15wt%.Using aprotic In the example of polar solvent, the total amount based on halogenated epoxy propane is 100wt%, and the usage amount of the polar solvent of aprotic can It is 5wt% to 100wt%, wherein, it is preferable with 10wt% to 90wt%.
After de-hydrogen halide is completed, washing process is optionally carried out.Afterwards, removed using the mode of heating decompression Remove polar solvent of halogenated epoxy propane, alcohols and aprotic etc..Above-mentioned heating decompression be, for example, in temperature be 110 DEG C extremely 250 DEG C, and pressure is progress under the environment of 1.3kPa (10mmHg) below.
In order to avoid the epoxy resin of formation contains hydrolyzable halogen, the solution after de-hydrogen halide can be added Toluene, methyl iso-butyl ketone (MIBK) (methyl isobutyl ketone) equal solvent, and add the alkali such as NaOH, potassium hydroxide gold Belong to hydroxide aqueous solution, de-hydrogen halide is carried out again.In de-hydrogen halide, there is formula (II-2-1) based on above-mentioned Hydroxyl total yield in the compound of structure is 1 equivalent, and the usage amount of alkali metal hydroxide is 0.01 equivalent to 0.3 equivalent, Wherein, it is preferable to 0.2 equivalent with 0.05 equivalent.In addition, the operating temperature range of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, and its operating time scope is 0.5 hour to 2 hours.
After de-hydrogen halide is completed, salt is removed by the step such as filtering and washing.In addition, also subtracting using heating The mode of pressure, distillation is given by toluene, methyl iso-butyl ketone (MIBK) equal solvent, and can obtain has at least two as shown in formula (II-2) The epoxide (c-1-1) of individual epoxy radicals.Epoxide (the c-1- with least two epoxy radicals of above-mentioned formula (II-2) 1) can be including but not limited to the Japanese chemical drugs of such as trade name NC-3000, NC-3000H, NC-3000S and NC-3000P etc. Commodity manufactured by (Nippon Kayaku Co.Ltd.).
The foregoing compound (c-1-2) with least one carboxylic acid group and at least one ethene unsaturated group is, for example, choosing From in the group being made up of following (1) to (3)：(1) acrylic acid, methacrylic acid, 2- methylacryoyloxyethyl succinic acid (2-methacryloyloxyethylbutanedioic acid), 2- methacryl oxygen-butyls succinic acid, 2- metering systems Acyloxyethyl adipic acid, 2- methacryl oxygen-butyls adipic acid, 2- methylacryoyloxyethyls hexahydrophthalic acid, 2- first Base acrylyl oxy-ethyl maleic acid, 2- methacryloxypropyls maleic acid, 2- methacryl oxygen-butyls maleic acid, 2- methyl Acryloxypropyl succinic acid, 2- methacryloxypropyls adipic acid, 2- methacryloxypropyls tetrahydrophthalic acid, 2- methacryloxypropyls phthalic acid, 2- methacryl oxygen-butyl phthalic acids or 2- methacryloxypropyl fourths Base hydrogen phthalic acid；(2) compound as obtained by (methyl) acrylate of hydroxyl reacts with dicarboxylic acid compound, its Middle dicarboxylic acid compound is including but not limited to adipic acid, succinic acid, maleic acid, phthalic acid；(3) by (first of hydroxyl Base) half ester compound obtained by acrylate and compound carboxylic acid anhydride reaction, (methyl) acrylate of wherein hydroxyl includes But it is not limited to 2- hydroxyethylmethacry,ates [(2-hydroxyethyl) acrylate], 2- HEMAs [(2-hydroxyethyl) methacrylate], 2- acrylates [(2-hydroxypropyl) acrylate], 2- hydroxy propyl methacrylates [(2-hydroxypropyl) methacrylate], 4- hydroxybutyl acrylates [(4- Hydroxybutyl) acrylate], 4- hydroxybutyl methacrylates [(4-hydroxybutyl) methacrylate], Or pentaerythritol acrylate trimethyl etc..In addition, compound carboxylic acid anhydride described herein can be with following first alkali-soluble trees Compound carboxylic acid anhydride (c-1-3) contained by the mixture of fat (C-1) is identical, therefore is repeated no more in this.
The mixture of above-mentioned first alkali soluble resin (C-1) is more selectively included compound carboxylic acid anhydride (c-1-3) And/or the compound (c-1-4) containing epoxy radicals.Above-mentioned compound carboxylic acid anhydride (c-1-3) may be selected from by following (1) to (2) institute group Into group：(1) succinic anhydride (butanedioic anhydride), maleic anhydride (maleic anhydride), clothing Health acid anhydrides (Itaconic anhydride), phthalic anhydride (phthalic anhydride), tetrabydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic anhydride), Methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene tetrabydrophthalic anhydride (methyl Endo-methylene tetrahydro phthalic anhydride), chlorendic anhydride (chlorendic anhydride), The binary carboxylic such as glutaric anhydride or inclined three benzoyl oxide (1,3-dioxoisobenzofuran-5-carboxylic anhydride) Anhydride compound；And (2) benzophenone tetracarboxylic dianhydride (benzophenone tetracarboxylic Dianhydride, abbreviation BTDA), the quaternary compound carboxylic acid anhydride such as double PMDAs or double phenylate tetracarboxylic acid dianhydrides.
The above-mentioned compound (c-1-4) containing epoxy radicals is, for example, to be selected from GMA, 3,4- epoxy basic rings Hexyl methacrylate, the glycidyl ether compound containing unsaturated group, the unsaturated compound containing epoxy radicals or above-mentioned The constituted group of any combination.The foregoing glycidyl ether compound containing unsaturated group is including but not limited to trade name Denacol EX-111、EX-121 Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、 Denacol EX-171, Denacol EX-192 etc. compound (being above the commodity of Chang Lai chemical conversion industries Co., Ltd.).
Foregoing first alkali soluble resin (C-1) can by formula (II-1) the epoxide with least two epoxy radicals (c-1-1) carry out polymerizeing instead with the compound (c-1-2) with least one carboxylic acid group and at least one ethene unsaturated group Should, the reaction product of hydroxyl is formed, then, then is added obtained by compound carboxylic acid anhydride (c-1-3) reacted.Based on above-mentioned The hydroxyl total yield of the reaction product of hydroxyl is 1 equivalent, the equivalent of the anhydride group contained by compound carboxylic acid anhydride (c-1-3) compared with Good is 0.4 equivalent to 1 equivalent, more preferably 0.75 equivalent to 1 equivalent., can be in when using multiple compound carboxylic acid anhydrides (c-1-3) Sequentially add or add simultaneously in reaction.When using dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride as carboxylic acid anhydridization During compound (c-1-3), the molar ratio of dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride are preferably 1/99 to 90/10, More preferably 5/95 to 80/20.In addition, the operating temperature range of above-mentioned reaction is, for example, the scope at 50 DEG C to 130 DEG C.
Foregoing first alkali soluble resin (C-1) can by formula (II-2) the epoxide with least two epoxy radicals (c-1-1) reacted with the compound (c-1-2) with least one carboxylic acid group and at least one ethene unsaturated group, shape Into the reaction product of hydroxyl, then, then by adding compound carboxylic acid anhydride (c-1-3) and/or compound (c- containing epoxy radicals 1-4) carry out obtained by polymerisation.Having on the epoxide (c-1-1) of at least two epoxy radicals based on formula (II-2) Epoxy radicals total yield be 1 equivalent, the above-mentioned compound with least one carboxylic acid group and at least one ethene unsaturated group (c-1-2) acid value equivalent is preferably 0.8 equivalent to 1.5 equivalents, more preferably 0.9 equivalent to 1.1 equivalents.Based on above-mentioned hydroxyl The hydroxyl total amount of reaction product be 100 molar percentages (mole %), the usage amount of compound carboxylic acid anhydride (c-1-3) is preferably 10 moles of % to 100 moles of %, more preferably 20 moles % to 100 moles of %, particularly good is 30 moles of % to 100 moles of %.
When preparing above-mentioned first alkali soluble resin (C-1), in order to accelerate reaction, it will usually added in reaction solution Alkali compounds is used as catalysts.Above-mentioned catalysts can be used alone or as a mixture, and above-mentioned catalysts are included But it is not limited to：Triphenylphosphine (triphenyl phosphine), antimony triphenyl (triphenyl stibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethyl ammonium Chloride), benzyltriethylammonium chloride (benzyltriethyl ammonium chloride) etc..Had extremely based on above-mentioned The epoxide (c-1-1) of few two epoxy radicals with least one carboxylic acid group and at least one ethene unsaturated group The usage amount summation of compound (c-1-2) is 100 parts by weight, and the usage amount of catalysts is preferably 0.01 parts by weight to 10 weights Measure part, more preferably 0.3 parts by weight to 5 parts by weight.
In addition, in order to control the degree of polymerization, polymerization inhibitor (polymerization generally can be also added in reaction solution inhibitor).Above-mentioned polymerization inhibitor can be including but not limited to：Methoxyl group phenol (methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), the tributyl paracresol (2,6-di-t-butyl- of 2,6- bis- ) or phenthazine (phenothiazine) etc. p-cresol.In general, above-mentioned polymerization inhibitor individually or can be mixed and a variety of made With.Based on the above-mentioned epoxide (c-1-1) with least two epoxy radicals with having at least one carboxylic acid group and at least one The usage amount summation of the compound (c-1-2) of individual ethene unsaturated group is 100 parts by weight, and the usage amount of polymerization inhibitor is preferable For 0.01 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 5 parts by weight.
When preparing the first alkali soluble resin (C-1), polymerization solvent can be used if necessary.It is used as above-mentioned polymerization The concrete example of reaction dissolvent, can enumerate as：Ethanol, propyl alcohol, isopropanol, butanol, isobutanol, 2- butanol, hexanol or ethylene glycol etc. Alcohol compound；The ketone compounds such as MEK or cyclohexanone；The aromatic hydrocarbon compound such as toluene or dimethylbenzene；Match Luo element Or the match Luo chlorins compound such as butyl match Luo plain (butyl cellosolve) (cellosolve)；Card must appropriate (carbitol) or Butyl card must the card such as appropriate (butyl carbitol) must appropriate class compound；Propylene glycol monomethyl ether (propylene glycol Monomethyl ether) etc. propylene glycol alkyl ether compound；Dipropylene glycol monomethyl ether [di (propylene glycol) Methyl ether] etc. many propylene glycol alkyl ethers [poly (propylene glycol) alkyl ether] class compound；Acetic acid Ethyl ester, butyl acetate, ethylene glycol ether acetate (ethylene glycol monoethyl ether acetate) or the third two The acetic ester compounds such as alcohol methyl ether acetate (propylene glycol methyl ether acetate)；Ethyl lactate (ethyl lactate) or butyl lactate (butyl lactate) etc. lactic acid alkyl ester (alkyl lactate) class compound；Or Dialkyl group glycol ethers；Or 3- ethoxyl ethyl propionates.Above-mentioned polymerization solvent typically individually or can be mixed and a variety of used.Separately Outside, the acid value of above-mentioned first alkali soluble resin (C-1) is preferably 50mgKOH/g to 200mgKOH/g, more preferably 60mgKOH/g To 150mgKOH/g.
In addition, above-mentioned first alkali soluble resin (C-1) passes through colloid osmotic chromatograph (Gel Permeation Chromatography, GPC) determine polystyrene conversion number mean molecule quantity be generally 500 to 10,000, preferably 800 to 8,000, more preferably 1,000 to 6,000.
In the concrete example of the present invention, the usage amount based on the alkali soluble resin (C) is 100 parts by weight, first alkali The usage amount scope of soluble resin (C-1) is 0 parts by weight to 90 parts by weight；Preferably 10 parts by weight are to 80 parts by weight；More preferably For 20 parts by weight to 70 parts by weight.When using the first alkali soluble resin (C-1), the photosensitive resin composition is formed Colored filter its hot solvent Thickness Variation rate more preferably.
Second alkali soluble resin (C-2) can be further included according to the alkali soluble resin (C) of the present invention, it is by with one Individual or more than one carboxylic acid or carboxylic acid anhydrides ethylene unsaturated monomer (c-2-1) and other copolymerizable ethene insatiable hungers After monomer (c-2-2) combined polymerization, react and obtain with the ethylene unsaturated monomer (c-2-3) with epoxy radicals.
In one embodiment, second alkali soluble resin (C-2) is that will first have one or more carboxylic acids or carboxylic The ethylene unsaturated monomer (c-2-1) of acid anhydrides carries out double bond with other copolymerizable ethylene unsaturated monomers (c-2-2) Copolymerization, to form a polymer, the side chain of wherein this polymer has carboxylic acid group.Then, in the side chain of this polymer Carboxylic acid group with epoxy radicals ethylene unsaturated monomer (c-2-3) carry out addition reaction, and be made the second alkali-soluble Resin (C-2).
In another embodiment, second alkali soluble resin (C-2) is first by other copolymerizable ethene insatiable hungers Double bond copolymerization is carried out with the ethylene unsaturated monomer (c-2-3) with epoxy radicals with monomer (c-2-2), to form one The side chain of polymer, wherein this polymer has epoxy radicals.Then, the epoxy radicals in the side chain of this polymer with one or The ethylene unsaturated monomer (c-2-1) of more than one carboxylic acid or carboxylic acid anhydrides carries out addition reaction, and it is solvable that second alkali is made Property resin (C-2).
In another embodiment, second alkali soluble resin (C-2) is first by other copolymerizable ethene insatiable hungers Double bond copolymerization is carried out with the ethylene unsaturated monomer (c-2-3) with epoxy radicals with monomer (c-2-2), to form one The side chain of polymer, wherein this polymer has epoxy radicals.Then, the epoxy radicals in the side chain of this polymer with one or The ethylene unsaturated monomer (c-2-1) of more than one carboxylic acid or carboxylic acid anhydrides is carried out after addition reaction, further with anhydrides Compound carries out half-esterification reaction and second alkali soluble resin (C-2) is made.
The foregoing ethylene unsaturated monomer (c-2-1) with one or more carboxylic acids or carboxylic acid anhydrides, wherein, should Ethylene unsaturated monomer with one or more carboxylic acids can be including but not limited to unsaturated monocarboxylic compound, insatiable hunger Polycyclic compound with multi-carboxylic acid compounds, with unsaturated group and a carboxylic acid group, or with unsaturated group and multiple carboxylic acids The polycyclic compound of base.
Foregoing unsaturated monocarboxylic compound can be including but not limited to (methyl) acrylic acid, butenoic acid, α-chloroacrylic acid, second Base acrylic acid, cinnamic acid, 2- (methyl) acryloyloxyethyls succinate (2- (meth) acryloyloxy ethyl Succinate monoester), 2- (methyl) acryloyloxyethyl hexahydrobenzene dicarboxylic acid esters, 2- (methyl) acryloyl ethoxy Base phthalic acid ester or omega- carboxylic acid group's polycaprolactone polyol mono acrylic esters etc..Omega- carboxylic acid group's polycaprolactones are more First alcohol mono acrylic ester can be synthetically produced for East Asia, model ARONIX M-5300 commodity.
Foregoing unsaturated multi-carboxylic acid compounds can including but not limited to maleic acid, fumaric acid, mesaconic acid, itaconic acid or Citraconic acid etc..
The foregoing polycyclic compound with unsaturated group and a carboxylic acid group can be bicyclic including but not limited to 5- carboxylic acid groups [2.2.1] hept-2-ene", 5- carboxylic acid group -5- methyl bicycles [2.2.1] hept-2-ene", 5- carboxylic acid group's -5- ethyls are bicyclic [2.2.1] Hept-2-ene", 5- carboxylic acid group -6- methyl bicycles [2.2.1] hept-2-ene"s or bicyclic [2.2.1] hept-2-ene" of 5- carboxylic acid group's -6- ethyls Deng.
The foregoing polycyclic compound with unsaturated group and multiple carboxylic acid groups can such as ring of 5,6- dicarboxyls acidic group two [2.2.1] Hept-2-ene" etc..
It is preferred that the foregoing ethylene unsaturated monomer with one or more carboxylic acids is to be selected from acrylic acid, first Base acrylic acid, 2- methacryloyloxyethyls succinate, 2- methacryl base oxethyl hexahydrobenzene dicarboxylic acid esters, or on State any combination of compound.
The foregoing ethylene unsaturated monomer (c-2-1) with one or more carboxylic acids or carboxylic acid anhydrides, wherein, it is foregoing Ethylene unsaturated monomer with one or more carboxylic acid anhydrides can including but not limited to unsaturated carboxylic acid anhydrides compound or Polycyclic compound with unsaturated group and carboxylic acid anhydrides.
Foregoing unsaturated carboxylic acid anhydrides compound can be including but not limited to maleic anhydride, fumaric acid anhydride, mesaconic acid acid anhydride, clothing Health acid anhydrides or citraconic anhydride etc..The foregoing polycyclic compound with unsaturated group and carboxylic acid anhydrides can be including but not limited to 5,6- dicarboxyls The ring of acid anhydrides two [2.2.1] hept-2-ene" etc..
It is preferred that the foregoing ethylene unsaturated monomer with one or more carboxylic acid anhydrides is maleic anhydride.
The above-mentioned ethylene unsaturated monomer (c-2-1) with one or more carboxylic acids or carboxylic acid anhydrides can independent one Plant or mix a variety of use.
In the concrete example of the present invention, one or more should be had based on second alkali soluble resin (C-2) The ethylene unsaturated monomer (c-2-1) of carboxylic acid or carboxylic acid anhydrides and other copolymerizable ethylene unsaturated monomer (c-2- 2) usage amount of combined polymerization monomer is 100 parts by weight, should have the ethene of one or more carboxylic acids or carboxylic acid anhydrides not The usage amount of saturation monomer (c-2-1) is 10 parts by weight to 90 parts by weight；Preferably 15 parts by weight are to 85 parts by weight；More preferably 20 Parts by weight are to 80 parts by weight.
Other foregoing copolymerizable ethylene unsaturated monomers (c-2-2) can be including but not limited to (methyl) alkyl acrylate Base ester, (methyl) acrylic acid alicyclic ester, (methyl) benzyl acrylate, unsaturated dicarboxylic ester, (methyl) acrylic acid hydroxyl alkane Ester, with the unsaturated compound beyond (methyl) acrylate-based polyethers, distyryl compound or above-claimed cpd.
Above-mentioned (methyl) alkyl acrylate can be including but not limited to (methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) i-butyl Ester, the second butyl ester of (methyl) acrylic acid or (methyl) acrylic acid tributyl ester etc..
Above-mentioned (methyl) acrylic acid alicyclic ester can be including but not limited to (methyl) cyclohexyl acrylate, (methyl) propylene Acid -2- methyl cyclohexyls, the bicyclic pentyl ester of (methyl) acrylic acid { or three ring [5.2.1.02,6] decyl- 8- bases (methyl) acrylic acid Ester }, the cyclopentyloxy ethyl ester of (methyl) acrylic acid two, (methyl) isobornyl acrylate or (methyl) acrylic acid tetrahydrofuran ester Deng.
Above-mentioned (methyl) benzyl acrylate can be including but not limited to (methyl) phenyl acrylate or methacrylic acid benzene Methyl esters etc..
Foregoing unsaturated dicarboxylic ester can be including but not limited to diethyl maleate, diethyl fumarate or itaconic acid diethyl Ester etc..
Foregoing (methyl) hydroxyalkyl acrylate can be including but not limited to (methyl) 2-Hydroxy ethyl acrylate or (methyl) third Olefin(e) acid -2- hydroxy propyl esters etc..
The foregoing polyethers acrylate-based with (methyl) can be including but not limited to polyethyleneglycol (methyl) acrylate Or polypropylene glycol list (methyl) acrylate etc..
Foregoing styrene is that compound can be p- including but not limited to styrene, α-methylstyrene, m- methyl styrene Methyl styrene or p-methoxystyrene etc..
Unsaturated compound beyond above-claimed cpd can be including but not limited to acrylonitrile, methacrylonitrile, vinyl chloride, partially Dichloroethylene, acrylamide, Methacrylamide, ethene ethyl ester, 1,3- butadiene, isoprene, 2,3- dimethyl 1,3- fourths Diene, N- succimide base -3- maleimidobenzoyls ester, N- succimide base -4- malimidobutanoates, N- Succimide base -6- maleimidohexanoic acids ester, N- succimide base -3- maleimidopropionic acids ester, N- (9- acridines Base) maleimide, N- octyl groups maleimide (N-octylmaleimide), N- N-cyclohexylmaleimides (N- ) or N-phenylmaleimide (N-phenylmaleimide) etc. cyclohexylmaleimide.
Other foregoing copolymerizable ethylene unsaturated monomers (c-2-2) can be individually a kind of or mix a variety of use.
It is preferred that other foregoing copolymerizable ethylene unsaturated monomers (c-2-2) are to be selected from (methyl) acrylic acid Methyl esters, (methyl) butyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid tributyl ester, (methyl) third Olefin(e) acid benzene methyl, the bicyclic pentyl ester of (methyl) acrylic acid, isobornyl methacrylate, the cyclopentyloxy second of (methyl) acrylic acid two Ester, styrene, any combination of p-methoxystyrene or above-claimed cpd.
In the concrete example of the present invention, one or more should be had based on second alkali soluble resin (C-2) The ethylene unsaturated monomer (c-2-1) of carboxylic acid or carboxylic acid anhydrides and other copolymerizable ethylene unsaturated monomer (c-2- 2) the usage amount summation of combined polymerization monomer is 100 parts by weight, other copolymerizable ethylene unsaturated monomers (c-2-2) Usage amount be 10 parts by weight to 90 parts by weight；Preferably 15 parts by weight are to 85 parts by weight；More preferably 20 parts by weight are to 80 weight Part.
This has the ethylene unsaturated monomer (c-2-3) of epoxy radicals can be including but not limited to (methyl) with epoxy radicals Acrylate compounds, the alpha-alkyl acrylate compounds with epoxy radicals or glycidyl ether compounds etc..
Foregoing (methyl) acrylate compounds with epoxy radicals can be including but not limited to (methyl) acrylic acid epoxy third Ester, (methyl) acrylic acid 2- methyl polyglycidyl, (methyl) acrylic acid 3,4- epoxies butyl ester, (methyl) acrylic acid 6,7- epoxy heptan Ester, (methyl) acrylic acid 3,4- epoxies cyclohexyl or (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates etc..
