CN108020989A - Photosensitive resin composition, color filter, method for manufacturing the same, and application thereof - Google Patents

Photosensitive resin composition, color filter, method for manufacturing the same, and application thereof Download PDF

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Publication number
CN108020989A
CN108020989A CN201711057616.2A CN201711057616A CN108020989A CN 108020989 A CN108020989 A CN 108020989A CN 201711057616 A CN201711057616 A CN 201711057616A CN 108020989 A CN108020989 A CN 108020989A
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alkyl
group
phenyl
mixed
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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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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)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a photosensitive resin composition, a color filter, a manufacturing method thereof and application thereof. The photosensitive resin composition comprises a pigment (A), an alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (C), a photoinitiator (D) and a solvent (E), wherein the ethylenically unsaturated group-containing compound (C) comprises an ethylenically unsaturated group-containing compound (C-1) having a structure represented by formula (1). The color filter prepared by the photosensitive resin composition has good sputtering resistance.

Description

Photosensitive polymer combination, colored filter and its manufacture method and its application
Technical field
The invention relates to a kind of photosensitive polymer combination, colored filter and its manufacture method and its application, and In particular to a kind of photosensitive polymer combination, the colored filter obtained by the photosensitive polymer combination has good Resistance to sputter.
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 mainstream processing procedure.
The processing procedure of dispersion method is that first coloring pigment is scattered in photoresist, then the photoresist is coated on glass On glass substrate, through overexposure, imaging and etc., you can be made specific pattern.It is repeated to operate three times, you can red (R) is made, The pattern of the pixel shader layer of green (G) and blue (B), can optionally protect in applying on the pattern of pixel shader layer afterwards Film.
The photosensitive polymer combination disclosed in Japanese Unexamined Patent Publication 2001-075273, it includes the unsaturated monomer of carboxylic acid group Monomer with containing glycidyl polymerize obtained by alkali soluble resin of the polymer as photoresist.However, this is practised Know that colored filter made from the photosensitive polymer combination of technology but has the problem of resistance to sputter is bad.
Therefore, the problem of how overcoming resistance to sputter bad is to reach the requirement of current industry, for technology belonging to the present invention Make great efforts the target of research in field.
The content of the invention
One aspect of the present invention is to provide a kind of photosensitive polymer combination, and it includes pigment (A), alkali-soluble tree Fat (B), the compound (C) of the unsaturated group containing ethene, light initiator (D) and solvent (E), wherein unsaturated group containing ethene Compound (C) include the compound (C-1) of the unsaturated group containing ethene.
Another aspect of the present invention is to provide a kind of manufacture method of colored filter, it is to use above-mentioned photonasty Resin combination forms a pixel layer.
Another aspect of the invention is to provide a kind of colored filter, it is made by above-mentioned manufacture method.
Another aspect of the invention is to provide a kind of liquid crystal display device, it can include foregoing colored filter.
Above-mentioned aspect according to the present invention, provides a kind of photosensitive polymer combination first.Above-mentioned photosensitive resin composition Thing can include pigment (A), alkali soluble resin (B), the compound (C) of the unsaturated group containing ethene, light initiator (D) and molten Agent (E), following division it.
Photosensitive polymer combination
Pigment (A)
Present invention pigment (A) referred to herein can be such as, but not limited to the group of inorganic pigment, organic pigment or both Close.
Above-mentioned inorganic pigment is such as, but not limited to the metallic compounds such as metal oxide, metal complex；It is preferred that the nothing Machine pigment can be selected from the oxide of the metals such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, sub- lead, antimony, aforementioned metal it is compound Oxide and metal complex.
In a specific example of the present invention, above-mentioned organic pigment 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 face Material can the individually a kind of or a variety of uses of mixing.
In one embodiment, the average grain diameter of pigment (A) is preferably 10nm to 200nm, is more preferably 20nm to 150nm, again More preferably 30nm to 130nm.
In one embodiment of the invention, the usage amount based on alkali soluble resin (B) is 100 parts by weight, pigment (A) Usage amount scope is 5 parts by weight to 300 parts by weight, preferably 10 parts by weight to 250 parts by weight, so with 15 parts by weight to 200 weights Part is measured as more preferably.
When if necessary, pigment (A) also can optionally use dispersant, such as, but not limited to：Cationic system, anion The interfacial agent of system, nonionic system, both sexes, polysiloxane series, fluorine system etc..
Foregoing interfacial agent be such as, but not limited to polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether, The polyethylene oxide alkyl ethers class of polyethylene oxide oil ether etc.；Polyethylene oxide octyl group phenylate, polyethylene oxide nonyl phenylate etc. Polyethylene oxide alkylbenzene ethers interfacial agent；Polyethylene glycol dilaurate, polyglycol distearate etc. gather Ethylene glycol diester class interfacial agent；Sorbitan fatty acid ester class interfacial agent；The polyesters interface of aliphatic acid modification Activating agent；The polyurethanes interfacial agent of tertiary amine modification；The commodity of the model KP of SHIN-ETSU HANTOTAI's chemical industry manufacture, Commodity, the type of common prosperity society oil chemical industry manufacture of the model SF-8427 of Toray Dow Corning Silicon manufactures Number for Polyflow commodity, get Ke Mu companies (Tochem Products Co., Ltd.) manufacture model F-Top business The production of the product for the model Megafac that product, big Japanese printing ink chemical industry manufacture, the model Fluorad of Sumitomo 3M manufactures The commodity of model Asahi Guard and Surflon that product, Asahi Glass manufacture.Above-mentioned interfacial agent can be individually a kind of or mixed Close a variety of uses.