The foregoing alpha-alkyl acrylate compounds with epoxy radicals can be including but not limited to α-ethylacrylate epoxy third Ester, α-n-propyl Glycidyl Acrylate, α-n-butyl polyglycidyl or α-ethylacrylate -6,7- epoxy heptyl esters Deng.
Aforementioned epoxy ether compound can be including but not limited to o- vinyl benzene methyl glycidyl ethers (o- Vinylbenzylglycidylether), m- vinyl benzene methyl glycidyl ethers (m-vinylbenzylglycidylether) Or p- vinyl benzene methyl glycidyl ethers (p-vinylbenzylglycidylether) etc..
There is the ethylene unsaturated monomer (c-2-3) of epoxy radicals can be individually a kind of or to mix a variety of use for this.
It is preferred that the foregoing ethylene unsaturated monomer (c-2-3) with epoxy radicals is to be selected from glycidyl Propyl ester, methacrylic acid 2- methyl polyglycidyl, methacrylic acid 3,4- epoxycyclohexanecarboxylates, methacrylic acid 6,7- epoxies Heptyl ester, o- vinyl benzene methyl glycidyl ethers, m- vinyl benzene methyl glycidyl ethers, p- vinyl benzene methyl glycidyl ethers Or any combination of above-claimed cpd.
In the concrete example of the present invention, one or more should be had based on second alkali soluble resin (C-2) The ethylene unsaturated monomer (c-2-1) of carboxylic acid or carboxylic acid anhydrides and other copolymerizable ethylene unsaturated monomer (c-2- 2) the usage amount summation of combined polymerization monomer is 100 parts by weight, should be with the ethylene unsaturated monomer (c-2-3) of epoxy radicals Usage amount scope is 1 parts by weight to 35 parts by weight；Preferably 3 parts by weight are to 30 parts by weight；More preferably 5 parts by weight are to 25 weight Part.
In addition, above-mentioned second alkali soluble resin (C-2) passes through colloid osmotic chromatograph (Gel Permeation Chromatography, GPC) determine polystyrene conversion number mean molecule quantity be generally 1000 to 35,000, preferably For 3,000 to 30,000, more preferably 5,000 to 25,000.
In the concrete example of the present invention, the usage amount based on the alkali soluble resin (C) is 100 parts by weight, second alkali The usage amount of soluble resin (C-2) is 10 parts by weight to 100 parts by weight；Preferably 20 parts by weight are to 90 parts by weight；More preferably 30 parts by weight to 80 parts by weight.
Can be included according to the compound (D) with ethene unsaturated group of the present invention has at least one ethene insatiable hunger With the unsaturated compound of base and the unsaturated compound with least two ethene unsaturated groups.
The concrete example of the above-mentioned unsaturated compound with least one ethene unsaturated group can be including but not limited to third Acrylamide, acryloyl morpholine, metering system morpholide, acrylic acid -7- amido -3,7- dimethyl monooctyl ester, methacrylic acid -7- amine Base -3,7- dimethyl monooctyl ester, isobutoxymethyl acrylamide, isobutoxymethyl Methacrylamide, isobomyl acrylate Base 2-ethoxyethyl acetate, methacrylic acid isobornyl 2-ethoxyethyl acetate, isobornyl acrylate, isobornyl methacrylate, acrylic acid -2- Octyl Nitrite, methacrylic acid -2- Octyl Nitrites, ethyl diethylene glycol (DEG) acrylate, ethyl diethylene glycol (DEG) methacrylate, the 3rd Octyl acrylamide, tricaprylmethyl acrylamide, diacetone acrylamide, two acetone Methacrylamides, acrylic acid two Methylamine base ester, dimethylaminoethyl ester, dodecylacrylate, lauryl methacrylate, acrylic acid two Cyclopentene 2-ethoxyethyl acetate, methacrylic acid dicyclopentenyl 2-ethoxyethyl acetate, acrylic acid dicyclopentenyl ester, methacrylic acid dicyclopentenyl ester, Nitrogen, nitrogen-DMAA, nitrogen, nitrogen-dimethylmethacryl amide, acrylic acid tetrachloro phenyl ester, methacrylic acid tetrachlorobenzene Ester, acrylic acid -2- tetrachloros phenoxy ethyl, methacrylic acid -2- tetrachloros phenoxy ethyl, tetrahydrofurfuryl acrylate, methyl-prop Olefin(e) acid tetrahydrochysene chaff ester, tetrabromophenyl acrylate, methacrylic acid tetrabromo phenyl ester, acrylic acid -2- tetrabromos phenoxy ethyl, methyl-prop Olefin(e) acid -2- tetrabromos phenoxy ethyl, acrylic acid -2- Trichlorophenoxies ethyl ester, methacrylic acid -2- Trichlorophenoxies ethyl ester, third Olefin(e) acid tribromophenyl, methacrylic acid tribromophenyl, acrylic acid -2- tribromophenoxies ethyl ester, methacrylic acid -2- tribromo-benzene oxygen Base ethyl ester, acrylic acid -2- hydroxyl ethyl esters, 2-hydroxyethyl methacry-late, 2-hydroxypropyl acrylate, methacrylic acid -2- hydroxypropyls Ester, caprolactam, nitrogen-vinyl skin junket alkanone, acrylate, phenoxyethyl methacrylate, third Olefin(e) acid pentachlorophenyl ester, methacrylic acid pentachlorophenyl ester, acrylic acid pentabromo- phenyl ester, methacrylic acid pentabromo- phenyl ester, poly- single acrylic acid Glycol ester, poly- monomethacrylate glycol ester, poly- mono acrylic acid propylene glycol ester, poly- monomethacrylate acid propylene glycol ester, third Olefin(e) acid norbornene ester, or methacrylic acid norbornene ester etc..Wherein, should the unsaturated chemical combination with least one ethene unsaturated group Thing individually a kind of can use or mix a variety of use.
The concrete example of the above-mentioned unsaturated compound with least two ethene unsaturated groups can be including but not limited to second Omega-diol diacrylate, ethylene glycol dimethacrylate, diacrylate dicyclopentenyl ester, dimethacrylate dicyclopentenyl Ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, three (2- ethoxys) isocyanic acids Ester diacrylate, three (2- ethoxys) isocyanates dimethylacrylates, the acrylic acid of three (2- ethoxys) isocyanates three Ester, three (2- ethoxys) isocyanates trimethyl acrylic esters, the propylene of three (2- ethoxys) isocyanates three of caprolactone modification Acid esters, three (2- ethoxys) isocyanates trimethyl acrylic esters of caprolactone modification, three acrylic acid trihydroxy methyl propyl ester, front three Base acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of oxirane (hereinafter referred to as EO) modification, EO are modified Trimethacrylate acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of expoxy propane (hereinafter referred to as PO) modification, PO change The sour trihydroxy methyl propyl ester of the trimethacrylate of matter, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol two Acrylate, neopentylglycol dimethacrylate, 1,4 butanediol diacrylate, 1,4- butanediol dimethacrylates Ester, 1,6 hexanediol diacrylate, 1,6-HD dimethylacrylate, pentaerythritol triacrylate, pentaerythrite Trimethyl acrylic ester, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, polyester diacrylate, polyester Dimethylacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol acrylate (dipentaerythritol hexaacrylate；DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol 5 third Olefin(e) acid ester, dipentaerythritol pentamethacrylates, dipentaerythritol tetraacrylate, dipentaerythritol tetramethyl acrylic acid Ester, the dipentaerythritol acrylate of caprolactone modification, the dipentaerythritol hexamethacrylate of caprolactone modification, in oneself The Dipentaerythritol Pentaacrylate of ester modification, the dipentaerythritol pentamethacrylates of caprolactone modification, tetrapropylene acid two Trihydroxy methyl propyl ester, the trihydroxy methyl propyl ester of tetramethyl acrylic acid two, the bisphenol a diacrylate of EO modifications, the bisphenol-A of EO modifications Dimethylacrylate, the bisphenol a diacrylate of PO modifications, the bisphenol a dimethacrylate of PO modifications, the hydrogen of EO modifications Change bisphenol a diacrylate, the hydrogenated bisphenol A dimethylacrylate of EO modifications, the hydrogenated bisphenol A diacrylate of PO modifications Ester, the hydrogenated bisphenol A dimethylacrylate of PO modifications, the glycerin tripropionate of PO modifications, the Bisphenol F diacrylate of EO modifications Ester, the Bisphenol F dimethylacrylate of EO modifications, phenolic aldehyde polyglycidyl ether acrylate, phenolic aldehyde polyglycidyl ether methyl The commodity of acrylate, Japanese Toagosei Co., Ltd's manufacture and model TO-1382, or it is limited by Japanese chemical drug share Company manufactures and its model KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 commodity etc..Wherein, one kind it should individually can make with the unsaturated compound of at least two ethene unsaturated groups With or mix and a variety of use.
It is preferred that should be to be selected from three acrylic acid trihydroxy methyl propyl ester, EO with the compound (D) of ethene unsaturated group Three acrylic acid trihydroxy methyl propyl ester of modification, three acrylic acid trihydroxy methyl propyl ester of PO modifications, pentaerythritol triacrylate, season Penta tetra-acrylate, dipentaerythritol acrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol tetrapropylene acid Ester, the dipentaerythritol acrylate of caprolactone modification, the sour two trihydroxy methyl propyl ester of tetrapropylene, the propionic acid of glycerine three of PO modifications Ester, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or above-mentionedization Any combination of compound.
The above-mentioned compound (D) with ethene unsaturated group individually a kind of can use or mix a variety of use.
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, should the compound with ethene unsaturated group (D) usage amount is 20 parts by weight to 200 parts by weight；Preferably 30 parts by weight are to 180 parts by weight；More preferably 50 parts by weight are extremely 150 parts by weight.
A smooth initiator (E-1) with the structure as shown in formula (III) can be included according to the light initiator (E) of the present invention：
In formula (III), E1、E2、E3、E4、E5、E6、E7And E8It is 1 to 20 alkane independently to represent hydrogen atom, carbon number Base,COE16、OE17, halogen, NO2OrOr
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Independently represent warpSubstituted carbon number is 2 to 10 alkenyl；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Separately common representative-(CH2)p-W- (CH2)q-；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Separately representThe E of wherein at least one1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
E9、E10、E11And E12It is 1 to 20 alkyl independently to represent hydrogen atom, carbon number, and carbon number is for 1 to 20 alkyl Be unsubstituted or through at least one substituent group as follows, and at least one group be selected from phenyl, halogen, CN, OH, SH, carbon number are 1 to 4 alkoxy, (CO) OH or (CO) O (R1), wherein R1It is 1 to 4 alkyl to represent carbon number；Or
E9、E10、E11And E12Separately represent the phenyl being unsubstituted or taken through at least one group as follows The phenyl in generation, and the alkyl, halogen, CN, OE that it is 1 to 6 selected from carbon number that at least one group, which is,17、SE18Or NE19E20；Or
E9、E10、E11And E12Separately represent halogen, CN, OE17、SE18、SOE18、SO2E18Or NE19E20, wherein taking For base OE17、SE18Or NE19E20It is optionally via group E17、E18、E19And/or E20With a carbon of the naphthalene nucleus of formula (III) Atom formation five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Separately representCOE16Or NO2；
W represents O, S, NE26Or singly-bound, p represents 0 to 3 integer, and q represents 1 to 3 integer, Z1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, wherein at least one above-mentioned group is to be selected from halogen, E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2OrOr
E13It is 2 to 20 alkyl to represent carbon number, and the alkyl that carbon number is 2 to 20, which is mixed with, one or more O, S, SO, SO2、 NE26Or CO；Or
E13It is 2 to 12 alkenyl to represent carbon number, and carbon number is to have one or more without being mixed with or being mixed with for 2 to 12 alkenyl O, CO or NE26, wherein the alkenyl through being mixed with and alkyl that carbon number is 2 to 20 and carbon number without being mixed with or through being mixed with are 2 to 12 It is to be unsubstituted or replace through an at least halogen；Or
E13Represent carbon number as 4 to 8 cycloalkenyl group, carbon number as 2 to 12 alkynyl or without being mixed with or being mixed with have one or many Individual O, S, CO or NE26Carbon number be 3 to 10 cycloalkyl；Or
E13Phenyl or naphthyl is represented, and it is respectively unsubstituted or through at least one substituent group as follows, wherein should At least one group is to be selected from OE17、SE18、NE19E20、COE16、CN、NO2, halogen, carbon number be 1 The haloalkyl that alkyl, carbon number to 20 are 1 to 4, being mixed with has one or more O, S, CO or NE26And carbon number is 2 to 20 alkane Base；Or phenyl or naphthyl respectively has one or more O, S, CO or NE through not being mixed with or being mixed with26Be mixed with and carbon number be 3 to 10 cycloalkanes Base is replaced；
K represents 1 to 10 integer；
E14Represent hydrogen atom, carbon number as 3 to 8 cycloalkyl, carbon number as 2 to 5 alkenyl, carbon number as 1 to 20 alkoxy Or be unsubstituted or alkyl that carbon number through at least one substituent group as follows is 1 to 20, and at least one group is Selected from halogen, phenyl, the alkyl phenyl or CN that carbon number is 1 to 20；Or
E14Phenyl or naphthyl is represented, it is respectively unsubstituted or through at least one substituent group as follows, and at least one Haloalkyl that alkyl that it is 1 to 6 selected from carbon number that individual group, which is, carbon number are 1 to 4, halogen, CN, OE17、SE18And/or NE19E20； Or
E14Represent carbon number as 3 to 20 heteroaryl, carbon number as 1 to 8 alkoxy, benzyloxy or phenoxy group, benzyloxy and Phenoxy group is unsubstituted or through at least one substituent group as follows, and it selected from carbon number is 1 to 6 that at least one group, which is, Alkyl, carbon number be 1 to 4 haloalkyl and/or halogen；
E15It is 3 to 20 heteroaryl that carbon number, which is represented, as 6 to 20 aromatic radical or carbon number, and it is respectively unsubstituted or through following institute At least one substituent group shown, and at least one group be selected from phenyl, halogen, carbon number for 1 to 4 haloalkyl, CN, NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2And SO is bonded and carbon number is 1 to 10 alkyl and SO2It is bonded and carbon number is 1 Alkyl to 10, it is mixed with and has one or more O, S or NE26And carbon number is 2 to 20 alkyl；Or, carbon number is 6 to 20 fragrance The alkyl that it is 1 to 20 through carbon number that heteroaryl that base or carbon number are 3 to 20 is each replaces, wherein carbon number for 1 to 20 alkyl be without Replace or through at least one substituent group as follows, and at least one group is to be selected from halogen, COOE17、CONE19E20, benzene Aryloxycarbonyl that heteroaryl that cycloalkyl that base, carbon number are 3 to 8, carbon number are 3 to 20, carbon number are 6 to 20, carbon number are 3 to 20 Heteroaryloxycarbonyl, OE17、SE18Or NE19E20；Or
E15Represent hydrogen atom, carbon number as 2 to 12 alkenyl, without being mixed with or being mixed with have one or more O, CO or NE26And Carbon number is 3 to 8 cycloalkyl；Or
E15It is 1 to 20 alkyl to represent carbon number, carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one group is to be selected from halogen, OE17、SE18, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 Heteroaryl, carbon number be 6 to 20 aryloxycarbonyl, carbon number be 3 to 20 Heteroaryloxycarbonyl, NE19E20、COOE17、 CONE19E20、PO(OCkH2k+1)2、 Or phenyl, wherein the carbon number be 1 to 20 alkyl is replaced through phenyl, and alkyl that it is 1 to 20 through halogen, carbon number that phenyl, which is, carbon number be 1 to 4 haloalkyl, OE17、SE18Or NE19E20Substitution；Or
E15It is 2 to 20 alkyl to represent carbon number, and carbon number is to be mixed with to have one or more O, SO or SO for 2 to 20 alkyl2, Alkyl through being mixed with and carbon number is 2 to 20 is unsubstituted or through at least one substituent group as follows, and at least one Group is to be selected from halogen, OE17、COOE17、CONE19E20, phenyl or through OE17、SE18Or NE19E20Substituted phenyl；Or
E15It is 2 to 20 alkanoyl or benzoyl to represent carbon number, and it is unsubstituted or through as follows at least one Individual substituent group, and at least one group is selected from the alkyl that carbon number is 1 to 6, halogen, phenyl, OE17、SE18Or NE19E20；Or
E15Representative is unsubstituted or through at least one OE17Substituted naphthoyl or the heteroaryl carbonyl that carbon number is 3 to 14 Base；Or
E15It is 2 to 12 alkoxy carbonyl to represent carbon number, and carbon number is without being mixed with or being mixed with for 2 to 12 alkoxy carbonyl There are one or more O, wherein through being mixed with or without the alkoxy carbonyl being mixed with and carbon number is 2 to 12 being unsubstituted or through at least One hydroxyl substitution；Or
E15Phenyloxycarbonyl is represented, phenyloxycarbonyl is unsubstituted or through at least one substituent group as follows, And alkyl that it is 1 to 6 selected from carbon number that at least one group, which is, halogen, carbon number be 1 to 4 haloalkyl, phenyl, OE17、SE18 Or NE19E20；Or
E15Represent CN, CONE19E20、NO2, carbon number for 1 to 4 haloalkyl, S (O)r-R2And S (O)rThe phenyl of bond, Wherein with S (O)rThe phenyl of bond be unsubstituted or through carbon number be 1 to 12 alkyl or SO2-R2Substitution, and R2Represent carbon number For 1 to 6 alkyl；Or
E15Represent and SO2O bond phenyl, wherein with SO2The phenyl of O bonds is to be unsubstituted or is 1 to 12 through carbon number Alkyl substitution；Or
E15Represent diphenylphosphino or two (R3)-phosphono, and R3It is 1 to 4 alkoxy to represent carbon number；
R represents 1 to 2 integer；
E'14Represent to have and be directed to E14One of those in definition；
E'15Represent to have and be directed to E15One of those in definition；
Z2Representative-O- ,-S- ,-SO- or-SO2-；
Z3Representative-O- ,-CO- ,-S- or singly-bound；
E16It is 3 to 20 heteroaryl that carbon number, which is represented, as 6 to 20 aromatic radical or carbon number, and it is respectively unsubstituted or through following institute At least one substituent group shown, and at least one group be selected from phenyl, halogen, carbon number for 1 to 4 haloalkyl, CN, NO2、OE17、SE18、NE19E20, be mixed with and have one or more O, S or NE26And carbon number be 1 to 20 alkyl, or carbon number be 1 to 20 alkyl, wherein carbon number for 1 to 20 alkyl are unsubstituted or through at least one substituent group as follows, wherein extremely A few group is to be selected from halogen, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl Heteroaryloxycarbonyl that aryloxycarbonyl that base, carbon number are 6 to 20, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E16It is 1 to 20 alkyl to represent hydrogen atom or carbon number, and wherein carbon number for 1 to 20 alkyl is unsubstituted or through such as Lower at least one shown substituent group, and at least one group is 3 to 6 selected from halogen, phenyl, OH, SH, CN, carbon number Alkenyloxy group, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1), O (CO)-phenyl or (CO) OH or (CO) O (R1)；Or
E16It is 2 to 12 alkyl to represent carbon number, and carbon number is to be mixed with to have one or more O, S or NE for 2 to 12 alkyl26； Or
E16Represent (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 12 alkenyl or carbon number be 3 to 8 Cycloalkyl, the wherein R4It is 1 to 8 alkyl to represent carbon number；Or
E16Represent through SE18Substituted phenyl, wherein E18Bond is represented to COE16The phenyl or naphthalene of the carbazole moiety connected The singly-bound of basic ring；
N represents 1 to 20 integer；
E17Represent hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, its be unsubstituted or through it is as follows at least One substituent group, and at least one group is selected from halogen, OH, SH, CN, the alkenyloxy group that carbon number is 3 to 6, OCH2CH2CN、 OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6), with O (CO) be bonded phenyl, (CO) OH, (CO) O (R1), carbon number For 3 to 20 cycloalkyl, SO2-(R7)、O(R7) or be mixed with the cycloalkyl for thering is one or more O and carbon number to be 3 to 20, wherein R5 Represent alkyl of the carbon number as 1 to 3, R6It is 2 to 4 alkenyl to represent carbon number, and R7It is 1 to 4 haloalkyl to represent carbon number；Or
E17It is 2 to 20 alkyl to represent carbon number, and carbon number for 2 to 20 alkyl be mixed with have one or more O, S or NE26；Or
E17Represent (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 1 to 8 alkanoyl, carbon number be 2 to 12 The cycloalkyl that the enoyl- or carbon number that alkenyl, carbon number are 3 to 6 are 3 to 20, wherein carbon number for 3 to 20 cycloalkyl be without It is miscellaneous or be mixed with and have one or more O, S, CO or NE26；Or
E17It is 3 to 10 group that is formed of cycloalkyl bond, and above-mentioned base that carbon number, which is represented, by 1 to 8 alkyl and carbon number Group is that have one or more O without being mixed with or being mixed with；Or
E17Benzoyl is represented, benzoyl is unsubstituted or through at least one substituent group as follows, and at least The alkoxy that alkyl, halogen, OH or the carbon number that it is 1 to 6 selected from carbon number that one group, which is, are 1 to 3；Or
E17It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is respectively unsubstituted or through as follows at least one Individual substituent group, and alkyl that it is 1 to 12 selected from halogen, OH, carbon number that at least one group, which is, carbon number be 1 to 12 alkoxy, CN、NO2, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amido orWherein R8It is 1 to 3 alkoxy to represent carbon number, and R9It is 1 to 12 alkyl to represent carbon number；Or
E17With withPhenyl or naphthyl ring wherein one Individual carbon atom formation singly-bound；
E18It is 2 to 12 cycloalkyl or phenyl-R as 3 to 20 of alkenyl, carbon number to represent hydrogen atom, carbon number5, wherein carbon number The cycloalkyl for being 3 to 20 for 2 to 12 alkenyl, carbon number and phenyl-R5Be without be mixed with or be mixed with have one or more O, S, CO, NE26Or COOE17；Or
E18It is 1 to 20 alkyl to represent carbon number, and carbon number is unsubstituted or through as follows at least one for 1 to 20 alkyl Individual substituent group, and at least one group is selected from OH, SH, CN, the alkenyloxy group that carbon number is 3 to 6, OCH2CH2CN、OCH2CH2 (CO)O(R1)、O(CO)-(R6)、O(CO)-(R1), O (CO)-phenyl or (CO) OE17；Or
E18It is 2 to 20 alkyl to represent carbon number, carbon number for 2 to 20 alkyl be mixed with have one or more O, S, CO, NE26Or COOE17；Or
E18Represent (CH2CH2O)nH、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 8 alkanoyl or carbon number be 3 to 6 Enoyl-；Or
E18Benzoyl is represented, benzoyl is unsubstituted or through at least one substituent group as follows, and extremely The alkyl that the alkoxy or carbon number that alkyl that it is 1 to 6 selected from carbon number that a few group, which is, halogen, OH, carbon number are 1 to 4 are 1 to 4 Sulfenyl；Or
E18It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and its is each unsubstituted or through at least one as follows Substituent group, and at least one group is to be selected from the haloalkyl, carbon number that halogen, the alkyl that carbon number is 1 to 12, carbon number are 1 to 4 For 1 to 12 alkoxy, CN, NO2, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, two Phenyl amido, (CO) O (R4)、CO-R4、(CO)N(R4)2Or
E19And E20Separately represent hydroxy alkyl as 2 to 4 of alkyl, carbon number as 1 to 20 of hydrogen atom, carbon number, carbon Cycloalkyl that alkenyl that alkoxyalkyl that number is 2 to 10, carbon number are 2 to 5, carbon number are 3 to 20, phenyl-R5, carbon number be 1 to 8 Alkanoyl, carbon number be 1 to 8 alkanoyl epoxide, carbon number be 3 to 12 enoyl-, SO2-R7Or benzoyl；Or
E19And E20It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is respectively unsubstituted or through as follows At least one substituent group, and haloalkyl that it is 1 to 4 selected from halogen, carbon number that at least one group, which is, carbon number are 1 to 20 Alkoxy, carbon number be 1 to 12 alkyl, benzoyl or carbon number be 1 to 12 alkoxy；Or
E19And E20It is to be formed to have O, S or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or hexa-atomic Saturation or unsaturation ring, and five yuan or hexa-atomic saturation or unsaturation ring are unsubstituted or through at least one group as follows Substitution, alkoxy that alkyl that it is 1 to 20 selected from carbon number that wherein at least one group, which is, carbon number are 1 to 20 ,=O, OE17、 SE18、NE21E22、(CO)E23、NO2, halogen, carbon number for 1 to 4 haloalkyl, CN, phenyl,Or Person has one or more O, S, CO or NE without being mixed with or being mixed with17And carbon number is 3 to 20 cycloalkyl；Or
E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms connected, the heteroaromatic ring system is not It is substituted or through at least one substituent group as follows, and at least one group is selected from the alkyl, carbon that carbon number is 1 to 20 Alkoxy that haloalkyl that number is 1 to 4, carbon number are 1 to 20 ,=O, OE17、SE18、NE21E22、(CO)E23、Halogen, NO2, CN, phenyl, or have one or more O, S, CO or NE without being mixed with or being mixed with17 And carbon number is 3 to 20 cycloalkyl；
E21And E22Separately represent haloalkyl as 1 to 4 of alkyl, carbon number as 1 to 20 of hydrogen atom, carbon number, carbon Cycloalkyl or phenyl of the number for 3 to 10；
E21And E22Formed together with its bonded nitrogen-atoms has O, S or NE without being mixed with or being mixed with26Five yuan or hexa-atomic Saturation or unsaturation ring, wherein five yuan or hexa-atomic saturation or unsaturation ring are uncondensed or condensed with phenyl ring；
E23Represent hydrogen atom, OH, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have at least one O, CO or NE26And carbon number for 2 to 20 alkyl, without being mixed with or being mixed with have O, S, CO or NE26And carbon number is 3 to 20 cycloalkanes Base；Or
E23Represent phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represent (CO) OE17、CONE19E20、(CO)E17Or with for E19And E20One of those in definition；
E25Represent COOE17、CONE19E20、(CO)E17；Or E25With for E17One of those in definition；
E26Represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have one or more O Or the alkyl that CO and carbon number are 2 to 20；Or E26Represent phenyl-R1, without being mixed with or being mixed with have one or more O or CO and carbon number For 3 to 8 cycloalkyl；Or E26Represent (CO) E19；Or E26Represent phenyl, phenyl be unsubstituted or through it is as follows at least One substituent group, and the alkyl halide that alkyl that it is 1 to 20 selected from carbon number that at least one group, which is, halogen, carbon number are 1 to 4 Base, OE17、SE18、NE19E20OrBut condition is the light initiator of the structure as shown in formula (III) (E-1) there is at least one
It should be characterised by its carbazole moiety including at least one with the light initiator (E-1) of structure shown in formula (III) Individual cyclization (annelated) unsaturation ring.In other words, at least one pair of E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is
The alkyl that foregoing alleged carbon number is 1 to 20 be straight or branched and be such as carbon number be 1 to 18, carbon number be 1 to 4th, carbon number is that 1 to 12, carbon number is the alkyl that 1 to 8, carbon number is 1 to 8 or carbon number is 1 to 4, or carbon number is 4 to 12 or carbon number is 4 To 8 alkyl.Specific example such as methyl, ethyl, propyl group, isopropyl, normal-butyl, the second butyl, isobutyl group, tributyl, penta Base, hexyl, heptyl, 2,4,4- tri-methyl-amyls, 2- ethylhexyls, octyl group, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, Palmityl, octadecyl and 20 bases.The alkyl identical definition that it is 1 to 20 with above-mentioned carbon number that the alkyl that carbon number is 1 to 6, which has, And with the corresponding carbon number of highest.