Alkali soluble resin (B)
First alkali soluble resin (B-1)
The alkali soluble resin (B) of the present invention can include the first alkali soluble resin (B-1).First alkali soluble resin (B-1) it is as obtained by a mixture carries out polymerisation, the mixture, which includes one, has the epoxy of at least two epoxy groups Compound (b-1-1), and a compound (b-1-2) with least one carboxylic acid group and at least one ethene unsaturated group. Said mixture is also selectively included in compound carboxylic acid anhydride (b-1-3) and compound (b-1-4) containing epoxy group at least One.
It is preferred that the epoxide (b-1-1) with least two epoxy groups is with as shown in formula (4) or formula (5) Structure.The narration of " epoxide (b-1-1) can be with the structure as shown in formula (4) or formula (5) " also contemplated with such as formula (4) compound of the structure shown in and the compound with the structure as shown in formula (5) exist and are used as epoxide at the same time (b-1-1) situation.
Specifically, it is, for example, with such as formula (4) Suo Shi to be somebody's turn to do the epoxide (b-1-1) with least two epoxy groups Structure：
In formula (4), R1c、R2c、R3cAnd R4cHydrogen atom, halogen atom, the alkane that carbon number is 1 to 5 are represented independently of one another The aralkyl that the aromatic radical or carbon number that alkoxy that base, carbon number are 1 to 5, carbon number are 6 to 12 are 6 to 12.
The epoxide (b-1-1) with least two epoxy groups of previously described formula (4) may include by bisphenol fluorene type chemical combination Thing (bisphenol fluorene) and the bisphenol fluorene containing epoxy group obtained by halogenated epoxy propane (epihalohydrin) reaction Type compound, but be not limited to this.
As the concrete example of above-mentioned bisphenol fluorene type compound, it is such as, but not limited to：Double (4- hydroxy phenyls) fluorenes [9,9- of 9,9- Bis (4-hydroxy phenyl) fluorene], double (the 4- hydroxy-3-methyls phenyl) fluorenes [9,9-bis (4-hydroxy- of 9,9- 3-methylphenyl) fluorene], double (4- hydroxyl -3- chlorphenyls) fluorenes [9,9-bis (4-hydroxy-3- of 9,9- 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) is such as, but not limited to epichlorohydrin (epichlorohydrin) or bromo- 1,2 epoxy prapanes of 3- (epibromohydrin) etc..
The above-mentioned bisphenol fluorene type compound containing epoxy group by obtained by bisphenol fluorene type compound and the reaction of halogenated epoxy propane Including but not limited to：(1) commodity manufactured by Nippon Steel chemical (Nippon Steel Chemical Co., Ltd)：Such as ESF-300 etc.；(2) commodity manufactured by Osaka gas (Osaka Gas Co., Ltd)：Such as PG-100, EG-210 etc.；(3) Commodity manufactured by short message science and technology (S.M.S Technology Co., Ltd)：Such as SMS-F9PhPG, SMS-F9CrG, SMS- F914PG etc..
It is preferred that the epoxide (b-1-1) with least two epoxy groups also can be with the knot as shown in formula (5) Structure：
In formula (5), R5cTo R18cHydrogen atom, halogen atom, the alkyl or carbon number that carbon number is 1 to 8 are represented independently of one another For 6 to 15 aromatic radical；And g represents 0 to 10 integer.
The epoxide (b-1-1) with least two epoxy groups of previously described formula (5) is, for example, by alkali metal hydrogen In the presence of oxide, make that there is the compound of following formula (5-1) structure to be reacted and be obtained with halogenated epoxy propane.
In formula (5-1), R5cTo R18cAnd the definition of g be respectively with the R in formula (5)5cTo R18cAnd the definition phase of g Together, do not repeat separately herein.
The epoxide (b-1-1) with least two epoxy groups of previously described formula (5) is, for example, to exist in acid catalyst Under, after with such as condensation reaction is carried out with the compound of following formula (5-2) structure and phenol (phenol) class, formation has formula The compound of (5-1) structure.Then, de-hydrogen halide is carried out by the halogenated epoxy propane for adding excess (dehydrohalogenation), the epoxide (b-1- with least two epoxy groups as shown in formula (5) is obtained 1)。
In formula (5-2), R19cWith R20cIndependently of one another represent hydrogen atom, halogen atom, carbon number be 1 to 8 alkyl or Carbon number is 6 to 15 aromatic radical；T1And T2The alkyl or carbon number that expression halogen atom, carbon number are 1 to 6 independently of one another are 1 to 6 Alkoxy.It is preferred that the halogen atom is, for example, chlorine or bromine, which is, for example, methyl, ethyl or the tert-butyl group, the alkoxy For example, methoxy or ethoxy.
Above-mentioned phenols is such as, but not limited to：Phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), the third phenol of n- (n-propylphenol), isobutyl phenol (isobutylphenol), t- fourths phenol (t-butylphenol), octyl phenol (octylphenol), nonyl phenol (nonylphenol), stubble phenol (xylenol), methyl butyl phenol (methylbutylphenol), di-tert-butylphenol (di-t-butylphenol), phenol ethylene (vinylphenol), propylene benzene Phenol (propenylphenol), acetylene phenol (ethinylphenol), penta phenol of ring (cyclopentylphenol), cyclohexyl Phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc..Above-mentioned phenols can individually a kind of or mixing A variety of uses.