It is as aftermentioned for 1 to 20 alkyl that this contains the carbon number for being unsubstituted or being substituted of at least one carbon-to-carbon multikey Alkenyl.
The carbon number is definition as be described hereinafter through halogen substitution by 1 to 4 haloalkyl and carbon number is 1 as previously defined To 4 alkyl.Alkyl group may be, for example, list-or many halogenations, until all hydrogen atoms replace with halogen, and may be, for example, CjHwXy, wherein w+y=2j+1 and X are halogen, preferably fluorine atom.Specific example such as chloromethyl, trichloromethyl, trifluoromethyl Or 2- bromopropyls, in particular trifluoromethyl or trichloromethyl.
The alkyl that it is 2 to 4 through the carbon number that one or two oxygen atoms replace that the hydroxy alkyl that the carbon number is 2 to 4, which means,.Alkyl It can be straight or branched.Specific example such as 2- hydroxyethyls, 1- hydroxyethyls, 1- hydroxypropyls, 2- hydroxypropyls, 3- hydroxyls third Base, 1- hydroxybutyls, 4- hydroxybutyls, 2- hydroxybutyls, 3- hydroxybutyls, 2,3- dihydroxypropyls or 2,4- dihydroxy fourths Base.
The alkyl that it is 2 to 10 through the O carbon numbers being mixed with that the alkoxyalkyl that the carbon number is 2 to 10, which is,.Carbon number is 2 to 10 Alkyl has the identical definition for 1 to 20 alkyl with foregoing carbon number, and with the corresponding carbon number of highest.Specific example such as first Epoxide methyl, methoxy ethyl, methoxy-propyl, ethoxyl methyl, ethoxyethyl group, ethoxycarbonyl propyl, propoxy methyl, third Epoxide ethyl, propoxypropyl.
This, which is mixed with, one or more O, S, NE26Or CO carbon number is for example through O, S, NE for 2 to 20 alkyl26Or CO It is mixed with 1 to 9 time, 1 to 5 time, 1 to 3 time, 1 time or 2 times.If exist it is more than one be mixed with group, it is identical type or not Together.Two oxygen atoms are separated by least one methylene, preferably at least two methylene (stretching ethyl).The grade alkyl is straight Chain or side chain.For example, there will be following construction unit：-CH2-CH2-O-CH2CH3、-[CH2CH2O]y-CH3(wherein y=1 To 9) ,-(CH2-CH2O)7-CH2CH3、-CH2-CH(CH3)-O-CH2-CH2CH3、-CH2-CH(CH3)-O-CH2-CH3、-CH2- CH2-S-CH2CH3、-CH2-CH(CH3)-NE26-CH2-CH3、-CH2-CH2-COO-CH2CH3Or-CH2-CH(CH3)-OCO-CH2- CH2CH3。
In the present invention, the cycloalkanes that the cycloalkyl and carbon number that cycloalkyl that carbon number is 3 to 10, carbon number are 3 to 10 are 3 to 8 Base can be regarded as comprising at least the alkyl of a ring.Specific example for example cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl, Amyl group cyclopenta and cyclohexyl.In the present invention, carbon number is that 3 to 10 cycloalkyl also covers the example of two rings, that is, bridging Ring, specific example can be such as And other corresponding rings.Its He may be, for example, at concrete example (for example) OrEtc. structure, and bridging or fused ring system, for example, definition herein is also includedEtc. structure, wherein R10Alkyl, R are stretched in representative11Represent alkyl.
This is through O, S, NE26Or the carbon number that CO is mixed with is that 3 to 20 cycloalkyl has definition as hereinbefore, wherein alkyl At least one-CH2- group is to replace with O, S, NE26Or CO.Specific example is such as (for example)、 Etc. structure.
The carbon number by 1 to 8 alkyl and carbon number be 3 to 10 the group that is formed of cycloalkyl bond refer to through at least one Alkyl-substituted carbon number as previously defined with most 8 carbon atoms is 3 to 10 cycloalkyl.Specific example isDeng.
This be mixed with have one or more O carbon number by 1 to 8 alkyl be 3 to 10 with carbon number cycloalkyl bond formed Group refer to through at least one have most 8 carbon atoms it is alkyl-substituted be mixed with as previously defined have one or many Individual O carbon number is 3 to 10 cycloalkyl.Specific example is such asDeng.
The alkoxy that the carbon number is 1 to 12 is the alkyl that the carbon number through an oxygen atom substitution is 1 to 12.Carbon number be 1 to 12 alkyl has the identical definition for 1 to 20 alkyl such as foregoing carbon number, and with the corresponding carbon number of highest.Carbon number is 1 to 4 alkoxy is straight or branched, for example methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, the second fourth oxygen Base, isobutoxy or the 3rd butoxy.The alkoxy that the alkoxy and carbon number that carbon number is 1 to 8 are 1 to 4 is and aforementioned definitions phase Together, and with the corresponding carbon number of highest.
The alkyl sulfenyl that the carbon number is 1 to 12 is the alkyl that the carbon number through a sulphur atom substitution is 1 to 12.The carbon number is 1 to 12 alkyl has the identical definition for 1 to 20 alkyl such as foregoing carbon number, and with the corresponding carbon number of highest.Carbon Number is straight or branched for 1 to 4 alkyl sulfenyl, such as methylsulfany, ethylsulfanyl, propyl group sulfenyl, isopropylsulfanyl, positive fourth Base sulfenyl, the second butyl sulfenyl, i-butylthio, tributyl sulfenyl.
The phenyl-R5Ke Li such as Wei Benzyl bases, phenylethyl, α-methylbenzyl or α, in particular alpha-alpha-dimethyl-benzyl, benzyl Base.
The phenyl-R8May be, for example, benzyloxy, phenyl ethoxy, Alpha-Methyl benzyloxy or α, alpha-alpha-dimethyl benzyloxy, especially It is benzyloxy.
The alkenyl that the carbon number is 2 to 12 is list-or how unsaturated and is that alkenyl, carbon number that for example, carbon number is 2 to 10 are 2 The alkenyl that alkenyl, carbon number to 8 are 2 to 5.Specific example such as vinyl, pi-allyl, methacrylic, 1,1- dimethallyls Base, 1- cyclobutenyls, 3- cyclobutenyls, 2- cyclobutenyls, 1,3-pentadiene base, 5- hexenyls, 7- octenyls or laurylene base, in particular Pi-allyl.The alkenyl that carbon number is 2 to 5 has the identical definition for the alkenyl for being 2 to 12 such as foregoing carbon number, and corresponding with highest Carbon number.
Being mixed with has one or more O, S, NE26Or CO carbon number is for example through O, S, NE for 2 to 12 alkenyl26Or between CO Miscellaneous 1 to 9 time, 1 to 5 time, 1 to 3 time, 1 time or 2 times.If exist it is more than one be mixed with group, it is identical type or not Together.Two oxygen atoms are separated by least one methylene, preferably at least two methylene (stretching ethyl).Alkenyl be straight chain or Side chain and as defined above.For example, following construction unit can be formed：- CH=CH-O-CH2CH3,-CH=CH-O-CH= CH2Deng.
The carbon number has at least one double bond for 4 to 8 cycloalkenyl group, and may be, for example, cycloalkenyl group or carbon that carbon number is 4 to 6 Number is 6 to 8 cycloalkenyl group.Specific example such as cyclobutane base, cyclopentenyl, cyclohexenyl group or cyclo-octene base, in particular cyclopentene Base and cyclohexenyl group, preferably cyclohexenyl group.
The carbon number is single or multiple unsaturation for 3 to 6 alkenyloxy group, and one of them with the definition such as foregoing alkenyl, And connection epoxide has the corresponding carbon number of highest.Specific example such as allyloxy, methyl allyloxy, butenyloxy, penta Alkenyloxy group, 1,3- pentadienes epoxide, 5- hexene epoxides.
The alkynyl that the carbon number is 2 to 12 is single or multiple unsaturated straight or branched, and may be, for example, the alkynes that carbon number is 2 to 8 The alkynyl that the alkynyl or carbon number that base, carbon number are 2 to 6 are 2 to 4.Specific example such as acetenyl, propinyl, butynyl, 1- butine Base, 3- butynyls, 2- butynyls, pentynyl hexin base, 2- hexin bases, 5- hexin bases, octynyl etc..
The carbon number is straight or branched for 2 to 20 alkanoyl, and may be, for example, carbon number be 2 to 18, carbon number be 2 to 14, Carbon number be 2 to 12, carbon number be the alkanoyl or carbon number that 2 to 8, carbon number is 2 to 6 or carbon number is 2 to 4 be 4 to 12 or carbon number be 4 to 8 alkanoyl.Specific example such as acetyl group, propiono, bytyry, isobutyryl, valeryl, caproyl, heptanoyl group, decoyl Base, pelargonyl group, capryl, dodecanoyl, myristoyl base, pentadecanoyl base, hexadecanoyl group, octadecanoyl, 20 acyl groups, preferably Acetyl group.The alkanoyl that carbon number is 1 to 8 has the alkanoyl identical definition that carbon number as the aforementioned is 2 to 20, and with highest Corresponding carbon number.
The carbon number is straight or branched for 2 to 12 alkoxy carbonyl, and be for example methoxycarbonyl, ethoxy carbonyl, Propoxycarbonyl, n-butoxycarbonyl, isobutoxy carbonyl, 1,1- dimethyl propylenes Epoxide carbonyl, pentyloxy carbonyl, hexyloxy carbonyl Base, Epoxide carbonyl in heptan, carbonyl octyloxy, nonyl epoxide carbonyl, decyloxy carbonyl or 12 Epoxide carbonyls, in particular methoxyl group carbonyl Base, ethoxy carbonyl, propoxycarbonyl, n-butoxycarbonyl or isobutoxy carbonyl, preferably methoxycarbonyl.
It can be straight or branched that this, which is mixed with the alkoxy carbonyl that the carbon number for having one or more O is 2 to 12,.Two oxygen atoms Separated by least two methylene (stretching ethyl).The alkoxy carbonyl through being mixed with is unsubstituted or through one or more hydroxyls Substitution.Carbon number for 6 to 20 aryloxycarbonyl may be, for example, phenyloxycarbonyl (=phenyl-O- (CO) O-), naphthoxycarbonyl, Anthracene Epoxide carbonyl etc..The heteroaryl that it is 5 to 20 with the-O-CO- carbon numbers being bonded that the Heteroarylcarbonyl that carbon number is 5 to 20, which can be,.
The cycloalkyl that it is 3 to 10 with the CO carbon numbers being bonded that the naphthene base carbonyl that the carbon number is 3 to 10, which can be, wherein cycloalkyl With definition as hereinbefore, and with the corresponding carbon number of highest.Being mixed with has one or more O, S, NE26Or CO carbon Number refers to through being mixed with the cycloalkyl being bonded with CO for 3 to 10 naphthene base carbonyl, wherein cycloalkyl through being mixed with have with it is preceding State identical definition.
The cycloalkyl that it is 3 to 10 with the carbon number of-O- (CO)-bond that the cyclo alkoxy carbonyl that the carbon number is 3 to 10, which can be, its Middle cycloalkyl has definition as hereinbefore, and with the corresponding carbon number of highest.Being mixed with has one or more O, S, NE26 Or CO carbon number refers to the cycloalkyl with-O- (CO)-bond through being mixed with for 3 to 10 cyclo alkoxy carbonyl, wherein through being mixed with Cycloalkyl there is definition as hereinbefore.
The carbon number refers to through at least one alkyl-substituted phenyl, the wherein sum total of carbon atom for 1 to 20 alkyl phenyl Up to 20.
The carbon number may be, for example, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, 1,2- benzos phenanthryl and four for 6 to 20 aryl Phenyl, connection stretch triphenyl etc., in particular phenyl or naphthyl, preferably phenyl.Naphthyl is 1- naphthyls or 2- naphthyls.
In the content of the light initiator (E-1) of the present invention, the carbon number includes monocyclic or polycyclic system for 3 to 20 heteroaryl System, such as fused ring system.Concrete example is thienyl, benzo [b] thienyl, naphtho- [2,3-b] thienyl, thianthrene group, furans Base, dibenzofuran group,Sigh base, xanthyl, thioxanthene base, coffee dislike thiophene base, pyrrole radicals, imidazole radicals, pyrazolyl, pyrazinyl, phonetic Piperidinyl, pyridazinyl, indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizine base, isoquinolyl, quinolyl, phthalein Piperazine base, naphthyridines base, quinoxaline base, quinazolyl,Quinoline base, pteridine radicals, carbazyl, B-carboline base, phenanthridinyl, acridinyl, naphthalene Embedding pyrimidyl, phenanthroline, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furan Xanthones bases, phenoxazine base, 7- phenanthryl, Anthraquinone -2- bases (the side epoxide -9,10- dihydroanthracene -2- bases of=9,10- bis-), 3- benzos [b] thienyl, 5- benzos [b] thienyl, 2- benzos [b] thienyl, 4- dibenzofuran groups, 4,7- dibenzofuran groups, 4- methyl -7- dibenzofuran groups, 2- xanthenes Base, 8- methyl -2- xanthyls, 3- xanthyls, 2- coffee evil thiophene base, 2,7- coffee evil thiophene base, 2- pyrrole radicals, 3- pyrrole radicals, 5- methyl - 3- pyrrole radicals, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 2- methyl -4- imidazole radicals, 2- ethyl -4- imidazole radicals, 2- ethyls -5- Imidazole radicals, 1H-TETRAZOLE -5- bases, 3- pyrazolyls, 1- methyl -3- pyrazolyls, 1- propyl group -4- pyrazolyls, 2- pyrazinyls, 5,6- bis- Methyl -2- pyrazinyls, 2- indolizine base, 2- methyl -3- isoindolyls, 2- methyl isophthalic acids-isoindolyl, 1- methyl -2- indyls, 1- methyl -3- indyls, 1,5- dimethyl -2- indyls, 1- methyl -3- indazolyls, 2,7- dimethyl -8- purine radicals, 2- first Epoxide -7- methyl -8- purine radicals, 2- quinolizines base, 3- isoquinolyls, 6- isoquinolyls, 7- isoquinolyls, 3- methoxyl groups -6- are different Quinolyl, 2- quinolyls, 6- quinolyls, 7- quinolyls, 2- methoxyl group -3- quinolyls, 2- methoxyl group -6- quinolyls, 6- phthalazines Base, 7- phthalazinyls, 1- methoxyl group -6- phthalazinyls, 1,4- dimethoxy -6- phthalazinyls, 1,8- naphthyridines -2- bases, 2- quinoxalines base, 6- quinoxalines base, 2,3- dimethyl -6- quinoxalines base, 2,3- dimethoxy -6- quinoxalines base, 2- quinazolyls, 7- quinazolines Base, 2- dimethyl amido -6- quinazolyls, 3-Quinoline base, 6-Quinoline base, 7-Quinoline base, 3- methoxyl group -7- quinolines base, 2- talk endlessly Piperidinyl, 6- pteridine radicals, 7- pteridine radicals, 6,7- dimethoxy -2- pteridine radicals, 2- carbazyls, 3- carbazyls, 9- methyl -2- carbazoles Base, 9- methyl -3- carbazyls, B-carboline -3- bases, 1- methyl-ss-carboline -3- bases, 1- methyl-ss-carboline -6- bases, 3- phenanthridines Base, 2- acridinyls, 3- acridinyls, 2- perimidinyls, 1- methyl -5- perimidinyls, 5- phenanthrolines, 6- are luxuriant and rich with fragrance Cough up quinoline base, 1- phenazinyl, 2- phenazinyl, 3- isothiazolyls, 4- isothiazolyls, 5- isothiazolyls, 2- phenothiazinyls, 3- phenthazine Base, 10- methyl -3- phenothiazinyls, 3- isoxazolyls, 4- isoxazolyls, 5- isoxazolyls, 4- methyl -3- furan Xanthones bases, 2- phenoxazines Base, 10- methyl -2- phenoxazine bases etc..
It is preferred that the heteroaryl that the carbon number is 3 to 20 can be thienyl, benzo [b] thienyl, thianthrene group, thioxanthene base, 1- Methyl -2- indyls or 1- methyl -3- indyls.More preferably, the heteroaryl that carbon number is 3 to 20 can be thienyl.
The carbon number is to be connected to molecule remainder as defined above via CO groups for 4 to 20 Heteroarylcarbonyl Carbon number be 3 to 20 heteroaryl.
The aryl being substituted (heteroaryl that the aryl or carbon number that phenyl, naphthyl, carbon number are 6 to 20 are 5 to 20) is point Not through 1 to 7 time, 1 to 6 time or 1 to 4 time, preferably through 1 time, 2 times or 3 times substitution.Defined aryl can not have than virtue Free position on basic ring is many substituents.
In the position 4 of substituent on the benzyl ring preferably on the phenyl ring or in 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6- configurations.