In a specific example of the present invention, the usage amount based on the above-mentioned compound with formula (5-2) structure is 1 mole, The usage amount scope of phenols is 0.5 mole to 20 moles, preferably 2 moles to 15 moles.
Above-mentioned acid catalyst is such as, but not limited to：Hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid (p-toluenesulfonic Acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous Aluminum chloride (anhydrous Aluminium chloride), zinc chloride (zinc chloride) etc., wherein preferable with p-methyl benzenesulfonic acid, sulfuric acid or hydrochloric acid. Above-mentioned acid catalyst can the individually a kind of or a variety of uses of mixing.
Though the usage amount of above-mentioned acid catalyst is not particularly limited, based on the above-mentioned compound with formula (5-2) structure Usage amount is 100wt%, and the usage amount scope 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.Above-mentioned organic solvent is for example but unlimited In：Toluene (toluene), dimethylbenzene (xylene) or methyl iso-butyl ketone (MIBK) (methyl isobutyl ketone) etc..It is above-mentioned Organic solvent can the individually a kind of or a variety of uses of mixing.
In a specific example of the present invention, it is based on the compound with formula (5-2) structure and the usage amount summation of phenols 100wt%, the usage amount scope of above-mentioned organic solvent is 50wt% to 300wt%, preferably 100wt% to 250wt%.It is above-mentioned The operation temperature of condensation reaction be 40 DEG C to 180 DEG C, the operating time for 1 hour to 8 it is small when.
After above-mentioned condensation reaction is completed, it can be neutralized or washing process.Above-mentioned neutralisation treatment is by after reaction The pH value of solution be adjusted to 3 to 7, preferably 5 to 7.Neutralizer can be used in above-mentioned washing process, which is basic species Matter, such as, but not limited to：The alkali such as sodium hydroxide (sodium hydroxide), potassium hydroxide (potassium hydroxide) Metal hydroxides；The alkaline earths such as calcium hydroxide (calcium hydroxide), magnesium hydroxide (magnesium hydroxide) Metalloid hydroxide；Secondary second triamine (diethylene triamine), three times second tetramine (triethylene Tetramine), the organic amine such as aniline (aniline), phenylenediamine (phenylene diamine)；And ammonia (ammonia), phosphorus Acid dihydride sodium (sodium dihydrogen phosphate) etc..Above-mentioned washing process can use prior art method to carry out, for example, In solution after the reaction, the aqueous solution containing neutralizer is added, extraction is repeated.Neutralized processing or washing process Afterwards, handled through heating under reduced pressure, unreacted phenols and solvent are given into distillation, and concentrated, you can acquisition has formula (5-1) The compound of shown structure.
Above-mentioned halogenated epoxy propane is such as, but not limited to such as：Epichlorohydrin (3-chloro-1,2- Epoxypropane), the bromo- 1,2 epoxy prapanes of 3- (3-bromo-1,2-epoxypropane) or combinations of the above.Carry out Before above-mentioned de-hydrogen halide, it can in advance add or the alkali metal hydrogen-oxygens such as sodium hydroxide, potassium hydroxide are added in reaction process Compound.The operation temperature of above-mentioned de-hydrogen halide be 20 DEG C to 120 DEG C, operating time scope for 1 hour to 10 it is small when.
Its aqueous solution can also be used in the alkali metal hydroxide added in above-mentioned de-hydrogen halide.In this concrete example In, can be in decompression or normal while above-mentioned alkali metal hydroxide aqueous solution is continuously added in de-hydrogen halide system Pressure, continuous still water outlet and halogenated epoxy propane, thereby separate and remove water, while can continuously return halogenated epoxy propane It flow in reaction system.
Before above-mentioned de-hydrogen halide carries 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 it is small when, add alkali metal hydroxide or its aqueous solution, at a temperature of 20 DEG C to 120 DEG C, make its react 1 hour to 10 Hour, to carry out de-hydrogen halide.
It is 1 based on the hydroxyl total yield in the above-mentioned compound with formula (5-1) structure in a specific example of the present invention Equivalent, the usage amount of above-mentioned halogenated epoxy propane can be 1 equivalent to 20 equivalents, preferably 2 equivalents to 10 equivalents.Based on above-mentioned tool It is 1 equivalent to have the hydroxyl total yield in the compound of formula (5-1) structure, the alkali metal hydrogen-oxygen added in above-mentioned de-hydrogen halide The usage amount of compound can be 0.8 equivalent to 15 equivalents, preferably 0.9 equivalent to 11 equivalents.
In order to be smoothed out above-mentioned de-hydrogen halide, except the alcohols such as methanol, ethanol can be added, diformazan can be also added The polarity of the aprotics (aprotic) such as sulfone (dimethyl sulfone), dimethyl sulfoxide (dimethyl sulfoxide) is molten Matchmaker etc. is reacted.In the case of using alcohols, the total amount based on above-mentioned halogenated epoxy propane is 100wt%, alcohols Usage amount can be 2wt% to 20wt%, preferably 4wt% to 15wt%.In the example using the polarity solvent of aprotic, Total amount based on halogenated epoxy propane is 100wt%, and the usage amount of the polarity solvent of aprotic can be 5wt% to 100wt%, Preferably 10wt% to 90wt%.
After de-hydrogen halide is completed, washing process is optionally carried out.Afterwards, removed using the mode of heating decompression Remove polarity solvent of halogenated epoxy propane, alcohols and aprotic etc..Above-mentioned heating decompression be, for example, in temperature for 110 DEG C extremely 250 DEG C, and pressure is to be carried out 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 sodium hydroxide, potassium hydroxide gold Belong to hydroxide aqueous solution, carry out de-hydrogen halide again.In de-hydrogen halide, there is formula (5-1) institute based on above-mentioned Hydroxyl total yield in the compound for the structure shown is 1 equivalent, the usage amount scope of alkali metal hydroxide for 0.01 mole extremely 0.3 mole, preferably 0.05 mole to 0.2 mole.The operating temperature range of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, Operating time scope for 0.5 hour to 2 it is small when.