The group through being mixed with least one times be through be mixed with such as 1 to 19 time, 1 to 15 time, 1 to 12 time, 1 to 9 time, 1 to 7 Secondary, 1 to 5 time, 1 to 4 time, 1 to 3 time or 1 time or 2 times (being mixed with the number of carbon number that atomicity depends on intending being mixed with).Through The group replaced at least one times has such as 1 to 7,1 to 5,1 to 4,1 to 3 or 1 or 2 identical or different substitutions Base.
The group replaced through at least one substituent as defined above refers to have at least one identical or different Substituent.Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.
For example, if E1And E2、E2And E3、E3And E4Or E5And R6、E6And E7、E7And E8It is separatelyThe structure for example shown in following formula (IIIa) to formula (IIIi) is then formed, wherein with formula (IIIa) Structure is preferable.
Structure wherein using formula (IIIa) is preferable.
The compound of the formula (III) is characterised by that at least one benzyl ring is condensed with carbazole moiety, to form " naphthyl " Ring.That is, one into formula (IIIi) structure of above-mentioned formula (IIIa) is according to represented by formula (III).
If E1And E2、E2And E3、E3And E4Or E5And R6、E6And E7、E7And E8It is separately-(CH2)p-W-(CH2)q-, Then formed for example Etc. structure.
If the substituent OE on phenyl or naphthyl ring17、SE18、SOE18、SO2E18Or NE19E20Via group E17、E18、E19 And/or E20With a carbon atom of naphthyl ring formation five yuan or hexatomic ring, then obtain comprising 3 or more rings (including naphthyl Ring) structure.Specific example may be, for example,
Deng.
If E17With withOne of phenyl or naphthyl ring of group Carbon atom formation singly-bound, then form for example Etc. structure.
If E16It is through SE18Substituted phenyl, wherein E18Represent bond to COE16Carbazole moiety phenyl or naphthyl The singly-bound of ring, the structure formed may be, for example, That is, if E16It is through SE18Substitution Phenyl, wherein group E18Represent bond to COE16Carbazole moiety phenyl or naphthyl ring singly-bound, and formed simultaneously tool There is a phenyl or naphthyl ring of thioxanthene base section and carbazole moiety.
If E19And E20It is to be formed to have O, S or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or six First saturation or unsaturation ring, the then saturation or unsaturation ring formed may be, for example, aziridine, pyrroles, thiazole, Pyrrolizidine, evil Azoles, pyridine, 1,3- diazines, 1,2- diazines, hexahydropyridine or morpholine.If it is preferred that E19And E20It is the nitrogen-atoms one with being bonded Rise to be formed and have O, S or NE without being mixed with or being mixed with17Five yuan or hexa-atomic saturation or unsaturation ring, then formed without being mixed with or being mixed with There is O or NE17, especially the five of O yuan or hexa-atomic saturated rings.
If E21And E22It is to be formed to have O, S or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded26Five yuan or six First saturation or unsaturation ring, and phenyl ring is optionally with the saturation or unsaturation ring fusion, then the saturation or unsaturation formed Ring can be aziridine, pyrroles, thiazole, Pyrrolizidine, oxazole, pyridine, 1,3- diazines, 1,2- diazines, hexahydropyridine or morpholine or phase Answer cyclization (for example)。
If E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms being bonded, then heteroaromatic ring system is Refer to comprising more than one ring (such as 2 or 3 rings) and from identical type or it is different types of one or more Hetero atom.Suitable hetero atom may be, for example, N, S, O or P, especially N, S or O.Specific example such as carbazole, indoles, iso-indoles, Yin Azoles, purine, isoquinolin, quinoline, carboline, phenthazine etc..
Described " and/or " or " and/or " it is to represent that defined substituent not only may be present in the context of the present invention In one, and may be present it is altogether some defined in substituents, i.e., the mixture of different substitutes (substituent).
Described " at least " is to define one or more, such as one or two or three, preferably one or two.
In entire disclosure and claims below, unless the context otherwise requires, otherwise word " is included " or variant (for example, " comprises " or " comprising ") is interpreted as inferring including the integer or step (comprise) Rapid or integer group or step group, but it is not precluded from other any integers or step or integer group or step group.It is described " (methyl) acrylate " refer to acrylate and corresponding methacrylate in the context of the present invention.
Preferably is intended to refer to all authority requirement class shown in word in the context of the invention for the compounds of this invention Not, the claim for composition, purposes, method, colored filter etc. is also referred to.
Oxime ester shown in the formula (III) is prepared by well known method, such as corresponding by making under the following conditions Oxime and carboxylic acid halides, particularly chloride or anhydride reaction：In atent solvent (for example：Tributyl-methyl phosphonium ether, tetrahydrofuran (THF) Or dimethylformamide) in, in the presence of alkali (such as triethylamine or pyridine), or in basic solvent (such as pyridine).At this Invention an embodiment in, as the compound of formula (IIIa) be with following formula (i) shown in method prepare, wherein E7It is oxime ester base Group () and Z1It is singly-bound.And the compound as shown in formula (IIIb) to formula (IIIh) is in the same way Prepare, but select suitable oxime to carry out.
In formula (i), E1、E2、E5、E6、E8、E13、E14And E15It is that as defined above, X refers to halogen atom, in particular chlorine Atom.
It is preferred that E14For methyl.
The above-mentioned reaction as shown in formula (i) is to know in those skilled in the art of the present technique, and generally at -15 DEG C to+50 DEG C At a temperature of implement, preferably implement at a temperature of 0 DEG C to 25 DEG C.
Work as Z1When being CO, corresponding oxime be by using alkyl nitrite (for example methyl nitrite, nitrous ether (ethyl nitrite), Propyl nitrite, butyl nitrite or isoamyl nitrite) methylene nitrosation is synthesized.Then, esterification be with it is foregoing Implement under the same conditions, shown in detailed preparation method such as formula (ii).
Therefore, can by make in the presence of the mixture of alkali or alkali corresponding oxime compound with such asCarboxylic acid halides or such asAnhydride reaction, be made formula (III) as defined above compound, wherein X be halogen atom, and Particularly chlorine atom, and E14Definition know as foregoing.
The required oxime as parent material can pass through standard chemical teaching material (such as J.March, Advanced Organic Chemistry, the 4th edition, Wiley Interscience, 1992) or monograph (such as S.R.Sandler＆W.Karo, Organic Functional group preparations, volume 3, Academic Press) described in a variety of methods obtain.
A kind of most convenient method is (for example) in polar solvent (such as dimethylacetylamide (DMA), the DMA aqueous solution, second Alcohol or ethanol water) in make aldehydes or ketones and azanol or its reactant salt.In this case, the alkali such as sodium acetate or pyridine is added To control the pH of reactant mixture.It is well known that reaction speed has pH dependences, and it can connect when starting or during reaction Alkali is added continuously.Also the basic solvents such as pyridine can be used to be used as alkali and/or solvent or cosolvent.Reaction temperature is usually room The warm reflux temperature to mixture, typically about 20 DEG C to 120 DEG C.
Corresponding ketone intermediate is (for example) by document (such as standard chemical teaching material, such as J.March, Advanced Organic Chemistry, the 4th edition, Wiley Interscience, 1992) described in method prepare.In addition, continuously not Reed-Kerafyrm thatch reaction (Friedel-Crafts reaction) can be effectively used for synthetic intermediate.These reactions are by ability Known to field technique personnel.
Another convenient synthesis of oxime is to use nitrous acid or alkyl nitrite by " activity " methylene nitrosation.Alkalescence condition (such as (e.g.) the VI volumes of Organic Syntheses coll. (J.Wiley＆Sons, New York, 1988), page 199 and Described in page 840) with acid condition (such as (e.g.) the V volumes, page 32 and the 373rd of Organic Synthesis coll. Page, I volumes of coll. iis, page 191 and page 513, coll. vol. iis, described in page 202, page 204 and page 363) It is both adapted to prepare the oxime for being used as parent material in the present invention.It is general to produce nitrous acid from natrium nitrosum.Alkyl nitrite Can be (for example) methyl nitrite, nitrous ether (ethyl nitrite), propyl nitrite, butyl nitrite or isoamyl nitrite.
In another embodiment, light initiator (E-1) is free type oxime compound, and with as shown in following formula (IIIA) Structure：
In formula (IIIA), E1、E2、E3、E4、E5、E6、E7And E8It is 1 to 20 alkane independently to represent hydrogen atom, carbon number Base,COE16、OE17, halogen atom, NO2OrOr
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Independently represent warp Substituted carbon number is 2 to 10 alkenyl, or E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Separately altogether With representative-(CH2)p-W-(CH2)q-；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is separately common to representThe E of wherein at least one1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
E9、E10、E11And E12It is 1 to 20 alkyl independently to represent hydrogen atom, carbon number, and carbon number is for 1 to 20 alkyl Be unsubstituted or through at least one substituent group as follows, and at least one group be selected from phenyl, halogen atom, CN, OH, SH, carbon number are 1 to 4 alkoxy, (CO) OH or (CO) O (R1), wherein R1It is 1 to 4 alkyl to represent carbon number；Or
E9、E10、E11And E12Separately represent the phenyl being unsubstituted or taken through at least one group as follows The phenyl in generation, alkyl, halogen atom, CN, OE that it is 1 to 6 selected from carbon number that at least one group, which is,17、SE18Or NE19E20；Or
E9、E10、E11And E12Separately represent halogen atom, CN, OE17、SE18、SOE18、SO2E18Or NE19E20, its Middle substituent OE17、SE18Or NE19E20It is optionally via group E17、E18、E19And/or E20With the naphthalene nucleus in formula (IIIA) Carbon atom formation five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Separately representCOE16Or NO2；
W represents O, S, NE26Or singly-bound, p represents 0 to 3 integer, and q represents 1 to 3 integer, Z1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, wherein at least one above-mentioned group is to be selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2OrOr
E13It is 2 to 20 alkyl to represent carbon number, carbon number for 2 to 20 alkyl be mixed with have one or more O, S, SO, SO2、NE26Or CO；Or
E13It is 2 to 12 alkenyl to represent carbon number, and carbon number is to have one or more without being mixed with or being mixed with for 2 to 12 alkenyl O, CO or NE26, wherein the alkenyl through being mixed with and alkyl that carbon number is 2 to 20 and carbon number without being mixed with or through being mixed with are 2 to 12 It is to be unsubstituted or replace through at least one halogen atom；Or
E13Represent carbon number as 4 to 8 cycloalkenyl group, carbon number as 2 to 12 alkynyl or without being mixed with or being mixed with have one or many Individual O, S, CO or NE26Carbon number be 3 to 10 cycloalkyl；Or
E13Phenyl or naphthyl is represented, and it is respectively unsubstituted or through at least one substituent group as follows, wherein should At least one group is to be selected from OE17、SE18、NE19E20、COE16、CN、NO2, halogen atom, carbon number be 1 to 20 alkyl, the haloalkyl that carbon number is 1 to 4, being mixed with has one or more O, S, CO or NE26And carbon number is 2 to 20 alkyl； Or it respectively has one or more O, S, CO or NE through not being mixed with or being mixed with26And carbon number is replaced by 3 to 10 cycloalkyl；
K represents 1 to 10 integer；
E15It is 3 to 20 heteroaryl that carbon number, which is represented, as 6 to 20 aromatic radical or carbon number, and it is respectively unsubstituted or through following institute At least one substituent group shown, and at least one group be selected from phenyl, halogen atom, carbon number for 1 to 4 haloalkyl, CN、NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2And SO is bonded and carbon number is 1 to 10 alkyl and SO2Bond and carbon number For 1 to 10 alkyl, it is mixed with and has one or more O, S or NE26And carbon number is 2 to 20 alkyl；Or it is respectively 1 to 20 through carbon number Alkyl substitution, wherein carbon number for 1 to 20 alkyl is unsubstituted or through at least one substituent group as follows, and extremely A few group is to be selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 Heteroaryloxycarbonyl that aryloxycarbonyl that heteroaryl, carbon number are 6 to 20, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E15Represent hydrogen atom, carbon number as 2 to 12 alkenyl, without being mixed with or being mixed with have one or more O, CO or NE26And Carbon number is 3 to 8 cycloalkyl；Or
E15It is 1 to 20 alkyl to represent carbon number, carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one group is to be selected from halogen atom, OE17、SE18, carbon number be 3 to 8 cycloalkyl, carbon number be 3 Heteroaryloxycarbonyl that aryloxycarbonyl that heteroaryl, carbon number to 20 are 6 to 20, carbon number are 3 to 20, NE19E20、COOE17、 CONE19E20、PO(OCkH2k+1)2、 Or phenyl, wherein carbon number is that 1 to 20 alkyl is Replace through phenyl, and alkyl that it is 1 to 20 through halogen atom, carbon number that phenyl, which is, carbon number be 1 to 4 haloalkyl, OE17、SE18 Or NE19E20Substitution；Or
E15It is 2 to 20 alkyl to represent carbon number, and carbon number is to be mixed with to have one or more O, SO or SO for 2 to 20 alkyl2, Alkyl through being mixed with and carbon number is 2 to 20 is unsubstituted or through at least one substituent group as follows, and at least one Group is to be selected from halogen atom, OE17、COOE17、CONE19E20, phenyl or through OE17、SE18Or NE19E20Substituted phenyl；Or
E15It is 2 to 20 alkanoyl or benzoyl to represent carbon number, and it is unsubstituted or through as follows at least one Individual substituent group, and at least one group is selected from the alkyl that carbon number is 1 to 6, halogen atom, phenyl, OE17、SE18Or NE19E20；Or
E15Representative is unsubstituted or through at least one OE17Substituted naphthoyl or the heteroaryl carbonyl that carbon number is 3 to 14 Base；Or
E15It is 2 to 12 alkoxy carbonyl to represent carbon number, and carbon number is without being mixed with or being mixed with for 2 to 12 alkoxy carbonyl There are one or more O, wherein through being mixed with or without the alkoxy carbonyl being mixed with and carbon number is 2 to 12 being unsubstituted or through at least One hydroxyl substitution；Or
E15Phenyloxycarbonyl is represented, phenyloxycarbonyl is unsubstituted or through at least one substituent group as follows, And alkyl that it is 1 to 6 selected from carbon number that at least one group, which is, halogen atom, carbon number be 1 to 4 haloalkyl, phenyl, OE17、 SE18Or NE19E20；Or
E15Represent CN, CONE19E20、NO2, carbon number for 1 to 4 haloalkyl, S (O)r-R2And the phenyl that S (O) r is bonded, Wherein with S (O)rThe phenyl of bond be unsubstituted or through carbon number be 1 to 12 alkyl or SO2-R2Substitution, and R2Represent carbon number For 1 to 6 alkyl；Or
E15Represent and SO2Phenyl, diphenylphosphino or the two (R of O bonds3)-phosphono, wherein with SO2The benzene of O bonds Base is to be unsubstituted or replace through carbon number for 1 to 12 alkyl, and R3It is 1 to 4 alkoxy to represent carbon number；
R represents 1 to 2 integer；
E'15Represent to have and be directed to E15One of those in definition；
Z2Represent O, S, SO or SO2；
Z3Represent O, CO, S or singly-bound；
E16It is 3 to 20 heteroaryl that carbon number, which is represented, as 6 to 20 aryl or carbon number, and it is respectively unsubstituted or through as follows At least one substituent group, and at least one group be selected from phenyl, halogen atom, carbon number for 1 to 4 haloalkyl, CN, NO2、OE17、SE18、NE19E20, be mixed with and have one or more O, S or NE26And carbon number be 1 to 20 alkyl, or carbon number be 1 to 20 alkyl, wherein carbon number for 1 to 20 alkyl are unsubstituted or through at least one substituent group as follows, wherein extremely A few group is to be selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 Heteroaryloxycarbonyl that aryloxycarbonyl that heteroaryl, carbon number are 6 to 20, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E16It is 1 to 20 alkyl to represent hydrogen atom or carbon number, and wherein carbon number for 1 to 20 alkyl is unsubstituted or through such as At least one lower shown substituent group, and at least one group be selected from halogen atom, phenyl, OH, SH, CN, carbon number be 3 to 6 alkenyloxy group, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1), O (CO) phenyl or (CO) OH or (CO) O (R1)；Or
E16It is 2 to 12 alkyl to represent carbon number, and carbon number is to be mixed with to have one or more O, S or NE26 for 2 to 12 alkyl； Or
E16Represent (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 12 alkenyl or carbon number be 3 to 8 Cycloalkyl, the wherein R4It is 1 to 8 alkyl to represent carbon number；Or
E16Represent through SE18Substituted phenyl, wherein E18Bond is represented to COE16The phenyl or naphthalene of the carbazole moiety connected The singly-bound of basic ring；
N represents 1 to 20 integer；
E17Represent hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, its be unsubstituted or through it is as follows at least One substituent group, and at least one group be selected from halogen atom, OH, SH, CN, carbon number for 3 to 6 alkenyloxy group, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6), with O (CO) be bonded phenyl, (CO) OH, (CO) O (R1), carbon number for 3 to 20 cycloalkyl, SO2-(R7)、O(R7) or be mixed with the cycloalkanes for thering is one or more O and carbon number to be 3 to 20 Base, wherein R5Represent alkyl of the carbon number as 1 to 3, R6It is 2 to 4 alkenyl to represent carbon number, and R7It is 1 to 4 halo to represent carbon number Alkyl；Or
E17It is 2 to 20 alkyl to represent carbon number, and carbon number for 2 to 20 alkyl be mixed with have one or more O, S or NE26；Or
E17Represent (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 1 to 8 alkanoyl, carbon number be 2 to 12 The cycloalkyl that the enoyl- or carbon number that alkenyl, carbon number are 3 to 6 are 3 to 20, its be without be mixed with or be mixed with have one or more O, S, CO or NE26；Or
E17It is 3 to 10 group that is formed of cycloalkyl bond, and above-mentioned base that carbon number, which is represented, by 1 to 8 alkyl and carbon number Group is without being mixed with or having one or more O through being mixed with；Or
E17Benzoyl is represented, benzoyl is unsubstituted or through at least one substituent group as follows, and this is extremely The alkoxy that alkyl, halogen atom, OH or the carbon number that it is 1 to 6 selected from carbon number that a few group, which is, are 1 to 3；Or
E17It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is respectively unsubstituted or through as follows at least one Individual substituent group, and the alkane that alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that at least one group, which is, carbon number are 1 to 12 Epoxide, CN, NO2, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amido orWherein R8It is 1 to 3 alkoxy to represent carbon number, and R9It is 1 to 12 alkyl to represent carbon number；Or
E17With withOne of carbon atom of phenyl or naphthyl ring form list Key；
E18It is 2 to 12 cycloalkyl or phenyl-R as 3 to 20 of alkenyl, carbon number to represent hydrogen atom, carbon number5, wherein carbon number The cycloalkyl for being 3 to 20 for 2 to 12 alkenyl, carbon number and phenyl-R5Be without be mixed with or be mixed with have one or more O, S, CO, NE26Or COOE17；Or
E18It is 1 to 20 alkyl to represent carbon number, and carbon number is unsubstituted or through as follows at least one for 1 to 20 alkyl Individual substituent group, and at least one group is selected from OH, SH, CN, the alkenyloxy group that carbon number is 3 to 6, OCH2CH2CN、OCH2CH2 (CO)O(R1)、O(CO)-(R6)、O(CO)-(R1), O (CO)-phenyl or (CO) OE17；Or
E18It is 2 to 20 alkyl to represent carbon number, carbon number for 2 to 20 alkyl be mixed with have one or more O, S, CO, NE26Or COOE17；Or
E18Represent (CH2CH2O)nH、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 8 alkanoyl or carbon number be 3 to 6 Enoyl-；Or
E18Benzoyl is represented, benzoyl is unsubstituted or through at least one substituent group as follows, and extremely It is 1 to 4 to lack a group to be alkoxy or carbon number that the alkyl for being 1 to 6 selected from carbon number, halogen atom, OH, carbon number are 1 to 4 Alkyl sulfenyl；Or
E18It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and its is each unsubstituted or through at least one as follows Substituent group, and alkyl that it is 1 to 12 selected from halogen atom, carbon number that at least one group, which is, carbon number be 1 to 4 haloalkyl, Alkoxy, CN, NO that carbon number is 1 to 122, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl amido, (CO) O (R4)、CO-R4、(CO)N(R4)2Or
E19And E20Separately represent hydroxy alkyl as 2 to 4 of alkyl, carbon number as 1 to 20 of hydrogen atom, carbon number, carbon Cycloalkyl that alkenyl that alkoxyalkyl that number is 2 to 10, carbon number are 2 to 5, carbon number are 3 to 20, phenyl-R5, carbon number be 1 to 8 Alkanoyl, carbon number be 1 to 8 alkanoyl epoxide, carbon number be 3 to 12 enoyl-, SO2-R7Or benzoyl；Or
E19And E20It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is respectively unsubstituted or through as follows At least one substituent group, and haloalkyl that it is 1 to 4 selected from halogen atom, carbon number that at least one group, which is, carbon number are 1 The alkoxy that alkyl, benzoyl or the carbon number that alkoxy, carbon number to 20 are 1 to 12 are 1 to 12；Or
E19And E20It is to be formed to have O, S or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or hexa-atomic Saturation or unsaturation ring, and five yuan or hexa-atomic saturation or unsaturation ring are unsubstituted or through at least one group as follows Substitution, alkoxy that alkyl that it is 1 to 20 selected from carbon number that wherein at least one group, which is, carbon number are 1 to 20 ,=O, OE17、 SE18、NE21E22、(CO)E23、NO2, halogen atom, carbon number for 1 to 4 haloalkyl, CN, phenyl,Or Without being mixed with or through at least one O, S, CO or NE17Be mixed with and carbon number be 3 to 20 cycloalkyl；Or
E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms connected, the heteroaromatic ring system is not Be substituted or through at least one substituent group as follows, and at least one group be selected from carbon number for 1 to 20 alkyl, Alkoxy that haloalkyl that carbon number is 1 to 4, carbon number are 1 to 20 ,=O, OE17、SE18、NE21E22、(CO)E23、Halogen atom, NO2, CN, phenyl, or have one or more O, S, CO or NE without being mixed with or being mixed with17And Carbon number is 3 to 20 cycloalkyl；
E21And E22Separately represent haloalkyl as 1 to 4 of alkyl, carbon number as 1 to 20 of hydrogen atom, carbon number, carbon Cycloalkyl or phenyl of the number for 3 to 10；
E21And E22Formed together with its bonded nitrogen-atoms has O, S or NE without being mixed with or being mixed with26Five yuan or hexa-atomic Saturation or unsaturation ring, wherein this five yuan or hexa-atomic saturation or unsaturation ring are uncondensed or condensed with phenyl ring；
E23Represent hydrogen atom, OH, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have at least one O, CO or NE26And carbon number for 2 to 20 alkyl, without being mixed with or being mixed with have O, S, CO or NE26And carbon number is 3 to 20 cycloalkanes Base；Or
E23Represent phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represent (CO) OE17、CONE19E20、(CO)E17Or with for E19And E20One of those in definition；
E25Represent COOE17、CONE19E20、(CO)E17；Or with for E17One of those in definition；
E26Represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with have at least one O or The alkyl that CO and carbon number are 2 to 20；Or E26Represent phenyl-R1, without being mixed with or being mixed with have one or more O or CO and carbon number is 3 to 8 cycloalkyl；Or E26Represent (CO) E19；Or E26Represent phenyl, E26It is to be unsubstituted or through at least one as follows Substituent group, and the alkyl halide that alkyl that it is 1 to 20 selected from carbon number that at least one group, which is, halogen atom, carbon number are 1 to 4 Base, OE17、SE18、NE19E20OrBut condition is light initiator (E-1) tool of the structure as shown in formula (IIIA) There is at least one
For group defined in the compound shown in formula (IIIA), preferably correspond to be directed to formula (III) as following Compound institute definien, simply defined in oxime ester base group (for example) all replace with corresponding dissociate Oximido group
Each oxime ester base group can two kinds of configurations (Z) or (E) exist.Isomers can be separated by traditional methods, but also Isomer mixture can be used to be used as (such as) light initial substance.Therefore, light initiator (E-1) of the invention, such as formula (III) institute The compound shown, the mixture comprising configurational isomer.
In a preferred embodiment, light initiator (C) includes the light initiator (E-1) of the structure as shown in formula (III), Wherein E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom, carbon number as 1 to 20 alkyl,COE16Or NO2；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is separately common to representThe E of wherein at least one1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
Z1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one group is to be selected from halogen atom, OE17、SE18、COOE17、CONE19E20Or PO (OCkH2k+1)2；Or
It is 2 to 20 alkyl that E13, which represents carbon number, and it is to be mixed with to have one or more O, S, NE26Or CO；Or
E13Phenyl or naphthyl is represented, both this is unsubstituted or through at least oneOr COE16 Substitution；
E14Represent carbon number as 1 to 20 alkyl, phenyl or carbon number as 1 to 8 alkoxy；
E15It is 3 to 20 heteroaryl to represent phenyl, naphthyl, carbon number, and it is respectively unsubstituted or through as follows at least one Individual substituent group, and at least one group is selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, OE17、SE18、 It is mixed with the alkyl for having that at least one O or S and carbon number are 2 to 20, or it respectively takes through one or more carbon numbers for 1 to 20 alkyl Generation, the carbon number for 1 to 20 alkyl is unsubstituted or through at least one substituent group as follows, and at least one base Group is to be selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl, Heteroaryloxycarbonyl that aryloxycarbonyl that carbon number is 6 to 20, carbon number are 4 to 20, OE17、SE18、NE19E20Or PO (OCkH2k+1)2；Or
E15It is 1 to 20 alkyl to represent carbon number, and it is unsubstituted or through at least one substituent group as follows, and At least one group is to be selected from OE17、SE18, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl, NE19E20、 COOE17、CONE19E20Or PO (OCkH2k+1)2；
E'14Represent to have and be directed to E14One of those in definition；
E'15Represent to have and be directed to E15One of those in definition；
E16Phenyl is represented, it is unsubstituted or through at least one substituent group as follows, and at least one group It is to be selected from OE17、SE18、NE19E20, be mixed with least one O, S or NE26And carbon number is 2 to 20 alkyl；Or
E16Phenyl is represented, it is to replace through at least one carbon number for 1 to 20 alkyl, and wherein carbon number is 1 to 20 alkyl It is to be unsubstituted or through at least one substituent group as follows, and at least one group is to be selected from halogen atom, COOE17、 CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl, carbon number be 6 to 20 aryloxycarbonyl, Heteroaryloxycarbonyl, OE that carbon number is 4 to 2017、SE18Or NE19E20；Or
E16It is 1 to 20 alkyl, E to represent carbon number16It is to be unsubstituted or through at least one substituent group as follows, And at least one group is selected from halogen atom, phenyl, OH, SH, CN, the alkenyloxy group that carbon number is 3 to 6, OCH2CH2(CO)O (R1)、O(CO)-(R1) or (CO) O (R1)；
E17It is 1 to 20 alkyl to represent carbon number, and it is unsubstituted or through at least one substituent group as follows, and At least one group is to be selected from halogen atom, OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1), carbon number be 3 to 20 cycloalkanes Base, wherein carbon number are not to be mixed with or be mixed with least one O for 3 to 20 cycloalkyl；Or
E17It is 2 to 20 alkyl to represent carbon number, and carbon number is to be mixed with least one O for 2 to 20 alkyl；
E18Represent and pass through (CO) OE17Substituted methyl；
E19And E20Independently represent hydrogen atom, phenyl, carbon number as 1 to 20 alkyl, carbon number as 1 to 8 alkanoyl or Carbon number is 1 to 8 alkanoyl epoxide；Or
E19And E20That heteroaromatic ring system is formed together with the nitrogen-atoms being bonded, heteroaromatic ring system be without Substitution is passed throughSubstitution, but condition is the light initiator (E-1) tool of the structure as shown in formula (III) There is at least one
Formula as defined above (III) compound, wherein E must be paid attention to1、E2、E3、E4、E5、E6、E7And E8It is only respectively It is vertical represent hydrogen atom,COE16Or NO2；
E3And E4It is together
E9、E10、E11And E12For hydrogen atom；
Z1For singly-bound；
E13It is the alkyl that carbon number is 1 to 20；
E14It is the alkyl that carbon number is 1 to 20；
E15It is alkyl or phenyl through at least one following substituent group that carbon number is 1 to 20, wherein at least one base Group can be OE17Or the alkyl that carbon number is 1 to 20；
E16It is phenyl, phenyl is that, through at least one following substituent group, wherein at least one group can be OE17Or carbon Number is 1 to 20 alkyl；
E17It is that the carbon number for being unsubstituted or replacing through at least one halogen atom is 1 or 20 alkyl or is mixed with and has at least one The carbon number of individual oxygen atom is 1 to 20 alkyl, but condition is has at least one in the compound of structural formula as shown in formula (III) It is individual
In one more preferably embodiment, light initiator (C) includes the light initiator (E-1) of the structure as shown in formula (III), Wherein E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom；Or
E1And E2、E3And E4Or E5And E6It is separately common to representAnd an at least E1And E2、E3And E4Or E5And E6ForOr
E2RepresentCOE16、NO2OrOr
E7RepresentOr COE16；
E9、E11And E12Represent hydrogen atom；
E10Represent hydrogen atom, OE17Or COE16；
Z1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, and it is unsubstituted or through at least one substituent group as follows, and At least one group is to be selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2；Or
E13It is 2 to 20 alkyl to represent carbon number, and it is to be mixed with least one O；Or
E13Represent phenyl；
K represents integer 2；
E14It is 1 to 20 alkyl or thienyl to represent carbon number；
E15Phenyl or naphthyl is represented, and it is respectively unsubstituted or through at least one OE17Or carbon number takes for 1 to 20 alkyl Generation；Or
E15It is 1 to 20 alkyl to represent thienyl, hydrogen atom or carbon number, and wherein carbon number is without taking for 1 to 20 alkyl Generation or through at least one substituent group as follows, and at least one group is to be selected from OE17、SE18, carbon number be 3 to 8 ring Alkyl, NE19E20Or COOE17；Or
E15It is 2 to 20 alkyl to represent carbon number, and carbon number is mixed with for 2 to 20 alkyl and has SO2；
E16Phenyl or naphthyl is represented, it is respectively unsubstituted or through at least one substituent group as follows, and at least one Individual group is to be selected from OE17、SE18、NE19E20Or the alkyl that carbon number is 1 to 20；Or
E16Represent thienyl；
E17It is 1 to 20 alkyl that hydrogen atom, carbon number, which are represented, as 1 to 8 alkanoyl or carbon number, and carbon number is 1 to 20 alkyl It is to be unsubstituted or through at least one substituent group as follows, and at least one group is to be selected from halogen atom, O (CO)-(R1)、O(CO)-(R6), or it is mixed with the cycloalkyl that at least one O and carbon number are 3 to 20；Or
E17It is 2 to 20 alkyl to represent carbon number, and carbon number is mixed with least one O for 2 to 20 alkyl；
E18Represent carbon number as 3 to 20 cycloalkyl, carbon number be 1 to 20 alkyl, it is unsubstituted or through at least one OH、O(CO)-(R6) or (CO) OE17Substitution；Or
E18Phenyl is represented, it is to be unsubstituted or replace through at least one halogen atom；
E19And E20It is that separately to represent carbon number as 1 to 8 alkanoyl or carbon number be 1 to 8 alkanoyl epoxide；Or
E19And E20It is to be formed to be mixed with have O five yuan or hexa-atomic saturated rings together with the nitrogen-atoms being bonded, but condition is such as The light initiator (E-1) of structure shown in formula (III) has at least one
The chemical combination for the formula (IIIa) to (IIIg) that the specific example of the light initiator (E-1) of the present invention is as defined above Thing, especially formula (IIIa), formula (IIIb), formula (IIIc), formula (IIIa) or formula (IIIc) or formula (IIIa), formula (IIIc) or formula (IIId), the compound of especially formula (IIIa) attracts people's attention.
In an example, E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom, Or COE16, or E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is separately common to represent
In an example, E1And E2Or E3And E4It is jointlyOr E3And E4、E5And E6Jointly ForE3And E4Especially it is jointly
In an example, E1、E5、E6And E8Represent hydrogen atom.It is preferred that E7Represent hydrogen atom, Or COE16, or E7RepresentOr COE16, so with E7RepresentFor more preferably.It is preferred that E2RepresentCOE16OrOr E2And E1It is jointly So with E2Represent COE16For more preferably.Z1Preferably singly-bound.
In an example, E9、E10、E11And E12Separately represent hydrogen atom, carbon number as 1 to 20 alkyl, without taking The phenyl in generation or the phenyl through at least one substituent group as follows, and at least one group is 1 to 6 selected from carbon number Alkyl, halogen atom, OE17Or SE18；Or
E9、E10、E11And E12Separately represent halogen atom, OE17、SE18Or NE19E20, wherein substituent OE17、 SE18Or NE19E20It is optionally via group E17、E18、E19And/or E20With a carbon atom shape of the naphthalene nucleus in formula (III) Into five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Separately representOr COE16。
In a specific example, E9、E10、E11And E12Separately represent hydrogen atom, carbon number as 1 to 20 alkyl, The phenyl being unsubstituted or the phenyl through at least one substituent group as follows, and at least one group is to be selected from carbon number 1 to 6 alkyl, halogen atom, OE17Or SE18；Or
E9、E10、E11And E12Separately represent halogen atom, OE17、SE18Or NE19E20；Or
E9、E10、E11And E12Separately representOr COE16。
In an example, E9、E10、E11And E12Separately represent hydrogen atom, carbon number as 1 to 20 alkyl, without taking The phenyl in generation or through one or more carbon numbers be 1 to 6 alkyl-substituted phenyl；Or E9、E10、E11And E12Separately generation TableOr COE16。
In another example, E9、E10、E11And E12Independently represent hydrogen atom, carbon number as 1 to 20 alkyl, without taking The phenyl in generation or the phenyl through at least one substituent group as follows, and at least one group is 1 to 6 selected from carbon number Alkyl, halogen atom, OE17Or SE18；Or
E9、E10、E11And E12Independently represent halogen atom, OE17、SE18Or NE19E20, wherein substituent OE17、SE18 Or NE19E20It is optionally via group E17、E18、E19And/or E20With the carbon atom formation five of the naphthalene nucleus in formula (III) Yuan of rings or hexatomic ring.
In addition, in an example, E9、E10、E11And E12It is 1 to 20 alkyl, not independently to represent hydrogen atom, carbon number The phenyl being substituted or the phenyl through at least one substituent group as follows, at least one group be selected from carbon number be 1 to 6 Alkyl, halogen atom, OE17Or SE18；Or E9、E10、E11And E12Independently represent halogen atom, OE17、SE18、NE19E20 Or COE16。
Or, in an example, E9、E10、E11And E12It is 1 to 20 alkyl, not independently to represent hydrogen atom, carbon number The phenyl being substituted or the phenyl through at least one substituent group as follows, at least one group be selected from carbon number be 1 to 6 Alkyl, halogen atom, OE17Or SE18；Or E9、E10、E11And E12Independently represent halogen atom, OE17、COE16Or NE19E20。
It is preferred that E9、E11And E12It is hydrogen atom, and E10For hydrogen atom, OE17Or COE16。
E13It is that for example to represent carbon number be 1 to 20 alkyl, it is unsubstituted or through at least one group as follows Substitution, wherein at least one above-mentioned group is to be selected from halogen atom, COOE17Or CONE19E20；Or
E13It is 2 to 20 alkyl to represent carbon number, carbon number for 2 to 20 alkyl be mixed with have one or more O, S, SO, SO2、NE26Or CO；
E13It is 2 to 12 alkenyl to represent carbon number, carbon number for 2 to 12 alkenyl be not mixed with or be mixed with have one or more O, CO or NE26；Or
E13It is 3 to 10 cycloalkyl to represent carbon number, cycloalkyl be not mixed with or be mixed with have one or more O, S, CO or NE26；Or
E13Phenyl or naphthyl is represented, and it is respectively to be unsubstituted or through at least one substituent group as follows, wherein At least one group is to be selected from OE17、SE18、NE19E20、COE16、NO2, halogen atom, carbon number be 1 to 20 alkyl, carbon number are 1 to 4 haloalkyl, are mixed with through at least one O and alkyl that carbon number is 2 to 20；Or represent carbon Number is 1 to 20 alkyl, and it is unsubstituted or through at least one substituent group as follows, wherein at least one above-mentioned Group is to be selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20Or PO (OCkH2k+1)2；Or it is 2 to 20 to represent carbon number Alkyl, it is to be mixed with to have one or more O.
In addition, E13It is 1 to 20 alkyl to represent carbon number, and it is to be unsubstituted or taken through at least one group as follows Generation, wherein at least one above-mentioned group is to be selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20Or PO (OCkH2k+1)2；Or it is 2 to 20 alkyl to represent carbon number, carbon number is to be mixed with to have an O for 2 to 20 alkyl；Or represent carbon number as 2 to 12 alkenyl, the cycloalkyl that carbon number is 3 to 10；Or E13Represent phenyl or naphthyl, and it is respectively to be unsubstituted or through following institute At least one substituent group shown, wherein at least one group is to be selected from OE17、SE18、NE19E20、COE16、NO2, halogen atom, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 haloalkyl, The alkyl that the carbon number that being mixed with has one or more O is 2 to 20.
In another embodiment, E13It is 1 to 20 alkyl to represent carbon number, its be unsubstituted or through it is as follows at least One substituent group, wherein at least one above-mentioned group is to be selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2； Or represent be mixed with have one or more O and carbon number as 2 to 20 alkyl；Or represent carbon number as 2 to 12 alkenyl, carbon number as 3 to 10 cycloalkyl, phenyl or naphthyl.
Or, E13It is 1 to 20 alkyl that carbon number, which can for example be represented, and it is unsubstituted or through at least one as follows Substituent group, wherein at least one above-mentioned group is to be selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2；Or represent The alkyl that at least one O is mixed with and carbon number is 2 to 20；Or it is 3 to 10 to represent phenyl, carbon number as 2 to 12 alkenyl or carbon number Cycloalkyl.
Or, E13It as 2 to 12 alkenyl or carbon number is 3 to 10 that carbon number, which can be represented, as 1 to 20 alkyl, phenyl, carbon number Cycloalkyl.Or E13Be carbon number be 1 to 20 alkyl, carbon number be 2 to 12 alkenyl or carbon number be 3 to 10 cycloalkyl.It is preferred that E13It is the alkyl that 1 to 20 alkyl, especially carbon number are 1 to 8, such as 2- ethylhexyls that carbon number, which can be represented,.
E14Can for example represent hydrogen atom, carbon number as 3 to 8 cycloalkyl, carbon number as 2 to 5 alkenyl, carbon number be 1 to 20 Alkoxy or the alkyl that carbon number is 1 to 20, it is to be unsubstituted or replace through at least one halogen atom or phenyl；Or
E14Phenyl or naphthyl is represented, it is unsubstituted or through at least one substituent group as follows, and at least Haloalkyl that alkyl that it is 1 to 6 selected from carbon number that one group, which is, carbon number are 1 to 4, halogen atom, OE17、SE18And/or NE19E20；Or
E14It is 3 to 5 heteroaryl, such as thienyl to represent carbon number, or represent carbon number as 1 to 8 alkoxy, Benzyl epoxides or Phenoxy group.
Or, E14It is 1 to 20 alkyl that carbon number, which can for example be represented, and carbon number is through at least one halogen for 1 to 20 alkyl Plain atom or phenyl substitution；Or
E14Represent carbon number as 3 to 5 heteroaryl (such as thienyl) or represent be unsubstituted or through it is as follows at least The phenyl of one substituent group, and alkyl that it is 1 to 6 selected from carbon number that at least one group, which is, carbon number be 1 to 4 haloalkyl, Halogen atom, OE17、SE18And/or NE19E20；Or
E14It is 1 to 8 alkoxy, Benzyl epoxides or phenoxy group to represent carbon number.
In another embodiment, E14The alkyl of carbon number 1 to 20 is represented, and the alkyl of carbon number 1 to 20 is to be unsubstituted or pass through Phenyl replaces；Or
E14It is phenyl, and phenyl is unsubstituted or replaced through at least one carbon number for 1 to 6 alkyl.
It is preferred that E14Be carbon number be 1 to 20 alkyl, carbon number be 3 to 5 heteroaryl (such as thienyl), or phenyl, In particular carbon number is 1 to 20 alkyl or thienyl, and more preferably carbon number is 1 to 8 alkyl.
E15May be, for example, the heteroaryl that aryl or carbon number that carbon number is 6 to 20 are 5 to 20, it is respectively unsubstituted or through as follows At least one shown substituent group, and at least one group is selected from phenyl, halogen atom, the alkyl halide that carbon number is 1 to 4 Base, CN, NO2、OE17、SE18、NE19E20, carbon number be 1 to 20 alkyl；Or
E15Hydrogen atom, the cycloalkyl that carbon number is 3 to 8, wherein carbon number is without being mixed with or being mixed with for 3 to 8 cycloalkyl There are one or more O, CO or NE26；Or
E15It is the alkyl that carbon number is 1 to 20, carbon number is unsubstituted or through at least one as follows for 1 to 20 alkyl Substituent group, and at least one group is to be selected from halogen atom, OE17, carbon number be 3 to 8 cycloalkyl, carbon number be 5 to 20 Heteroaryloxy-carbonyl that phenyloxycarbonyl that heteroaryl, carbon number are 8 to 20, carbon number are 5 to 20, NE19E20、COOE17、 CONE19E20、PO(OCkH2k+1)2、Phenyl or the phenyl through following substituent group, above-mentioned group is to be selected from Haloalkyl that alkyl that halogen atom, carbon number are 1 to 20, carbon number are 1 to 4, OE17Or NE19E20；Or
E15It is the alkyl that carbon number is 2 to 20, and carbon number is mixed with for 2 to 20 alkyl and has at least one O, S or SO2；Or
E15Be carbon number be 2 to 20 alkanoyl, benzoyl, carbon number be 2 to 12 alkoxy carbonyl, phenyloxycarbonyl, CONE19E20、NO2Or the haloalkyl that carbon number is 1 to 4.
In addition, E15May be, for example, hydrogen atom, the aryl that carbon number is 6 to 20, in particular phenyl or naphthyl, phenyl or naphthyl is Respectively it is unsubstituted or replaces through carbon number for 1 to 12 alkyl；Or the heteroaryl that carbon number is 3 to 5, such as thienyl；Or carbon The alkyl that cycloalkyl that number is 3 to 8, carbon number are 1 to 20, it is to be unsubstituted or taken through at least one group as follows Generation, and at least one group is to be selected from OE17、SE17, carbon number for 3 to 8 cycloalkyl, NE19E20Or COOE17；Or
E15It is the alkyl that carbon number is 2 to 20, and carbon number is mixed with for 2 to 20 alkyl and has at least one O or SO2。
In the compound as shown in formula (III), E15May be, for example, hydrogen atom, phenyl, naphthyl, it is respectively unsubstituted or passed through Carbon number replaces for 1 to 8 alkyl；Or
E15Be thienyl, carbon number be 1 to 20 alkyl, it is unsubstituted or taken through at least one group as follows Generation, and at least one group is to be selected from OE17、SE17, carbon number for 3 to 8 cycloalkyl, NE19E20Or COOE17；Or
E15It is the alkyl that carbon number is 2 to 20, and carbon number is mixed with for 2 to 20 alkyl and has at least one O or SO2。
E15The alkyl that in particular (for example) cycloalkyl or carbon number that carbon number is 3 to 8 are 1 to 20, preferably carbon number are 1 to 20 Alkyl, more preferably carbon number be 1 to 12 alkyl.
E'14And E'15Preferably respectively have as described above for E14And E15One of them in defining.
Z2It is (for example) O, S or SO, such as O or S, in particular O.
E16May be, for example, aryl (especially phenyl or naphthyl, especially phenyl) or carbon number that carbon number is 6 to 20 be 5 to 20 it is miscellaneous Aryl (especially thienyl), it is respectively unsubstituted or through at least one substituent group as follows, and at least one group is Haloalkyl, CN, NO selected from phenyl, halogen atom, carbon number for 1 to 42、OE17、SE18、NE19E20Or it is mixed with least one O Carbon number be 1 to 20 alkyl；Or it is each through the alkyl substitution that at least one carbon number is 1 to 20, the alkyl that carbon number is 1 to 20 is not It is substituted or through at least one substituent group as follows, and at least one group is to be selected from halogen atom, COOE17、 CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 5 to 20 heteroaryl, carbon number be 6 to 20 aryloxycarbonyl, Heteroaryloxycarbonyl, OE that carbon number is 5 to 2017、SE18Or NE19E20；Or
E16Hydrogen atom, the alkyl that carbon number is 1 to 20, and carbon number is unsubstituted or through as follows for 1 to 20 alkyl At least one substituent group, and at least one group be selected from halogen atom, phenyl, OH, SH, carbon number be 3 to 6 alkene oxygen Base, OCH2CH2(CO)O(R1)、O(CO)-(R1), O (CO)-phenyl, (CO) OH or (CO) O (R1)；Or
E16It is the alkyl that carbon number is 2 to 12, and carbon number is mixed with for 2 to 12 alkyl and has at least one O；Or
E16It is (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 12 alkenyl or carbon number be 3 to 8 ring Alkyl, and n is 1 to 20, such as 1 to 12 or 1 to 8, in particular 1 or 2.