After de-hydrogen halide is completed, by filtering and washing and etc. remove salt.Heating decompression can also be used Mode, gives distillation by toluene, methyl iso-butyl ketone (MIBK) equal solvent, and can obtain has at least two epoxies as shown in formula (5) The epoxide (b-1-1) of base.Above-mentioned formula (5) have the epoxide (b-1-1) of at least two epoxy groups for example but It is not limited to Japanese chemical drug (the Nippon Kayaku such as trade name NC-3000, NC-3000H, NC-3000S and NC-3000P Co.Ltd. the commodity manufactured by).
The foregoing compound (b-1-2) with least one carboxylic acid group and at least one ethene unsaturated group is, for example, to select From in the group being made 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) compounds as obtained by (methyl) acrylate of hydroxyl with dicarboxylic acid compound's reaction, Wherein dicarboxylic acid compound is including but not limited to adipic acid, succinic acid, maleic acid, phthalic acid；And (3) is by hydroxyl (methyl) acrylate and compound carboxylic acid anhydride reaction obtained by half ester compound, wherein hydroxyl (methyl) acrylate Such as, but not limited to 2- hydroxyethylmethacry,ates [(2-hydroxyethyl) acrylate], 2- hydroxy ethyl methyl acrylic acid Ester [(2-hydroxyethyl) methacrylate], 2- acrylates [(2-hydroxypropyl) Acrylate], 2- hydroxy propyl methacrylates [(2-hydroxypropyl) methacrylate], 4- hydroxybutyls third Olefin(e) acid ester [(4-hydroxybutyl) acrylate], 4- hydroxybutyl methacrylates [(4-hydroxybutyl) Methacrylate] or pentaerythritol acrylate trimethyl etc..Compound carboxylic acid anhydride described herein can be with following first alkali Compound carboxylic acid anhydride (b-1-3) contained by the mixture of soluble resin (B-1) is identical, therefore is repeated no more in this.
The mixture of above-mentioned first alkali soluble resin (B-1) is more selectively included compound carboxylic acid anhydride (b-1-3) And at least one of compound (b-1-4) containing epoxy group.Above-mentioned compound carboxylic acid anhydride (b-1-3) may be selected from by following (1) extremely (2) group formed：(1) succinic anhydrides (butanedioic anhydride), maleic anhydride (maleic Anhydride), itaconic anhydride (itaconic anhydride), phthalic anhydride (phthalic anhydride), tetrahydrochysene Phthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic Anhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene tetrahydrochysene O-phthalic Acid anhydrides (methyl endo-methylene tetrahydro phthalic anhydride), chlorendic anhydride (chlorendic Anhydride), glutaric anhydride or inclined three benzoyl oxides (1,3-dioxoisobenzofuran-5-carboxylic The dicarboxylic acid anhydride compound such as anhydride)；And (2) benzophenone tetracarboxylic dianhydrides (benzophenone Tetracarboxylic dianhydride, abbreviation BTDA), the quaternary such as double pyromellitic dianhydride or double phenylate tetracarboxylic acid dianhydrides Compound carboxylic acid anhydride.
The above-mentioned compound (b-1-4) containing epoxy group is, for example, selected from glycidyl methacrylate, 3,4- epoxy hexamethylenes Ylmethyl (methyl) acrylate, the glycidyl ether compound containing unsaturated group, the unsaturated compound containing epoxy group or on The group that the combination stated is formed.The foregoing glycidyl ether compound containing unsaturated group is such as, but not limited to trade name Denacol EX-111、EX-121Denacol、Denacol EX-141、Denacol EX-145、Denacol EX-146、 The compound (being above the commodity of Chang Lai chemical conversion industries Co., Ltd.) of Denacol EX-171, Denacol EX-192 etc..
Foregoing first alkali soluble resin (B-1) can be by the epoxide (b- with least two epoxy groups of formula (4) Polymerisation 1-1) is carried out with the compound (b-1-2) with least one carboxylic acid group and at least one ethene unsaturated group, The reaction product of hydroxyl is formed, then, then is added obtained by compound carboxylic acid anhydride (b-1-3) reacted.Contained based on above-mentioned The hydroxyl total yield of the reaction product of hydroxyl is 1 equivalent, and the equivalent of the anhydride group contained by compound carboxylic acid anhydride (b-1-3) is preferable It is more preferably 0.75 equivalent to 1 equivalent for 0.4 equivalent to 1 equivalent., can be in anti-when using multiple compound carboxylic acid anhydrides (b-1-3) Sequentially add in answering or add at the same time.When using dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride as carboxylic acid anhydrides chemical combination During thing (b-1-3), the molar ratio of dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride are preferably 1/99 to 90/10, more Good is 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 (B-1) can be by the epoxide (b- with least two epoxy groups of formula (5) 1-1) reacted, formed with the compound (b-1-2) with least one carboxylic acid group and at least one ethene unsaturated group The reaction product of hydroxyl, then, then by addition compound carboxylic acid anhydride (b-1-3) and/or the compound (b-1- containing epoxy group 4) carry out obtained by polymerisation.The epoxy having on the epoxide (b-1-1) of at least two epoxy groups based on formula (5) Base total yield is 1 equivalent, the above-mentioned compound (b-1-2) with least one carboxylic acid group and at least one ethene unsaturated group Acid value equivalent be preferably 0.8 equivalent to 1.5 equivalents, be more preferably 0.9 equivalent to 1.1 equivalents.Reaction based on above-mentioned hydroxyl The hydroxyl total amount of product is 100 molar percentages (mole %), and the usage amount of compound carboxylic acid anhydride (b-1-3) is preferably 10 and rubs You are % to 100 moles of %, is more preferably 20 moles of % to 100 moles of %, particularly good is 30 moles of % to 100 moles of %.