In addition, E16May be, for example, phenyl or naphthyl, in particular phenyl, thienyl or carbazole, it is respectively unsubstituted or through such as Lower at least one shown substituent group, and at least one group is selected from phenyl, halogen atom, the halo that carbon number is 1 to 4 Alkyl, OE17、SE18、NE19E20Or the alkyl that carbon number is 1 to 20；Or
E16It is the alkyl that carbon number is 1 to 20, carbon number is unsubstituted or through at least one as follows for 1 to 20 alkyl Substituent group, and at least one group is selected from halogen atom, phenyl, OH, SH, the alkenyloxy group that carbon number is 3 to 6, OCH2CH2 (CO)O(R1)、O(CO)-(R1), O (CO)-phenyl, (CO) OH or (CO) O (R1)；Or
E16It is the alkyl that carbon number is 2 to 12, and carbon number is to be mixed with to have at least one O for 2 to 12 alkyl；Or
E16It is (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 12 alkenyl or carbon number be 3 to 8 ring Alkyl, and n is 1 to 20, such as 1 to 12 or 1 to 8, in particular 1 or 2.
In addition, E16May be, for example, phenyl or naphthyl, in particular phenyl, it is respectively unsubstituted or through as follows at least one Individual substituent group, and at least one group is selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, OE17、SE18、 NE19E20Or the alkyl that carbon number is 1 to 20；Or
E16It is the heteroaryl that carbon number is 3 to 5, in particular thienyl.
E16In particular (for example) phenyl, phenyl is unsubstituted or through at least one substituent group as follows, and at least One group is to be selected from OE17、SE18、NE19E20Or the alkyl that carbon number is 1 to 20, or E16It is thienyl.
It is preferred that E16(for example) phenyl or naphthyl, its be respectively unsubstituted or through at least one carbon number be 1 to 20 alkyl Substitution.
E16In particular phenyl, and phenyl replaces through at least one carbon number for 1 to 20 alkyl.
E17May be, for example, hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, it is unsubstituted or through as follows At least one substituent group, and at least one group is to be selected from halogen atom, OH, OCH2CH2(CO)O(R1)、O(CO)- (R1)、O(CO)-(R6), O (CO)-phenyl, (CO) OH, (CO) O (R1), carbon number for 3 to 20 cycloalkyl or be mixed with and have at least one Individual O carbon number is 3 to 20 cycloalkyl；Or
E17It is the alkyl that carbon number is 2 to 20, and carbon number is mixed with for 2 to 20 alkyl and has at least one O；Or
E17It is (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 1 to 8 alkanoyl, carbon number be 2 to 12 alkene The cycloalkyl that the enoyl- or carbon number that base, carbon number are 3 to 6 are 3 to 20, it is that have at least one O without being mixed with or being mixed with；Or
E17It is benzoyl, and benzoyl is unsubstituted or through at least one substituent group as follows, and extremely The alkoxy substitution that alkyl, halogen atom, OH or the carbon number that it is 1 to 6 selected from carbon number that a few group, which is, are 1 to 3；Or
E17It is the heteroaryl that phenyl, naphthyl or carbon number are 5 to 20, it is respectively unsubstituted or through at least one as follows Substituent group, and the alkane that alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that at least one group, which is, carbon number are 1 to 12 Epoxide, CN, NO2, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amido or
In another embodiment, E17It is (for example) hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, it is without taking Generation or through at least one substituent group as follows, and at least one group is to be selected from halogen atom, O (CO)-(R1)、O (CO)-(R6) or be mixed with have at least one O carbon number be 2 to 20 alkyl；Or
E17Be carbon number be 1 to 8 alkanoyl, carbon number be 2 to 12 alkenyl, carbon number be 3 to 6 enoyl-, be mixed with have to Alkyl that few O carbon number is 2 to 20, without being mixed with or being mixed with the cycloalkyl that the carbon number for having at least one O is 3 to 20；Or
E17It is benzoyl, benzoyl is unsubstituted or through at least one substituent group as follows, and at least The alkoxy that alkyl, halogen atom, OH or the carbon number that it is 1 to 6 selected from carbon number that one group, which is, are 1 to 3；Or
E17It is phenyl or naphthyl, it is respectively unsubstituted or through at least one substituent group as follows, and at least one The alkoxy that the alkyl or carbon number that it is 1 to 12 selected from halogen atom, carbon number that group, which is, are 1 to 12.
E17Also it is (for example) hydrogen atom, phenyl-R5, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 20 alkyl, it is It is unsubstituted or through at least one substituent group as follows, and it selected from halogen atom, carbon number is 3 that at least one group, which is, Cycloalkyl, O (CO) to 20-(R1)、O(CO)-(R6) or be mixed with the alkyl that the carbon number for having at least one O is 2 to 20, or E17It is Carbon number is 2 to 20 alkyl, and it, which is mixed with, at least one O.
E17The alkyl that alkanoyl that in particular hydrogen atom, carbon number are 1 to 8, carbon number are 1 to 20, it is to be unsubstituted or pass through At least one substituent group as follows, and at least one group is to be selected from O (CO)-(R1)、O(CO)-(R6) or be mixed with and have At least one O carbon number is 2 to 20 alkyl, or E17It is the alkyl that carbon number is 2 to 20, it, which is mixed with, at least one O.
E18It is (for example) cycloalkyl that carbon number is 3 to 20, it has at least one O without being mixed with or being mixed with；Or
E18It is the alkyl that carbon number is 1 to 20, it is unsubstituted or through at least one substituent group as follows, and at least One group is to be selected from OH, O (CO)-(R6)、O(CO)-(R1) or (CO) OE17；Or
E18It is the alkyl that carbon number is 2 to 20, it, which is mixed with, at least one O, S, CO, NE26Or COOE17；Or
E18Be alkanoyl or carbon number that carbon number is 2 to 8 be 3 to 6 enoyl-, benzoyl；Or
E18It is the heteroaryl that phenyl, naphthyl or carbon number are 3 to 20, it is respectively unsubstituted or through at least one as follows Substituent group, and at least one group is to be selected from the alkyl halide that halogen atom, the alkyl that carbon number is 1 to 12, carbon number are 1 to 4 Base, carbon number are 1 to 12 alkoxy or NO2。
In another embodiment, E18Be (for example) carbon number be 3 to 20 cycloalkyl, carbon number be 1 to 20 alkyl, it is not It is substituted or through at least one substituent group as follows, and at least one group is to be selected from OH, O (CO)-(R6)、O (CO)-(R1) or (CO) OE17；Or
E18It is phenyl or naphthyl, it is respectively unsubstituted or through the alkyl that at least one halogen atom or carbon number are 1 to 12, especially Its halogen atom replaces.
E18Be (for example) carbon number be 1 to 20 alkyl, carbon number be 2 to 12 alkenyl, carbon number be 3 to 20 cycloalkyl, benzene Base-R5, carbon number for 2 to 8 alkanoyl, benzoyl, phenyl or naphthyl.
For example, E18It is the alkyl that carbon number is 1 to 20, it is through at least one substituent group as follows, and at least One group is to be selected from OH, O (CO)-(R6)、O(CO)-(R1) or (CO) OE17, or E18It is phenyl, it is through at least one halogen Atom replaces.
It is preferred that E18It is the alkyl that carbon number is 1 to 8, it is substituted as hereinbefore defined.
For example, E19And E20Be separately hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 2 to 4 hydroxyl Cycloalkyl, phenyl-R that alkyl, carbon number are 3 to 205, phenyl or naphthyl, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 8 alkane Acyloxy, carbon number are 3 to 12 enoyl- or benzoyl；Or
E19And E20It is to be formed to have O, S or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or hexa-atomic Saturation or unsaturation ring；Or
E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms being bonded, heteroaromatic ring system is without taking Generation or through at least one substituent group as follows, and at least one group is alkyl selected from carbon number for 1 to 20, carbon number Haloalkyl for 1 to 4 or
In addition, for example, E19And E20Be separately hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 2 to 4 Hydroxy alkyl, carbon number for 3 to 20 cycloalkyl, phenyl-R5, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 8 alkanoyl Epoxide, carbon number are 3 to 12 enoyl- or benzoyl；Or
E19And E20It is to be formed to have O or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or hexa-atomic full And ring；Or
E19And E20It is that carbazole ring is formed together with the nitrogen-atoms being bonded.
For example, E19And E20Be separately hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 2 to 4 hydroxyl Cycloalkyl, phenyl-R that alkyl, carbon number are 3 to 205, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 8 alkanoyl epoxide, carbon Number is 3 to 12 enoyl- or benzoyl；Or
E19And E20It is to be formed to have O or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or hexa-atomic full And ring.
It is preferred that E19And E20Be separately carbon number be 1 to 8 alkanoyl, carbon number be 1 to 8 alkanoyl epoxide； Or
E19And E20It is the nitrogen-atoms formation morpholine ring with being bonded.
For example, E21And E22Be separately hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 halo The cycloalkyl or phenyl of alkyl, carbon number for 3 to 10；Or
E21And E22It is the nitrogen-atoms formation morpholine ring with being bonded.E21And E22Especially it is separately hydrogen atom or carbon Number is 1 to 20 alkyl.
E23It is (for example) alkyl that hydrogen atom, OH, phenyl or carbon number are 1 to 20.E23In particular hydrogen atom, OH or carbon number For 1 to 4 alkyl.
E24Be preferably configured to such as E19And E20It is defined one of them.E25Be preferably configured to such as E17Defined One of them.
E26Be (for example) hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 haloalkyl, carbon number be 2 to 20 Alkyl, it, which is mixed with, at least one O or CO；Or
E26It is phenyl-R1, the cycloalkyl that carbon number is 3 to 8, and carbon number is without being mixed with or being mixed with one for 3 to 8 cycloalkyl Individual or multiple O or CO；Or
E26It is (CO) E19Or phenyl, and phenyl is unsubstituted or through at least one following substituent group, at least one base Group can be carbon number be 1 to 20 alkyl, halogen atom, carbon number be 1 to 4 haloalkyl, OE17、SE18、NE19E20。
Or E26Represent the haloalkyl that (for example) alkyl that hydrogen atom, carbon number are 1 to 20, carbon number are 1 to 4；Be phenyl- R1, carbon number for 3 to 8 cycloalkyl, (CO) E19Or phenyl, and phenyl be unsubstituted or through at least one carbon number be 1 to 20 Alkyl replaces.In addition, E26Be (for example) hydrogen or carbon number be 1 to 20 alkyl, the alkyl that in particular carbon number is 1 to 4.
The concrete example of the light initiator (E-1) of the foregoing structure with as shown in formula (III), which can be included, has such as following formula The light initiator of structure shown in (III-1) to formula (III-86).
Usage amount based on alkali soluble resin (C) is 100 parts by weight, and the usage amount of light initiator (E-1) is 0.1 weight Part to 15 parts by weight, preferably 1 parts by weight are to 12 parts by weight, and more preferably 3 parts by weight are to 10 parts by weight.Originated when using the light During agent (E-1), the colored filter that the photosensitive resin composition is formed its hot solvent Thickness Variation rate is more preferably.
Other free radical type light initiators (E-2) can further include according to the light initiator (E) of the present invention.
Other free radical type light initiators (E-2) can be selected from acetophenone compound (acetophenone), diimidazole Compound (biimidazole), acyl oxime compound (acyl oxime) or these combination.
Above-mentioned acetophenone compound is selected to dimethylamine acetophenone (p-dimethylamino- Acetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxy-acetophenone), 2,2 '-dimethyl -2- phenyl acetophenones (2,2 '-dimethyl-2-phenyl-acetophenone), acetanisole (p-methoxy-acetophenone), 2- methyl isophthalic acids-(4- methylthiophenyis) -2- morpholino -1- acetone [2-methyl- 1- (4-methylthio phenyl) -2-morpholino-1-propanone], 2- benzyl -2- nitrogen, nitrogen-dimethylamine -1- (4- Morphlinophenyl) -1- butanone [2-benzyl-2-N, N-di-methylamino-1- (4-morpholinophenyl) -1- butanone]。
Above-mentioned diimidazole compound be selected from 2,2 '-bis- (o- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-chlorophenyl) -4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-bis- (ortho-fluorophenyls Base) -4,4,5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-fluorophenyl) -4,4 ', 5,5 '-tetraphenyl- Biimidazole], 2,2 '-bis- (ortho-methyl phenyl) -4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-methyl Phenyl) -4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-bis- (o- methoxyphenyls) -4,4 ', 5,5 ' - Tetraphenyl diimidazole [2,2 '-bis (o-methoxyphenyl) -4,4 ', 5,5 '-tetraphenyl-biimidazole], 2, 2 '-bis- (o- ethylphenyls) -4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-ethylphenyl) -4,4 ', 5,5 ' - Tetraphenyl-biimidazole], 2,2 '-bis- (p-methoxyphenyls) -4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 ' - Bis (p-methoxyphenyl) -4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-bis- (2,2 ', 4,4 '-four Methoxyphenyl) -4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,2 ', 4,4 '-tetramethoxyphenyl) -4, 4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl diimidazole [2, 2 '-bis (2-chlorophenyl) -4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-bis- (2,4 dichloro benzenes Base) -4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,4-dichlorophenyl) -4,4 ', 5,5 ' - tetraphenyl-biimidazole]。
Above-mentioned acyl oxime compound is to be selected from ethane ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9 hydrogen-carbazole - 3- substituents] -, 1- (oxygen-acetyl oxime) [Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazole-3-yl]-, 1- (O-acetyl oxime), the trade name of such as Ciba Specialty Chemicals manufactures For CGI-242, shown in its structure such as following formula (E-2-1)], 1- [4- (phenyl) phenyl]-octane -1,2- diketone 2- (O- benzene Acyl group oxime) [1- [4- (phenylthio) phenyl]-octane-1,2-dione 2- (O-benzoyloxime), such as Ciba The trade name CGI-124 of Specialty Chemicals manufactures, its structure such as following formula (E-2-2) is shown], ethane ketone, 1- [9- ethyls -6- (the chloro- 4- benzyls of 2--thio-benzoyl) -9 hydrogen-carbazole -3- substituents] -, 1- (oxygen-acetyl oxime) [Ethanone,1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1- (O-acety loxime), such as rising sun electrification company system, shown in its structure such as following formula (E-2-3)]：
It is preferred that other free radical type light initiators (E-2) are 2- methyl isophthalic acids-(4- methylthiophenyis) -2- morpholines Generation -1- acetone, 2- benzyl -2- nitrogen, nitrogen-dimethylamine -1- (4- morphlinophenyls) -1- butanone, 2,2 '-bis- (o- chlorphenyls) -4, 4 ', 5,5 '-tetraphenyl diimidazole, ethane ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9 hydrogen-carbazole -3- substituents] -, 1- (oxygen-acetyl oxime) or these combination.
Other free radical type light initiators (E-2) of the present invention can further add following compound：Thioxanthones (thioxanthone), 2,4- diethyl thioxanthones (2,4-diethyl-thioxanthanone), thioxanthones -4- sulfones (thioxanthone-4-sulfone), benzophenone (benzophenone), 4,4 '-bis- (dimethylamine) benzophenone [4,4 '- Bis (dimethylamino) benzophenone], 4,4 '-bis- (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] etc. benzophenone (benzophenone) class compound；Benzil (benzil), second α-the diketone such as acyl group (acetyl) (α-diketone) class compound；Diphenylhydroxyethanone (benzoin) etc. keto-alcohol (acyloin) class Compound；Diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin Ethylether), the keto-alcohol ether (acyloin ether) such as diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) Class compound；2,4,6- trimethyl benzoyl diphenyl phosphine oxides (2,4,6-trimethyl-benzoyl-diphenyl- Phosphineoxide), double-(2,6- dimethoxys benzoyl) -2,4,4- trimethylpentyl phosphine oxides [bis- (2,6- Dimethoxy-benzoyl) -2,4,4-trimethyl-benzyl-phosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) class compound；Anthraquinone (anthraquinone), 1,4- naphthoquinones (1,4-naphthoquinone) Deng quinone (quinone) class compound；Chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl-phenylsulfone), three (trichloromethyl)-s- triazines [tris (trichloromethyl)-s- Triazine] etc. halide；And two-the peroxide such as tributyl peroxide (di-tertbutylperoxide).Its In, with benzophenone (benzophenone) class compound preferably, especially with 4,4 '-bis- (diethylamine) benzophenone are optimal.
Above-mentioned other free radical type light initiators (E-2) can be individually a kind of or mix a variety of use.
In the concrete example of the present invention, the usage amount based on the alkali soluble resin (C) is 100 parts by weight, and this is other certainly It is 9.9 parts by weight to 85 parts by weight by the usage amount of fundamental mode light initiator (E-2)；Preferably 14 parts by weight are to 78 parts by weight；More Good is 17 parts by weight to 70 parts by weight.
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, and the usage amount of the light initiator (E) is 10 weights Part is measured to 100 parts by weight；Preferably 15 parts by weight are to 90 parts by weight；More preferably 20 parts by weight are to 80 parts by weight.
Structure shown in formula (I) is had according to the hot acid propellant (F) of the present invention：
R1f(SO3R2f)aFormula (I)
In formula (I), R1fAnd R2fArbitrary substituent is represented independently of one another, and there is no particular restriction for the substituent, example Such as：Alkyl (alkyl, alkenyl, phenyl, Benzyl bases, tolyl, xylyl, naphthyl, alkyl naphthyl etc.) and perfluoroalkyl etc., its In, R2fPreferably (C6H5)COCH(C6H5)O-；And
A represents more than 1 integer；Preferably 1 to 4 integer；More preferably 1 to 2 integer.
The hot acid propellant (F) should with structure shown in formula (I) is preferably selected from by aromatic sulfonic acid ester, aliphatic sulfonic Group combined by ester and perfluoroalkyl sulfonate ester.
In the concrete example of the present invention, foregoing aromatic sulfonic acid ester is p- methyl tosylates, p- toluenesulfonic acids ethyl ester, P- butyl tosylates, 1,2,3- tri- (p- tosyloxies) benzene [1,2,3-tri (p-toluenesulfonyloxy) Benzene], p- toluenesulfonic acids benzoin ester (p-toluene sulfonic acid benzoin ester), detergent alkylate (for example king Industries societies manufacture, model K-PURE TAG's 2507 for methylmesylate, DBSA ethyl ester Commodity), naphthalenedisulfonic acid dimethyl ester, naphthalenedisulfonic acid diethylester, naphthalenesulfonate, naphthalene sulfonic acids ethyl ester, dinonylnaphthalene sulfonic acid methyl esters, two Nonyl naphthalene sulfonic acids ethyl ester (for example king Industries societies manufacture, model K-PURE CXC1762 commodity), dinonyl naphthalene Disulfonic acid ethyl ester (for example king Industries societies manufacture, model K-PURE CXC1764 commodity) or following formula (I-1) To the structure shown in formula (I-3) etc..
Wherein, m represents 1 to 3 integer
In the concrete example of the present invention, foregoing aliphatic sulphonic acid ester is Loprazolam methyl esters, Loprazolam ethyl ester, methane Sulfonic acid butyl ester, 1,2,3- tri- (methanesulfonyloxy group) benzene [1,2,3-tri (methanesulfonyloxy) benzene], methane Phenyl sulfonate, Loprazolam benzoin ester (methane sulfonic acid benzoin ester) etc..
In the concrete example of the present invention, foregoing perfluoroalkyl sulfonate ester is trifluoromethayl sulfonic acid methyl esters, fluoroform sulphur Acetoacetic ester, trifluoromethayl sulfonic acid butyl ester, 1,2,3- (trifluorometanesulfonyloxy) benzene [1,2,3- (trifluoromethanesulfonyloxy) benzene], trifluoromethayl sulfonic acid phenyl ester, trifluoromethayl sulfonic acid benzoin ester (trifluoromethanesulfonic acid benzoin ester) etc..
Above-mentioned sulphonic acid ester individually a kind of can use or mix a variety of use.
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, the usage amount scope of the hot acid propellant (F) For 0.1 parts by weight to 10 parts by weight；Preferably 0.6 parts by weight are to 8 parts by weight；More preferably 1 parts by weight are to 6 parts by weight.When not making During with hot acid propellant (F), the colored filter that the photosensitive resin composition is formed has hot solvent Thickness Variation rate Not good the problem of.As hot acid propellant (F) using the aromatic sulfonic acid ester, the coloured silk that the photosensitive resin composition is formed Colo(u)r filter its hot solvent Thickness Variation rate is more preferably.
The preparation of the photosensitive resin composition of the invention, is typically first to be dissolved in each composition beyond the pigment (A) In solvent (G), liquid constituent is modulated into, pigment (A) uniformly mixing is added.Solvent (G) need to select can dissolve dyestuff (B), Alkali soluble resin (C), the compound (D) with ethene unsaturated group, light initiator (E) and hot acid propellant (F), and Need the appropriate evaporative that do not react to each other and have with the grade composition.
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, and the usage amount of the solvent (G) is 500 parts by weight To 5000 parts by weight；Preferably 800 parts by weight are to 4500 parts by weight；More preferably 1000 parts by weight are to 4000 parts by weight.
In addition, solvent (G) can be identical with preparing solvent used in alkali soluble resin (C), it will not be repeated here.Preferably Ground, the solvent (G) is selected from propylene glycol methyl ether acetate, cyclohexanone or 3- ethoxyl ethyl propionates.
In the preferred embodiment of the present invention, the photosensitive resin composition also includes additive (H), for example：Filler, High-molecular compound, adherence accelerator beyond alkali soluble resin (C), antioxidant, ultra-violet absorber, anti-agglutinant Deng.