When preparing above-mentioned first alkali soluble resin (B-1), in order to accelerate to react, it will usually added in reaction solution Alkali compounds is as catalysts.Above-mentioned catalysts can be used alone or as a mixture, and above-mentioned catalysts include 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 (b-1-1) of few two epoxy groups with least one carboxylic acid group and at least one ethene unsaturated group The usage amount summation of compound (b-1-2) is 100 parts by weight, and the usage amount scope of catalysts is preferably 0.01 parts by weight extremely 10 parts by weight, so using 0.3 parts by weight to 5 parts by weight as more preferably.
In order to control the degree of polymerization, polymerization inhibitor (polymerization usually can be also added in reaction solution inhibitor).Above-mentioned polymerization inhibitor is such as, but not limited to：Methoxyl group phenol (methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), DBPC 2,6 ditertiary butyl p cresol (2,6-di-t-butyl-p- ) or phenthazine (phenothiazine) etc. cresol.Above-mentioned polymerization inhibitor can the individually a kind of or a variety of uses of mixing.It is based on The above-mentioned epoxide (b-1-1) with least two epoxy groups with least one carboxylic acid group and at least one ethene The usage amount summation of the compound (b-1-2) of unsaturated group is 100 parts by weight, and the usage amount scope of polymerization inhibitor is preferably 0.01 parts by weight to 10 parts by weight, so using 0.1 parts by weight to 5 parts by weight as more preferably.
When preparing the first alkali soluble resin (B-1), polymerization solvent can be used if necessary.It is anti-as above-mentioned polymerization Answer the concrete example of solvent, can enumerate as：The alcohol such as ethanol, propyl alcohol, isopropanol, butanol, isobutanol, 2- butanol, hexanol or ethylene glycol Class compound；The ketone compounds such as methyl ethyl ketone or cyclohexanone；The aromatic hydrocarbon compound such as toluene or dimethylbenzene；Match Luo element (cellosolve) or butyl matches the match Luo chlorins compound such as Luo plain (butyl 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. more 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 generally can individually or a variety of uses of mixing.Separately Outside, the acid value of above-mentioned first alkali soluble resin (B-1) is preferably 50mgKOH/g to 200mgKOH/g, is more preferably 60mgKOH/g To 150mgKOH/g.
In addition, above-mentioned first alkali soluble resin (B-1) is by colloid osmotic chromatograph (Gel Permeation Chromatography, GPC) measure polystyrene conversion number average molecular weight be generally 500 to 10,000, preferably 800 to 8,000, it is more preferably 1,000 to 6,000.
In a specific example of the present invention, the usage amount based on alkali soluble resin (B) is 100 parts by weight, and the first alkali can The usage amount scope of soluble resin (B-1) is 0 parts by weight to 90 parts by weight, preferably 10 parts by weight to 80 parts by weight, so with for 20 parts by weight to 70 parts by weight is more preferably.When using the first alkali soluble resin (B-1), thus photosensitive polymer combination institute The resistance to sputter of the colored filter of formation is more preferably.
Second alkali soluble resin (B-2)
Alkali soluble resin (B) can further include the second alkali soluble resin (B-2), be by with one or more carboxylics The ethylene unsaturated monomer (b-2-1) and other copolymerizable ethylene unsaturated monomers (b-2-2) of acid or carboxylic acid anhydrides After combined polymerization, react and obtain with the ethylene unsaturated monomer (b-2-3) with epoxy group.
In one embodiment, the second alkali soluble resin (B-2) is that will first have one or more carboxylic acids or carboxylic acid Ethylene unsaturated monomer (b-2-2) the progress double bond that the ethylene unsaturated monomer (b-2-1) of acid anhydride is copolymerizable with other is total to Polymerisation, to form a polymer, the wherein side chain of this polymer has carboxylic acid group.Then, in the side chain of this polymer Carboxylic acid group carries out addition reaction with the ethylene unsaturated monomer (b-2-3) with epoxy group, and the second alkali-soluble tree is made Fat (B-2).
In another embodiment, the second alkali soluble resin (B-2) is first that other copolymerizable ethene are unsaturated Monomer (b-2-2) carries out double bond copolymerization with the ethylene unsaturated monomer (b-2-3) with epoxy group, poly- to form one The side chain of compound, wherein this polymer has epoxy group.Then, the epoxy group in the side chain of this polymer is with having one or one The ethylene unsaturated monomer (b-2-1) of a above carboxylic acid or carboxylic acid anhydrides carries out addition reaction, and the second alkali-soluble tree is made Fat (B-2).
In another embodiment, the second alkali soluble resin (B-2) is first that other copolymerizable ethene are unsaturated Monomer (b-2-2) carries out double bond copolymerization with the ethylene unsaturated monomer (b-2-3) with epoxy group, poly- to form one The side chain of compound, wherein this polymer has epoxy group.Then, the epoxy group in the side chain of this polymer is with having one or one After the ethylene unsaturated monomer (b-2-1) of a above carboxylic acid or carboxylic acid anhydrides carries out addition reaction, further with anhydrides chemical combination Thing carries out half-esterification reaction and the second alkali soluble resin (B-2) is made.