The additive (H) can be used alone or as a mixture, and the additive (H) is including but not limited to fillers such as glass, aluminium； High-molecular compound beyond the alkali soluble resins (C) such as polyvinyl alcohol, polyalkylene glycol monoalkyl ether, poly- perfluoroalkyl acrylate alkyl ester； Vinyltrimethoxy silane, VTES, vinyl three (2- methoxyethoxies) silane, nitrogen-(2- amido second Base) -3- aminocarbonyl propyls methyl dimethoxysilane, nitrogen-(2- amidos ethyl) -3- aminocarbonyl propyl trimethoxy silanes, 3- amidos Propyl-triethoxysilicane, 3- epoxy prapanols propyl trimethoxy silicane, 3- epoxy prapanol hydroxypropyl methyls dimethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silicon The adherence accelerator such as alkane, 3- metacryloxies propyl trimethoxy silicane, 3- mercaptopropyl trimethoxy silanes；2,2- sulphur The antioxidants such as Dai Shuan (4- methyl -6- tributyl phenols), the tributyl phenols of 2,6- bis--the；2- (3- tributyl -5- first Base -2- hydroxy phenyls) -5- chlorphenyls change the ultra-violet absorbers such as nitrogen, alkoxy benzophenone；And the anti-agglutinant such as Sodium Polyacrylate.
Usage amount based on the alkali soluble resin (C) is 100 parts by weight, and the usage amount of the additive (H) is 0.1 weight Part to 10 parts by weight；Preferably 0.3 parts by weight are to 7 parts by weight；More preferably 0.5 parts by weight are to 4 parts by weight.
The present invention also provides a kind of manufacture method of colored filter, and it is using foregoing colored filter photonasty Resin combination, with forming a pixel layer on substrate.
The present invention provides a kind of colored filter again, and it is as obtained by foregoing method.
The manufacture method of the colored filter of the present invention, mainly by turning round coating, cast coat, ink-jet application (ink-jet) or the coating method such as print roll coating, the foregoing colored filter photosensitive compoistion of solution state will be mixed into It is coated on substrate.After coating, first in the way of being dried under reduced pressure, most solvent is removed, then with pre-baked (pre-bake) side Solvent is removed and forms a pre-baked film by formula.Wherein, it is dried under reduced pressure and pre-baked condition, according to the species of each composition, match ratio Rate and it is different, generally, it is to be carried out 1 second to 60 seconds under 0 to 200mmHg pressure to be dried under reduced pressure, and pre-baked is 70 Carried out 1 minute to 15 minutes at a temperature of to 110 DEG C.After pre-baked, the pre-baked film under specified light shield (mask) expose, in Developer solution is impregnated at a temperature of 23 ± 2 DEG C to be developed within 15 seconds to 5 minutes, remove should not part and form pattern.Exposure makes Light, is preferred with the ultraviolet of g lines, h lines, i lines etc., and UV-device can be (super) high-pressure mercury-vapor lamp or metal halogen Lamp.
Aforesaid base plate it is specific for example：Alkali-free glass, soda-lime glass, hard glass (group's Le for liquid crystal display This glass), quartz glass, soda-lime glass and in nesa coating accompanying on these glass；Or for solid-state image sensor Deng photo-electric conversion device substrate (such as：Silicon substrate) etc..These substrates are usually to be initially formed to isolate the black of each pixel shader layer Colour moment battle array (black matrix).
Furthermore, developer solution it is specific for example：NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potassium carbonate, bicarbonate Potassium, sodium metasilicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Choline, pyrroles, croak pyridine, the alkaline aqueous solution that the alkali compounds such as 1,8- diazabicylo-(5,4,0) -7- hendecenes is constituted, Its concentration is generally 0.001 to 10 weight %, more preferably preferably 0.005 to 5 weight %, 0.01 to 1 weight %.
It is usually in being cleaned again with water after development, secondly with pressure during the developer solution constituted using the aforementioned base aqueous solution Contracting air or compressed nitrogen air-dry pattern.
The substrate with photo-hardening film layer after air-drying, using heaters such as hot plate or baking ovens, temperature 100 to Heat 1 to 15 minute, the volatile ingredient in film is removed, and make unreacted ethene insatiable hunger in film at 280 DEG C Thermmohardening reaction is carried out with double bond.Using the photosensitive resin composition of assorted (main to include the color of red, green, blue three) predetermined Repeated three times with same step in pixel, you can obtain the pixel shader layer of the color of red, green, blue three.
Secondly, on pixel shader layer, it is deposited with 220 DEG C to 250 DEG C temperature in formation ITO (tin indium oxide) under vacuum Film, if necessary, implements after etching and connecting up to ITO evaporation films, is coated liquid crystal orienting film polyimides, and then burn till , you can it is used as the colored filter of liquid crystal display.
Furthermore, the foregoing liquid crystal orienting film used is the orientation for limiting liquid crystal molecule, herein and is not particularly limited, Such as inorganic matter or organic matter any one.Technology as formation liquid crystal orienting film is to appoint in the technical field of the invention Known to what technical staff, and the non-emphasis for the present invention, therefore do not repeat separately.
Another object of the present invention is to provide a kind of LCD assembly, and the LCD assembly includes foregoing colorized optical filtering Piece.
The LCD assembly of the present invention, the colorized optical filtering mainly formed by above-mentioned colored filter forming method Plate base, and be provided with the driving substrate of thin film transistor (TFT) (TFT, Thin Film Transistor) and constituted, wherein, Gap (structure cell interval is intervened between 2 plate bases；Cell gap) make oppositely disposed, the surrounding position of 2 plate bases is fitted with sealing agent, Filling injection liquid crystal, seals hand-hole and constitutes liquid crystal cell in the gap that substrate surface and sealing agent are distinguished (cell).Then, in the outer surface of liquid crystal cell, that is, on other sides of each substrate of composition liquid crystal cell, laminating is inclined Tabula rasa and be made LCD assembly.
As for the foregoing liquid crystal used, that is, liquid-crystal compounds or liquid-crystal composition, herein and it is not particularly limited, can be used Any liquid-crystal compounds and liquid-crystal composition.
The present invention is described in detail with the following example, is not intended to that present invention is limited only by involved by these embodiments Content.
Synthesis example
Prepare the first alkali soluble resin (C)
Synthesis example C-1-1
By fluorenes ring oxygen compound (the model ESF-300, Nippon Steel's chemistry system of 100 parts by weight；Epoxide equivalent 231), 30 weights Measure the acrylic acid, the benzyltriethylammonium chloride of 0.3 parts by weight, the tributyl paracresol of 2,6- bis- and 130 of 0.1 parts by weight of part The propylene glycol methyl ether acetate of parts by weight continuously added to 500mL four-hole boiling flask in, and pan feeding speed control 25 parts by weight/ Minute, temperature is maintained in the range of 100 DEG C to 110 DEG C, after reacting 15 hours, you can obtaining solid component concentration is 50wt% pale yellow transparent mixed liquor.
Then, the above-mentioned mixed liquor of 100 parts by weight is dissolved in the ethylene glycol ether acetate of 25 parts by weight, added simultaneously The benzophenone tetracarboxylic dianhydride of the tetrabydrophthalic anhydride of 6 parts by weight and 13 parts by weight, and it is heated to 110 DEG C to 115 DEG C, After reaction 2 hours, you can acquisition acid value is 98.0mgKOH/g, and number mean molecule quantity is 1,623 the first alkali-soluble tree Fat (C-1-1).
Synthesis example C-1-2
By fluorenes ring oxygen compound (the model ESF-300, Nippon Steel's chemistry system of 100 parts by weight；Epoxide equivalent 231), 30 weights Measure the acrylic acid, the benzyltriethylammonium chloride of 0.3 parts by weight, the tributyl paracresol of 2,6- bis- and 130 of 0.1 parts by weight of part The propylene glycol methyl ether acetate of parts by weight continuously added to 500mL four-hole boiling flask in, and pan feeding speed control 25 parts by weight/ Minute, temperature is maintained in the range of 100 DEG C to 110 DEG C, after reacting 15 hours, you can obtaining solid component concentration is 50wt% pale yellow transparent mixed liquor.
Then, the above-mentioned mixed liquor of 100 parts by weight is dissolved in the ethylene glycol ether acetate of 25 parts by weight, added simultaneously The benzophenone tetracarboxylic dianhydride of 13 parts by weight, reacts 2 hours, then, the tetrahydrochysene for adding 6 parts by weight is adjacent at 90 DEG C to 95 DEG C Phthalate anhydride, and in being reacted 4 hours at 90 DEG C to 95 DEG C, you can acquisitions acid value is 99.0mgKOH/g, and number mean molecule Measure the first alkali soluble resin (C-1-2) for 2,162.
Synthesis example C-1-3
By epoxide (the model NC-3000, Japanese chemical drug (strain) system of 400 parts by weight；Epoxide equivalent 288), 102 weights Measure acrylic acid, the methoxyl group phenol (methoxyphenol), the triphenylphosphine of 5 parts by weight and 264 parts by weight of 0.3 parts by weight of part Propylene glycol methyl ether acetate be placed in reaction bulb, temperature is maintained 95 DEG C, after reaction 9 hours, you can obtaining acid value is 2.2mgKOH/g intermediate product.Then, the tetrabydrophthalic anhydride (tetrahydrophthalic of 151 parts by weight is added Anhydride), reacted 4 hours at 95 DEG C, you can acquisition acid value is 102mgKOH/g, and number mean molecule quantity is 2,589 The first alkali soluble resin (C-1-3).
Synthesis example C-1-4
By epoxide (the model NC-3000, Japanese chemical drug (strain) system of 200 parts by weight；Epoxide equivalent 288), 60 weights Measure acrylic acid, the methoxyl group phenol (methoxyphenol), the triphenylphosphine of 2.5 parts by weight and 200 weight of 0.15 parts by weight of part The propylene glycol methyl ether acetate of part is placed in reaction bulb, and temperature is maintained into 95 DEG C, after reacting 9 hours, you can obtaining acid value is 2.5mgKOH/g intermediate product.Then, the tetrabydrophthalic anhydride (tetrahydrophthalic of 85 parts by weight is added Anhydride), reacted 4 hours at 95 DEG C, you can acquisition acid value is 105mgKOH/g, and number mean molecule quantity is 3,410 The first alkali soluble resin (C-1-4).
Prepare the second alkali soluble resin (C-2)
Synthesis example C-2-1
Agitator, thermometer, condenser pipe and nitrogen inlet are set on one or four cervical vertebras bottle, and import nitrogen.Then, add The propylene glycol methyl ether acetate (referred to as PGMEA) of 100 parts by weight, and temperature is warming up to 100 DEG C.Then, by 25 parts by weight 2- methacryloyloxyethyls succinate (referred to as HOMS), 70 parts by weight 2-hydroxyethyl methacrylate (referred to as For HEMA), the methacrylic acid 3,4- epoxycyclohexanecarboxylates (ECMMA) of 15 parts by weight, the o- vinyl benzene first of 10 parts by weight Glycidyl ether (referred to as VBGE), and 4.5 parts by weight 2, the double -2- methylbutyronitriles of 2 '-azo (referred to as AMBN) are dissolved in In the propylene glycol methyl ether acetate of 100 parts by weight, and by this mixed solution in being instilled dropwise in 2 hours in above-mentioned four cervical vertebra bottle. After 100 DEG C are reacted 6.5 hours, the acrylic acid (referred to as AA) of 5 parts by weight is added in the four cervical vertebras bottle full of nitrogen, and will Temperature rises to 110 DEG C.After reaction 6 hours, you can synthesis example C-2-1 the second alkali soluble resin is made.
Synthesis example C-2-2 to C-2-6 manufacture method
Synthesis example C-2-2 to C-2-6 is that the second alkali soluble resin is prepared with the step identical with synthesis example C-2-1 (C-2), different places is：Change reaction temperature, polymerization time, the species and usage amount of composition, and state in detail in table 1.
MAA methacrylic acids
HOMS 2- methacryloyloxyethyl succinates
AA acrylic acid
N-PMI N-phenylmaleimides
HEMA 2-hydroxyethyl methacrylates
BzMA benzyl methacrylates
ECMMA methacrylic acid 3,4- epoxycyclohexanecarboxylates
MGMA methacrylic acid 2- methyl polyglycidyls
The o- vinyl benzene methyl glycidyl ethers of VBGE
Double -2- the methylbutyronitriles of AMBN 2,2 '-azo
ADVN 2,2- azos-two-(2,4- dimethyl-pentens cyanogen)
PGMEA propylene glycol methyl ether acetates
EEP 3- ethoxy ethyl acrylates
Embodiment
Prepare photosensitive resin composition
Embodiment 1
By the second alkali soluble resin (C-2-1) of 100 parts by weight obtained by foregoing synthesis example, the C.I. face of 50 parts by weight Expect red 254 (hereinafter referred to as A-1), the C.I. solvent red 24s (hereinafter referred to as B-1) of 10 parts by weight, the dipentaerythritol of 30 parts by weight 1- [4- (phenyl) phenyl]-octane -1,2- diketone 2- (O- benzoyls of six acrylate (hereinafter referred to as D-2), 50 parts by weight Base oxime) (hereinafter referred to as E-2-1), 2,2 '-bis- (2,4 dichloro benzene bases) -4,4 ' of 5 parts by weight, 5,5 '-tetraphenyl diimidazole (with Lower abbreviation E-2-2), the Loprazolam ethyl ester (F-1) of 0.9 parts by weight, add 1500 parts by weight 3- ethoxyl ethyl propionates (with Lower abbreviation G-1) after, with swing-out stirrer, dissolved mixing, you can modulate and obtain photosensitive resin composition, this is photosensitive Property resin combination is evaluated in following each evaluation of measuring modes, and acquired results are as shown in table 2.
Embodiment 2 to 14 and comparative example 1 to 6
Embodiment 2 to 14 and comparative example 1 to 6 are using the preparation method phase with the photosensitive resin composition of embodiment 1 Same preparation method, difference is embodiment 2 to 14 and comparative example 1 to 6 is raw material in change photosensitive resin composition Species and usage amount, and its formula and evaluation result are as shown in table 2 respectively.
A-1 C.I. paratoneres 254
A-2 C.I. pigment green 36s
A-3 C.I. pigment blue 15s:6
A-4 C.I. alizarol saphirols 66
A-5 C.I. paratoneres 177
B-1 C.I. solvent red 24s
B-2 C.I. solvent red 49s
B-3 C.I. acid reds 289
The sour trihydroxy methyl propyl ester of trimethacrylate of D-1 EO modifications
D-2 dipentaerythritol acrylates
The dipentaerythritol acrylate of D-3 caprolactones modification
Compound shown in E-1-1 formulas (III-1)
Compound shown in E-1-2 formulas (III-8)
Compound shown in E-1-3 formulas (III-27)
E-2-1 1- [4- (phenyl) phenyl]-octane -1,2- diketone 2- (O- benzoyl groups oxime)
E-2-2 2,2 '-bis- (2,4 dichloro benzene base) -4,4 ', 5,5 '-tetraphenyl diimidazole
2,2’-bis(2,4-dichlorophenyl)-4,4’,5,5’-tetraphenyl-biimidazole
E-2-3 4,4 '-bis- (diethylamine) benzophenone 4,4 '-bis (diethylamino) benzophenone
E-2-4 2- benzyl -2- nitrogen, nitrogen-dimethylamine -1- (4- morphlinophenyls) -1- butanone
2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone
F-1 Loprazolam ethyl esters
F-2 trifluoromethayl sulfonic acid methyl esters
F-3 dinonylnaphthalene sulfonic acid ethyl esters
(for example king Industries societies manufacture, model K-PURE CXC1762 commodity)
F-4 DBSA ethyl esters
(for example king Industries societies manufacture, model K-PURE TAG 2507 commodity)
G-1 3- ethoxyl ethyl propionates
G-2 propylene glycol methyl ether acetates
G-3 cyclohexanone
H-1 3- mercaptopropyl trimethoxy silanes
H-2 2,2- thiobis (4- methyl -6- tributyl phenols)
H-3 ESCALOL 567s
Evaluation method
Hot solvent Thickness Variation rate
By the photosensitive resin composition obtained by embodiment 1 to 14 and comparative example 1 to 6 in the way of rotary coating, apply Cloth is in size on 100mm × 100mm glass substrate.Then, it is dried under reduced pressure, its pressure is 100mmHg and the time is 30 seconds.Then, hard baking is carried out, its temperature is 80 DEG C and the time is 2 minutes, and it is pre- for 2.5 μm to form a thickness Roasting film.Carry out after hard baking, using energy as 60mJ/cm2Ultraviolet light (exposure machine Canon PLA-501F) to irradiate this pre- Roasting film, and the pre-baked film after exposure is impregnated in 23 DEG C of developer solution.After 1 minute, the film is cleaned with pure water, And curing process after being carried out with 230 DEG C.Baked after progress after processing, measure the thickness (T of filmi).Afterwards, film leaching is placed in 60 DEG C Propylene glycol methyl ether acetate solvent.After 6 minutes, the thickness (T of film is measuredf), Thickness Variation rate is calculated as follows, and Evaluated according to following benchmark：
◎：Thickness Variation rate ＜ 1%.
○：1%≤Thickness Variation rate ＜ 3%.
△：3%≤Thickness Variation rate ＜ 5%.
╳：5%≤Thickness Variation rate.
The principle and its effect of above-described embodiment only to illustrate the invention, are not intended to limit the present invention.Know the skill of this technology The modification and change that art personnel are made to above-described embodiment are still without prejudice to the spirit of the present invention.The interest field of the present invention should be such as power Profit requires described.

Claims (13)

1. a kind of photosensitive resin composition, it is included：
Pigment (A)；
Dyestuff (B)；
Alkali soluble resin (C)；
Compound (D) with ethene unsaturated group；
Light initiator (E)；
Hot acid propellant (F) with structure shown in formula (I)；
And solvent (G)；
R1f(SO3R2f)aFormula (I)
In formula (I), R1fAnd R2fArbitrary substituent is represented independently of one another；
And a represents more than 1 integer.
2. photosensitive resin composition according to claim 1, wherein the alkali soluble resin (C) can comprising the first alkali Soluble resin (C-1), first alkali soluble resin (C-1) be as obtained by a mixture carries out polymerisation, it is and described Mixture include epoxide (c-1-1) with least two epoxy radicals and with least one carboxylic acid group and at least one The compound (c-1-2) of ethene unsaturated group.
3. photosensitive resin composition according to claim 2, wherein the epoxidation with least two epoxy radicals Compound (c-1-1) has the structure as shown in formula (II-1) or formula (II-2)；
In formula (II-1), R1c、R2c、R3cAnd R4cIt is respectively identical or different, and represent that hydrogen atom, halogen atom, carbon number are 1 The aralkyl that the aromatic radical or carbon number that alkoxy that alkyl, carbon number to 5 are 1 to 5, carbon number are 6 to 12 are 6 to 12；
In formula (II-2), R5cTo R18cIt is each independent to represent that alkyl or carbon number that hydrogen atom, halogen atom, carbon number are 1 to 8 are 6 To 15 aromatic radical；And g represents 0 to 10 integer.