Foregoing copolymerization is carried out in the presence of polymerization initiators and solvent, wherein the polymerization initiators It can be such as, but not limited to the double -2- methylbutyronitriles of 2,2'- azos or 2,2'- azo-two-(2,4 dimethyl-penten cyanogen), and it is described molten Agent can be identical with following solvents (E), does not repeat separately herein.
The above-mentioned ethylene unsaturated monomer (b-2-1) with one or more carboxylic acids or carboxylic acid anhydrides, wherein, have The ethylene unsaturated monomer of one or more carboxylic acids can be more including but not limited to unsaturated monocarboxylic compound, unsaturation Carboxylic acid compound, the polycyclic compound with unsaturated group and a carboxylic acid group, or with unsaturated group and multiple carboxylic acid groups Polycyclic compound.
Foregoing unsaturated monocarboxylic compound is such as, but not limited to (methyl) acrylic acid, butenoic acid, α-chloroacrylic acid, ethyl 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 polycaprolactone polyols Alcohol mono acrylic ester can be that East Asia is synthetically produced, the commodity of model ARONIX M-5300.
It is foregoing unsaturation multi-carboxylic acid compounds can including but not limited to maleic acid, fumaric acid, mesaconic acid, itaconic acid or Citraconic acid etc..
It is bicyclic that the foregoing polycyclic compound with unsaturated group and a carboxylic acid group is such as, 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.
Foregoing polycyclic compound such as two ring of 5,6- dicarboxyls acidic group [2.2.1] with unsaturated group and multiple carboxylic acid groups Hept-2-ene" etc..
It is preferred that the foregoing ethylene unsaturated monomer with one or more carboxylic acids is selected from acrylic acid, first Base acrylic acid, 2- methacryloyloxyethyls succinate, 2- methacryl base oxethyl hexahydrobenzene dicarboxylic acid esters, or on State the combination of compound.
The foregoing ethylene unsaturated monomer (b-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 is such as, but not limited to unsaturated carboxylic acid anhydrides compound or tool There is the polycyclic compound of unsaturated group and carboxylic acid anhydrides.
Foregoing unsaturated carboxylic acid anhydrides compound is such as, 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 is such as, but not limited to 5,6- dicarboxylic anhydrides Two rings [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 (b-2-1) with one or more carboxylic acids or carboxylic acid anhydrides can be individually a kind of Or a variety of uses of mixing.
In a specific example of the present invention, one or more carboxylics are had based on the second alkali soluble resin (B-2) Acid or the ethylene unsaturated monomer (b-2-1) of carboxylic acid anhydrides and other copolymerizable ethylene unsaturated monomers (b-2-2) are altogether The usage amount of polymerization monomer is 100 parts by weight, has the unsaturated list of the ethene of one or more carboxylic acids or carboxylic acid anhydrides The usage amount scope of body (b-2-1) is 10 parts by weight to 90 parts by weight, preferably 15 parts by weight to 85 parts by weight, so with 20 weight Part is to 80 parts by weight for more preferably.
Other foregoing copolymerizable ethylene unsaturated monomers (b-2-2) are such as, but not limited to (methyl) acrylic acid alkyl Ester, (methyl) acrylic acid alicyclic ester, (methyl) benzyl acrylate, unsaturated dicarboxylic ester, (methyl) hydroxyalkyl acrylate, With the unsaturated compound beyond (methyl) acrylate-based polyethers, styrenic or above-claimed cpd.
Above-mentioned (methyl) alkyl acrylate be such as, but not limited to (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, The second butyl ester of (methyl) acrylic acid or (methyl) acrylate tert-buthyl etc..
Above-mentioned (methyl) acrylic acid alicyclic ester for example contains but is not limited to (methyl) cyclohexyl acrylate, (methyl) propylene Acid -2- methyl cyclohexyls, the bicyclic pentyl ester of (methyl) acrylic acid { or tricyclic [5.2.1.02,6] decyl- 8- bases (methyl) acrylic acid Ester }, two cyclopentyloxy ethyl ester of (methyl) acrylic acid, (methyl) isobornyl acrylate or (methyl) acrylic acid tetrahydrofuran ester Deng.
Above-mentioned (methyl) benzyl acrylate is such as, but not limited to (methyl) phenyl acrylate or (methyl) acrylic acid benzene Methyl esters etc..
Foregoing unsaturated dicarboxylic ester is such as, but not limited to diethyl maleate, diethyl fumarate or diethyl itaconate Deng.
Foregoing (methyl) hydroxyalkyl acrylate is such as, but not limited to (methyl) 2-Hydroxy ethyl acrylate or (methyl) propylene Acid -2- hydroxy propyl esters etc..
It is foregoing with (methyl) acrylate-based polyethers be such as, but not limited to polyethyleneglycol (methyl) acrylate or Polypropylene glycol list (methyl) acrylate etc..
Foregoing styrenic is such as, but not limited to styrene, α-methylstyrene, m- methyl styrene, p- first Base styrene or p-methoxystyrene etc..