4. photosensitive resin composition according to claim 1, has such as formula wherein the smooth initiator (E) is included (III) the light initiator (E-1) of structure shown in：
In formula (III), E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom, carbon number as 1 to 20 alkyl,COE16、OE17, halogen atom, NO2OrOr
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Independently represent warp Substituted carbon number is 2 to 10 alkenyl；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Separately common representative-(CH2)p-W-(CH2)q-； Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is separately common to representThe E of wherein at least one1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
E9、E10、E11And E12It is 1 to 20 alkyl independently to represent hydrogen atom, carbon number, and the carbon number is for 1 to 20 alkyl Be unsubstituted or through at least one substituent group as follows, and at least one described group be selected from phenyl, halogen atom, CN, OH, SH, carbon number are 1 to 4 alkoxy, (CO) OH or (CO) O (R1), wherein R1It is 1 to 4 alkyl to represent carbon number；Or
E9、E10、E11And E12Separately represent the phenyl that is unsubstituted or through at least one substituent group as follows Phenyl, alkyl, halogen atom, CN, OE that it is 1 to 6 selected from carbon number that at least one described group, which is,17、SE18Or NE19E20；Or
E9、E10、E11And E12Separately represent halogen atom, CN, OE17、SE18、SOE18、SO2E18Or NE19E20, wherein institute State substituent OE17、SE18Or NE19E20It is without or via group E17、E18、E19And/or E20With a carbon atom shape of naphthalene nucleus Into five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Separately representCOE16Or NO2；
W represents O, S, NE26Or singly-bound, p represents 0 to 3 integer, and q represents 1 to 3 integer, Z1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, the carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, wherein at least one described group is to be selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2OrOr
E13It is 2 to 20 alkyl to represent carbon number, the carbon number for 2 to 20 alkyl its be mixed with have one or more O, S, SO, SO2、NE26Or CO；Or
E13It is 2 to 12 alkenyl to represent carbon number, the carbon number for 2 to 12 alkenyl its be to have one or many without being mixed with or being mixed with Individual O, CO or NE26,
It is wherein described through being mixed with and the alkyl that carbon number is 2 to 20 and the alkene that the carbon number without being mixed with or through being mixed with is 2 to 12 Base is to be unsubstituted or replace through at least one halogen atom；Or
E13Represent carbon number as 4 to 8 cycloalkenyl group, carbon number as 2 to 12 alkynyl or without be mixed with or be mixed with have one or more O, S, CO or NE26Carbon number be 3 to 10 cycloalkyl；Or
E13Phenyl or naphthyl is represented, and the phenyl or the naphthyl are respectively unsubstituted or through at least one group as follows Substitution, wherein at least one described group is to be selected from OE17、SE18、NE19E20、COE16、CN、 NO2, halogen atom, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 haloalkyl, be mixed with have one or more O, S, CO or NE26And carbon number is 2 to 20 alkyl；Or the phenyl or each cycloalkyl substitution through carbon number for 3 to 10 of the naphthyl or each warp Being mixed with has one or more O, S, CO or NE26And carbon number replaces for 3 to 10 cycloalkyl；
K represents 1 to 10 integer；
E14Represent hydrogen atom, carbon number as 3 to 8 cycloalkyl, carbon number as 2 to 5 alkenyl, carbon number as 1 to 20 alkoxy or not It is substituted or alkyl that carbon number through at least one substituent group as follows is 1 to 20, and at least one described group is Selected from halogen atom, phenyl, the alkyl phenyl or CN that carbon number is 1 to 20；Or
E14Phenyl or naphthyl is represented, it is respectively unsubstituted or through at least one substituent group as follows, and described at least one Haloalkyl that alkyl that it is 1 to 6 selected from carbon number that individual group, which is, carbon number are 1 to 4, halogen atom, CN, OE17、SE18And/or NE19E20；Or
E14Represent carbon number as 3 to 20 heteroaryl, carbon number as 1 to 8 alkoxy, benzyloxy or phenoxy group, the benzyloxy and The phenoxy group is unsubstituted or through at least one substituent group as follows, and at least one described group is to be selected from carbon Haloalkyl and/or halogen atom that alkyl that number is 1 to 6, carbon number are 1 to 4；
E15It is 3 to 20 heteroaryl that carbon number, which is represented, as 6 to 20 aromatic radical or carbon number, and it is respectively unsubstituted or through as follows At least one substituent group, and at least one described group be selected from phenyl, halogen atom, carbon number for 1 to 4 haloalkyl, CN、NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2And SO is bonded and carbon number is 1 to 10 alkyl and SO2Bond and carbon number For 1 to 10 alkyl, it is mixed with and has one or more O, S or NE26And carbon number is 2 to 20 alkyl；Or it is respectively 1 to 20 through carbon number Alkyl substitution, wherein the carbon number for 1 to 20 alkyl is unsubstituted or through at least one substituent group as follows, And at least one described group is to be selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number for 3 to 8 cycloalkyl, carbon number Heteroaryloxycarbonyl that the aryloxycarbonyl for being 6 to 20 for 3 to 20 heteroaryl, carbon number, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E15Represent hydrogen atom, carbon number as 2 to 12 alkenyl, without being mixed with or being mixed with have one or more O, CO or NE26And carbon number For 3 to 8 cycloalkyl；Or
E15It is 1 to 20 alkyl to represent carbon number, the carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one described group is to be selected from halogen atom, OE17、SE18, carbon number for 3 to 8 cycloalkyl, carbon Heteroaryloxycarbonyl that aryloxycarbonyl that heteroaryl that number is 3 to 20, carbon number are 6 to 20, carbon number are 3 to 20, NE19E20、 COOE17、CONE19E20、PO(OCkH2k+1)2、 Phenyl, wherein the carbon number For 1 to 20 alkyl replaced through phenyl, and alkyl that it is 1 to 20 through halogen atom, carbon number that the phenyl, which is, carbon number are 1 to 4 Haloalkyl, OE17、SE18Or NE19E20Substitution；Or
E15It is 2 to 20 alkyl to represent carbon number, and the carbon number is to be mixed with to have one or more O, SO or SO for 2 to 20 alkyl2, It is described through being mixed with and carbon number for 2 to 20 alkyl is unsubstituted or through at least one substituent group as follows, it is and described At least one group is to be selected from halogen atom, OE17、COOE17、CONE19E20, phenyl or through OE17、SE18Or NE19E20Substitution Phenyl；Or
E15It is 2 to 20 alkanoyl or benzoyl to represent carbon number, and it is unsubstituted or through at least one base as follows Group's substitution, and at least one described group is selected from the alkyl that carbon number is 1 to 6, halogen atom, phenyl, OE17、SE18Or NE19E20；Or
E15Representative is unsubstituted or through at least one OE17Substituted naphthoyl or the Heteroarylcarbonyl that carbon number is 3 to 14；Or
E15It is 2 to 12 alkoxy carbonyl to represent carbon number, and the carbon number is without being mixed with or through extremely for 2 to 12 alkoxy carbonyl A few O is mixed with, wherein described through being mixed with or without the alkoxy carbonyl being mixed with and carbon number is 2 to 12 being unsubstituted or through extremely Few hydroxyl substitution；Or
E15Phenyloxycarbonyl is represented, the phenyloxycarbonyl is unsubstituted or through at least one substituent group as follows, And alkyl that it is 1 to 6 selected from carbon number that at least one described group, which is, halogen atom, carbon number be 1 to 4 haloalkyl, phenyl, OE17、SE18Or NE19E20；Or
E15Represent CN, CONE19E20、NO2, carbon number for 1 to 4 haloalkyl, S (O)r-R2And S (O)rThe phenyl of bond, wherein Described and S (O)rThe phenyl of bond be unsubstituted or through carbon number be 1 to 12 alkyl or SO2-R2Substitution, and R2Represent carbon number For 1 to 6 alkyl；Or
E15Represent and SO2Phenyl, diphenylphosphino or the two (R of O bonds3)-phosphono, wherein described and SO2The benzene of O bonds Base is to be unsubstituted or replace through carbon number for 1 to 12 alkyl, and R3It is 1 to 4 alkoxy to represent carbon number；
R represents 1 to 2 integer；
E'14Represent to have and be directed to E14One of those in definition；
E'15Represent to have and be directed to E15One of those in definition；
Z2Represent O, S, SO or SO2；
Z3Represent O, CO, S or singly-bound；
E16Represent carbon number as 6 to 20 aryl or carbon number as 3 to 20 heteroaryl, its be respectively unsubstituted or through it is as follows extremely A few substituent group, and at least one described group be selected from phenyl, halogen atom, carbon number be 1 to 4 haloalkyl, CN, NO2、OE17、SE18、NE19E20, be mixed with and have one or more O, S or NE26And carbon number be 1 to 20 alkyl, or carbon number be 1 to 20 alkyl, wherein the carbon number for 1 to 20 alkyl is unsubstituted or through at least one substituent group as follows, its Described at least one group be selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number for 3 to 8 cycloalkyl, carbon number Heteroaryloxycarbonyl that the aryloxycarbonyl for being 6 to 20 for 3 to 20 heteroaryl, carbon number, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E16It is 1 to 20 alkyl to represent hydrogen atom or carbon number, wherein the carbon number for 1 to 20 alkyl is unsubstituted or through such as Lower at least one shown substituent group, and at least one described group is to be selected from halogen atom, phenyl, OH, SH, CN, carbon number For 3 to 6 alkenyloxy group, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1), O (CO)-phenyl or (CO) OH or (CO) O (R1)；Or
E16It is 2 to 12 alkyl to represent carbon number, and described 2 to 12 alkyl is to be mixed with to have one or more O, S or NE26；Or
E16Represent (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 12 alkenyl or carbon number be 3 to 8 cycloalkanes Base, wherein R4It is 1 to 8 alkyl to represent carbon number；Or
E16Represent through SE18Substituted phenyl, wherein E18Bond is represented to the COE16The phenyl of the carbazole moiety connected Or the singly-bound of naphthyl ring；
N represents 1 to 20 integer；
E17Represent hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, it is unsubstituted or through at least one as follows Substituent group, and at least one described group be selected from halogen atom, OH, SH, CN, carbon number for 3 to 6 alkenyloxy group, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6), with O (CO) be bonded phenyl, (CO) OH, (CO) O (R1), carbon number for 3 to 20 cycloalkyl, SO2-(R7)、O(R7) or be mixed with through at least one O and cycloalkyl that carbon number is 3 to 20, Wherein R5Represent alkyl of the carbon number as 1 to 3, R6It is 2 to 4 alkenyl to represent carbon number, and R7It is 1 to 4 alkyl halide to represent carbon number Base；Or
E17It is 2 to 20 alkyl to represent carbon number, and the carbon number for 2 to 20 alkyl be mixed with have one or more O, S or NE26；Or
E17Represent (CH2CH2O)n+1H、(CH2CH2O)n(CO)-(R4), carbon number be 1 to 8 alkanoyl, carbon number be 2 to 12 alkene The cycloalkyl that the enoyl- or carbon number that base, carbon number are 3 to 6 are 3 to 20, its be without be mixed with or be mixed with have one or more O, S, CO or NE26；Or
E17Alkyl and the carbon number that carbon number is represented by 1 to 8 are 3 to 10 group that is formed of cycloalkyl bond, and the group is Without being mixed with or being mixed with through at least one O；Or
E17Represent benzoyl, the benzoyl is unsubstituted or through at least one substituent group as follows, and described The alkoxy that alkyl, halogen atom, OH or the carbon number that it is 1 to 6 selected from carbon number that at least one group, which is, are 1 to 3；Or
E17It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is respectively unsubstituted or through at least one base as follows Group's substitution, and the alkane that alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that at least one described group, which is, carbon number are 1 to 12 Epoxide, CN, NO2, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amido orWherein R8It is 1 to 3 alkoxy to represent carbon number, and R9It is 1 to 12 alkyl to represent carbon number；Or
E17With withOrPhenyl or naphthyl ring one of carbon Atom formation singly-bound；
E18It is 2 to 12 cycloalkyl or phenyl-R as 3 to 20 of alkenyl, carbon number to represent hydrogen atom, carbon number5, wherein the carbon number The cycloalkyl for being 3 to 20 for 2 to 12 alkenyl, the carbon number and the phenyl-R5It is to have one or many without being mixed with or being mixed with Individual O, S, CO, NE26Or COOE17；Or
E18It is 1 to 20 alkyl to represent carbon number, and the carbon number is unsubstituted or through as follows at least one for 1 to 20 alkyl Individual substituent group, and at least one described group is selected from OH, SH, CN, the alkenyloxy group that carbon number is 3 to 6, OCH2CH2CN、 OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1), O (CO)-phenyl or (CO) OE17；Or
E18It is 2 to 20 alkyl to represent carbon number, and the carbon number is to be mixed with to have one or more O, S, CO, NE for 2 to 20 alkyl26 Or COOE17；Or
E18Represent (CH2CH2O)nH、(CH2CH2O)n(CO)-(R4), carbon number be 2 to 8 alkanoyl or carbon number be 3 to 6 alkene acyl Base；Or
E18Represent benzoyl, the benzoyl is unsubstituted or through at least one substituent group as follows, and institute It is 1 to state at least one group to be alkoxy or carbon number that the alkyl for being 1 to 6 selected from carbon number, halogen atom, OH, carbon number are 1 to 4 To 4 alkyl sulfenyl；Or
E18It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is unsubstituted or through at least one as follows Substituent group, and at least one described group is to be selected from the halo that halogen atom, the alkyl that carbon number is 1 to 12, carbon number are 1 to 4 Alkoxy, CN, NO that alkyl, carbon number are 1 to 122, phenyl-R8, phenoxy group, carbon number for 1 to 12 alkyl sulfenyl, phenylsulfartyl, N(R9)2, diphenyl amido, (CO) O (R4)、(CO)-R4、(CO)N(R4)2Or
E19And E20Separately represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 2 to 4 hydroxy alkyl, carbon number be 2 Cycloalkyl that alkenyl that alkoxyalkyl, carbon number to 10 are 2 to 5, carbon number are 3 to 20, phenyl-R5, carbon number be 1 to 8 alkane Enoyl- that alkanoyl epoxide that acyl group, carbon number are 1 to 8, carbon number are 3 to 12, SO2-R7Or benzoyl；Or
E19And E20It is 3 to 20 heteroaryl to represent phenyl, naphthyl or carbon number, and it is respectively unsubstituted or through as follows at least one Individual substituent group, and haloalkyl that it is 1 to 4 selected from halogen atom, carbon number that at least one described group, which is, carbon number are 1 to 20 Alkoxy, carbon number be 1 to 12 alkyl, benzoyl or carbon number be 1 to 12 alkoxy；Or
E19And E20It is to be formed to have O, S or NE without being mixed with or being mixed with together with the nitrogen-atoms being bonded17Five yuan or hexa-atomic saturation Or unsaturation ring, and described five yuan or hexa-atomic saturation or unsaturation ring are unsubstituted or through at least one group as follows Substitution, wherein the alkyl that it is 1 to 20 selected from carbon number that at least one described group, which is, carbon number be 1 to 20 alkoxy ,=O, OE17、 SE18、NE21E22、(CO)E23、NO2, halogen atom, carbon number for 1 to 4 haloalkyl, CN, phenyl,Or have one or more O, S, CO or NE without being mixed with or being mixed with17And carbon number is 3 to 20 Cycloalkyl；Or
E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms connected, the heteroaromatic ring system is without taking Generation or through at least one substituent group as follows, and at least one described group is alkyl selected from carbon number for 1 to 20, carbon Alkoxy that haloalkyl that number is 1 to 4, carbon number are 1 to 20 ,=O, OE17、SE18、NE21E22、(CO)E23、Halogen atom, NO2, CN, phenyl, or have one or more O, S, CO without being mixed with or being mixed with Or NE17And carbon number is 3 to 20 cycloalkyl；
E21And E22Separately represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, carbon number be 3 Cycloalkyl or phenyl to 10；
E21And E22Formed together with its bonded nitrogen-atoms has O, S or NE without being mixed with or being mixed with26Five yuan or hexa-atomic saturation Or unsaturation ring, wherein described five yuan or hexa-atomic saturation or unsaturation ring are uncondensed or condensed with phenyl ring；
E23Represent hydrogen atom, OH, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have at least one O, CO Or NE26And carbon number for 2 to 20 alkyl, without being mixed with or being mixed with have O, S, CO or NE26And carbon number is 3 to 20 cycloalkyl；Or
E23Represent phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represent (CO) OE17、CONE19E20、(CO)E17Or with for E19And E20One of those in definition；
E25Represent COOE17、CONE19E20、(CO)E17；Or E25With for E17One of those in definition；
E26Represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with have at least one O or CO and Carbon number is 2 to 20 alkyl；Or E26Represent phenyl-R1, without being mixed with or being mixed with through at least one O or CO and carbon number is 3 to 8 Cycloalkyl；Or E26Represent (CO) E19；Or E26Represent phenyl, E26It is to be unsubstituted or taken through at least one group as follows Generation, and alkyl that it is 1 to 20 selected from carbon number that at least one described group, which is, halogen atom, carbon number be 1 to 4 haloalkyl, OE17、SE18、NE19E20OrBut condition is the light starting of structure shown in formula (III) as described Agent (E-1) has at least one
5. photosensitive resin composition according to claim 4, wherein the light initiator of structure shown in the formula (III) (E-1) in, E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom, carbon number as 1 to 20 alkyl,COE16Or NO2；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is separately common to representThe E of wherein at least one1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8ForZ1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, the carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one described group is to be selected from halogen atom, OE17、SE18、COOE17、CONE19E20Or PO (OCkH2k+1)2；Or
E13It is 2 to 20 alkyl to represent carbon number, and the carbon number is to be mixed with to have one or more O, S, NE for 2 to 20 alkyl26Or CO；Or
E13Phenyl or naphthyl is represented, and it is respectively unsubstituted or through at least oneOr COE16Substitution；
E14Represent carbon number as 1 to 20 alkyl, phenyl or carbon number as 1 to 8 alkoxy；
E15It is 3 to 20 heteroaryl to represent phenyl, naphthyl, carbon number, and it is respectively unsubstituted or through at least one base as follows Group's substitution, and at least one described group is selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, OE17、SE18, It is miscellaneous to have the alkyl that at least one O or S and carbon number are 2 to 20, or it is respectively through the alkyl substitution that one or more carbon numbers are 1 to 20, The carbon number for 1 to 20 alkyl is unsubstituted or through at least one substituent group as follows, and it is described at least one Group is to be selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl Heteroaryloxycarbonyl that aryloxycarbonyl that base, carbon number are 6 to 20, carbon number are 4 to 20, OE17、SE18、NE19E20Or PO (OCkH2k+1)2；Or
E15It is 1 to 20 alkyl to represent carbon number, the carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one described group is to be selected from OE17、SE18, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 Heteroaryl, NE19E20、COOE17、CONE19E20Or PO (OCkH2k+1)2；
E'14Represent to have and be directed to E14One of those in definition；
E'15Represent to have and be directed to E15One of those in definition；
E16Represent phenyl, E16It is to be unsubstituted or through at least one substituent group as follows, and at least one described group It is to be selected from OE17、SE18、NE19E20, be mixed with least one O, S or NE26And carbon number is 2 to 20 alkyl；Or
E16Represent phenyl, and the phenyl is to replace through at least one carbon number for 1 to 20 alkyl, wherein the carbon number be 1 to 20 alkyl is unsubstituted or through at least one substituent group as follows, and at least one described group is to be selected from halogen Atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl, carbon number be 6 to 20 Heteroaryloxycarbonyl, OE that aryloxycarbonyl, carbon number are 4 to 2017、SE18Or NE19E20；Or
E16It is 1 to 20 alkyl to represent carbon number, and the carbon number that represents is unsubstituted as 1 to 20 alkyl or through as follows At least one substituent group, and at least one described group is 3 to 6 selected from halogen atom, phenyl, OH, SH, CN, carbon number Alkenyloxy group, OCH2CH2(CO)O(R1)、O(CO)-(R1) or (CO) O (R1)；
E17It is 1 to 20 alkyl to represent carbon number, the carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one described group is to be selected from halogen atom, OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1)、 Carbon number is 3 to 20 cycloalkyl, wherein the carbon number is not to be mixed with or be mixed with least one O for 3 to 20 cycloalkyl；Or
E17It is 2 to 20 alkyl to represent carbon number, and the carbon number is to be mixed with least one O for 2 to 20 alkyl；
E18Represent and pass through (CO) OE17Substituted methyl；
E19And E20Independently represent hydrogen atom, phenyl, carbon number as 1 to 20 alkyl, carbon number as 1 to 8 alkanoyl or carbon number For 1 to 8 alkanoyl epoxide；Or
E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms being bonded, the heteroaromatic ring system is without taking Generation or warpSubstitution, but condition is the smooth initiator (E- of structure shown in formula (III) as described 1) there is at least oneOr
6. photosensitive resin composition according to claim 4, wherein the light initiator of structure shown in the formula (III) (E-1) in, E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom；Or
E1And E2、E3And E4Or E5And E6It is separately common to representAnd an at least E1And E2、E3 And E4Or E5And E6ForOr
E3RepresentCOE16、NO2OrOr
E7RepresentOr COE16；
E9、E11And E12Represent hydrogen atom；
E10Represent hydrogen atom, OE17Or COE16；
Z1Represent CO or singly-bound；
E13It is 1 to 20 alkyl to represent carbon number, the carbon number for 1 to 20 alkyl be unsubstituted or through it is as follows at least One substituent group, and at least one described group is to be selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2；Or
E13It is 2 to 20 alkyl to represent carbon number, and the carbon number is mixed with least one O for 2 to 20 alkyl；Or
E13Represent phenyl；
K represents integer 2；
E14It is 1 to 20 alkyl or thienyl to represent carbon number；
E15Phenyl or naphthyl is represented, and it is respectively unsubstituted or through at least one OE17Or carbon number replaces for 1 to 20 alkyl；Or
E15It is 1 to 20 alkyl to represent thienyl, hydrogen atom or carbon number, wherein the carbon number is without taking for 1 to 20 alkyl Generation or through at least one substituent group as follows, and at least one described group is to be selected from OE17、SE18, carbon number be 3 to 8 Cycloalkyl, NE19E20Or COOE17；Or
E15It is 2 to 20 alkyl to represent carbon number, and the carbon number is mixed with for 2 to 20 alkyl and has SO2；
E16Phenyl or naphthyl is represented, it is respectively unsubstituted or through at least one substituent group as follows, and described at least one Individual group is to be selected from OE17、SE18、NE19E20Or the alkyl that carbon number is 1 to 20；Or
E16Represent thienyl；
E17It is 1 to 20 alkyl that hydrogen atom, carbon number, which are represented, as 1 to 8 alkanoyl or carbon number, and the carbon number is 1 to 20 alkyl It is to be unsubstituted or through at least one substituent group as follows, and at least one described group is to be selected from halogen atom, O (CO)-(R1)、O(CO)-(R6), or it is mixed with the cycloalkyl that at least one O and carbon number are 3 to 20；Or
E17It is 2 to 20 alkyl to represent carbon number, and the carbon number is mixed with least one O for 2 to 20 alkyl；
E18Represent carbon number as 3 to 20 cycloalkyl, carbon number as 1 to 20 alkyl, and the carbon number for 1 to 20 alkyl be without Replace or through at least one OH, O (CO)-(R6) or (CO) OE17Substitution；Or
E18Phenyl is represented, the phenyl is to be unsubstituted or replace through at least one halogen atom；
E19And E20It is that separately to represent carbon number as 1 to 8 alkanoyl or carbon number be 1 to 8 alkanoyl epoxide；Or
E19And E20It is to be formed to be mixed with have O five yuan or hexa-atomic saturated rings together with the nitrogen-atoms being bonded, but condition is as described The smooth initiator (E-1) of structure shown in formula (III) has at least
7. photosensitive resin composition according to claim 1, wherein the hot acid with structure shown in formula (I) occurs Agent (F) is selected from as the group combined by aromatic sulfonic acid ester, aliphatic sulphonic acid ester and perfluoroalkyl sulfonate ester.
8. photosensitive resin composition according to claim 1, wherein, the use based on the alkali soluble resin (C) Measure as 100 parts by weight, the usage amount of the pigment (A) is 30 parts by weight to 300 parts by weight；The usage amount of the dyestuff (B) is 5 Parts by weight are to 50 parts by weight；The usage amount of the compound (D) with ethene unsaturated group is 20 parts by weight to 200 weight Part；The usage amount of the smooth initiator (E) is 10 parts by weight to 100 parts by weight；The hot acid hair with structure shown in formula (I) The usage amount of raw agent (F) is 0.1 parts by weight to 10 parts by weight；The usage amount of the solvent (G) is 500 parts by weight to 5000 weight Part.
9. photosensitive resin composition according to claim 2, wherein, the use based on the alkali soluble resin (C) Measure as 100 parts by weight, the usage amount of first alkali soluble resin (C-1) is 0 parts by weight to 90 parts by weight.
10. photosensitive resin composition according to claim 4, wherein, the use based on the alkali soluble resin (C) Measure as 100 parts by weight, the usage amount of the light initiator (E-1) with structure shown in formula (III) is 0.1 parts by weight to 15 weights Measure part
11. a kind of manufacture method of colored filter, it is the photoresist any one of usage right requirement 1 to 10 Constituent one pixel layer of formation.
12. a kind of colored filter, it is as obtained by the method described in claim 11.
13. a kind of liquid crystal display, it is characterised in that include the colored filter described in claim 12.
CN201611234706.XA 2015-12-31 2016-12-28 Photosensitive resin composition and application thereof Withdrawn CN106959581A (en)

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Application publication date: 20170718