Unsaturated compound beyond above-claimed cpd is such as, but not limited to acrylonitrile, methacrylonitrile, vinyl chloride, inclined two Vinyl chloride, acrylamide, Methacrylamide, ethene ethyl ester, 1,3- butadiene, isoprene, 2,3- dimethyl 1,3- fourths two Alkene, N- succimide base -3- maleimidobenzoyls ester, N- succimide base -4- malimidobutanoates, N- fourths Imidodicarbonic diamide base -6- maleimidohexanoic acids ester, N- succimide base -3- maleimidopropionic acids ester, N- (9- acridinyls) Maleimide, N- octyl groups maleimide (N-octylmaleimide), N- N-cyclohexylmaleimides (N- ) or N-phenylmaleimide (N-phenylmaleimide) etc. cyclohexylmaleimide.
Other foregoing copolymerizable ethylene unsaturated monomers (b-2-2) can the individually a kind of or a variety of uses of mixing.
It is preferred that other foregoing copolymerizable ethylene unsaturated monomers (b-2-2) are to be selected from (methyl) acrylic acid Methyl esters, (methyl) butyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylate tert-buthyl, (methyl) propylene Sour benzene methyl, the bicyclic pentyl ester of (methyl) acrylic acid, isobornyl methacrylate, two cyclopentyloxy ethyl ester of (methyl) acrylic acid, Any combination of styrene, p-methoxystyrene or above-claimed cpd.
In a specific example of the present invention, one or more are had based on second alkali soluble resin (B-2) The ethylene unsaturated monomer of carboxylic acid or carboxylic acid anhydrides (b-2-1) and other copolymerizable ethylene unsaturated monomers (b-2-2) The usage amount summation of combined polymerization monomer is 100 parts by weight, other copolymerizable ethylene unsaturated monomer (b-2-2's) makes Amount ranges are 10 parts by weight to 90 parts by weight, preferably 15 parts by weight to 85 parts by weight, so with 20 parts by weight to 80 parts by weight For more preferably.
Ethylene unsaturated monomer (b-2-3) with epoxy group is such as, but not limited to (methyl) propylene with epoxy group Ester compound, the alpha-alkyl acrylate compounds with epoxy group or glycidyl ether compounds etc..
Foregoing (methyl) acrylate compounds with epoxy group be such as, but not limited to (methyl) Glycidyl Acrylate, (methyl) acrylic acid 2- methyl polyglycidyl, (methyl) acrylic acid 3,4- epoxies butyl ester, (methyl) acrylic acid 6,7- epoxies heptyl ester, 3,4- epoxycyclohexyls (methyl) acrylate or 3,4- epoxycyclohexyl-methyls (methyl) acrylate etc..
The foregoing alpha-alkyl acrylate compounds with epoxy group be such as, but not limited to α-ethylacrylate polyglycidyl, α-n-propyl Glycidyl Acrylate, α-n-butyl polyglycidyl or α-ethylacrylate -6,7- epoxy heptyl esters etc..
Aforementioned epoxy ether compound is such as, 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..
Ethylene unsaturated monomer (b-2-3) with epoxy group can the individually a kind of or a variety of uses of mixing.
It is preferred that the foregoing ethylene unsaturated monomer (b-2-3) with epoxy group is to be selected from glycidyl Propyl ester, methacrylic acid 2- methyl polyglycidyl, 3,4- epoxycyclohexyl-methyls methacrylate, methacrylic acid 6,7- rings Oxygen heptyl ester, o- vinyl benzene methyl glycidyl ethers, m- vinyl benzene methyl glycidyl ethers, p- vinyl benzene methyl epoxy third Any combination of ether or above-claimed cpd.
In a specific example of the present invention, one or more carboxylics are had based on the second alkali soluble resin (B-2) Acid or the ethylene unsaturated monomer (b-2-1) of carboxylic acid anhydrides and other copolymerizable ethylene unsaturated monomers (b-2-2) are altogether The usage amount summation of polymerization monomer is 100 parts by weight, has the usage amount of the ethylene unsaturated monomer (b-2-3) of epoxy group Scope is 1 parts by weight to 35 parts by weight, preferably 3 parts by weight to 30 parts by weight, so using 5 parts by weight to 25 parts by weight as more preferably.
In addition, above-mentioned second alkali soluble resin (B-2) is by colloid osmotic chromatograph (Gel Permeation Chromatography, GPC) measure polystyrene conversion number average molecular weight 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 alkali soluble resin (B) is 100 parts by weight, and the second alkali is solvable Property resin (B-2) usage amount scope be 10 parts by weight to 100 parts by weight, preferably 20 parts by weight to 90 parts by weight, so with 30 Parts by weight are to 80 parts by weight for more preferably.
The compound (C) of the unsaturated group containing ethene
The compound (C-1) of the unsaturated group containing ethene
The compound (C) of the unsaturated group containing ethene of the present invention includes the compound (C-1) of the unsaturated group containing ethene, It has the structure as shown in formula (1).
In formula (1), R1aThe alkyl for being 1 to 4 for identical or each different hydrogen atoms or carbon number；R2aTo be identical or each From the alkyl that different carbon numbers is 1 to 4；And s and the t mean values that each representative unit repeats, and the summation of s and t is 0.4 to 12.
In one embodiment, the summation of s and t preferably can be 0.8 to 8, so using the summation of s and t as 2 to 4 for more preferably.
Explanation is used in the compound of the unsaturated group containing ethene with the structure as shown in formula (1) of the present invention below (C-1) manufacture method.
The compound (C-1) of the unsaturated group containing ethene of the present invention, can first make 1,1 '-dinaphthol and oxirane compounds (alkylene oxide) or carbonic acid alkylidene ester (alkylene carbonate) react.Then, unsaturated group is being contained Monocarboxylic acid by dehydration condensation with the presence of acid catalyst, obtaining.In structure as shown in above formula (1), R1aDescribed The alkyl that carbon number is 1 to 4 is the alkyl of straight-chain or branched, alkenyl or alkynyl.In the present invention, R1aPreferably straight-chain Or the alkyl of branched.In structure as shown in above formula (1), R2aThe alkyl that the carbon number is 1 to 4 is straight-chain or branched Alkylidene.In the present invention, R2aPreferably carbon number is 2 or 3 alkylidene.1,1 '-dinaphthalene used in the present invention Phenol, although being not particularly limited, with (RS) -1,1 '-union -2-naphthol is preferred, and can be derived from S＆R CHIRAL CHEMICAL public affairs Department etc..In the present invention, the monocarboxylic acid containing unsaturated group can be exemplified as acrylic acid, methacrylic acid, ethylacrylic acid, Propylacrylate or butylacrylic acid etc., so the present invention is preferable using acrylic or methacrylic acid, and general city can be used Sell product.1, in the reaction of 1 '-dinaphthol and oxirane compounds, relative to 1 mole 1,1 '-dinaphthol, rubs using 0.5 to 24 Your oxirane compounds are reacted with 1,1 '-dinaphthol.In the reaction of 1,1 '-dinaphthol and carbonic acid alkylidene ester, phase 1 for 1 mole, 1 '-dinaphthol, using 2 to 5 moles of carbonic acid alkylidene ester and 1,1 '-dinaphthol is reacted.Alkylene oxide Compound or carbonic acid alkylidene ester are to can be used alone class, can also be mixed more than 2 species to use.
The concrete example of oxirane compounds, may be, for example, (carbon number 2 to 4) of ethylene oxide, propylene oxide, epoxy butane etc. Oxirane compounds.Also, the concrete example of carbonic acid alkylidene ester, may be, for example, ethylene carbonate (ethylene carbonate), (carbon number 1 to 4) of carbonic acid time propyl ester (propylene carbonate) or carbonic acid time butyl ester (butylene carbonate) etc. Carbonic acid alkylidene ester.
1, the reaction of 1 '-dinaphthol and oxirane compounds or carbonic acid alkylidene ester, is in sodium hydroxide, potassium hydroxide etc. Under base catalyst, when the reaction time 1 to 48 is small, carried out between 90 DEG C to 200 DEG C of reaction temperature.1,1 '-dinaphthol and alkylene oxide In the reaction of compound, it is 100 mass % based on reaction mixture, the base catalyst of 0.01 to 5 quality % can be used.1,1’- Dinaphthol is with the reaction of carbonic acid alkylidene ester, being 1 mole based on 1,1 '-dinaphthol, 0.01 to 0.5 mole of alkali can be used to urge Agent.
1,1 '-dinaphthol contracts with the reactant of oxirane compounds or carbonic acid alkylidene ester and the dehydration of (methyl) acrylic acid Close reaction in, relative to 1 mole 1,1 '-dinaphthol, (methyl) acrylic acid be use 0.1 to 10 mole.Dehydration condensation It is middle to be used as solvent person, the azeotropic solvent for the water that generation can be distilled off in the reaction can be used.Here, so-called azeotropic is molten Agent is the boiling point with 60 DEG C to 130 DEG C, and with the water person of can be easily detached, benzene, toluene, n-hexane, just particularly can be used 1 kind in the non-reacted organic solvent such as heptane, hexamethylene or mix two or more.The usage amount of solvent is mixed relative to reaction Thing is 100 mass %, and solvent is that 10 mass % to 70 mass % are preferred.
In dehydration condensation, the reaction time is that the scope that 60 DEG C to 150 DEG C of reaction temperature is when 1 hour small to 24 It is good, but from the reaction time shortening with for the viewpoint for preventing from polymerizeing, to be preferred at 75 DEG C to 120 DEG C.
For (methyl) acrylic acid of the commercially available product used as raw material, though it is generally the addition in (methyl) acrylic acid To polymerization inhibitors such as methoxyl group phenol, but also polymerization inhibitor can be added again in reaction.Polymerization inhibitor so can arrange Lift such as：Quinhydrones, to methoxyl group phenol, 2,4- dimethyl -6- tert-butyl phenols, 3- hydroxythiophenols, 1,4-benzoquinone, 2,5- dihydroxy-to benzene Quinone, phenthazine etc..It is 100 mass % relative to reaction mixture, the usage amount of polymerization inhibitor is 0.01 mass % to 1 matter Measure %.
The acid catalyst used in dehydration condensation, can arbitrarily select sulfuric acid, Loprazolam, trifluoromethayl sulfonic acid, The known person such as p-methyl benzenesulfonic acid.Relative to 1 mole (methyl) acrylic acid, the usage amount of above-mentioned acid catalyst is 0.01 mole of % To 10 moles of %, and it is preferred with 1 mole of % to 5 moles of %.According to the above method, the chemical combination of the unsaturated group containing ethene can be made Thing (C-1).
It is preferred that the specific example of the compound (C-1) of the unsaturated group containing ethene can include such as following formula (1-1), formula (1- 2) compound, 1,1 '-dinaphthol (poly-) methoxyl group, two (methyl) acrylate [1,1 '-binaphthol (poly) methoxy Di (meth) acrylate], 1,1 '-dinaphthol (poly-) ethyoxyl, two (methyl) acrylate [1,1 '-binaphthol (poly) Ethoxy di (meth) acrylate], 1,1 '-dinaphthol (poly-) propoxyl group, two (methyl) acrylate [1,1 '- Binaphthol (poly) propoxy di (meth) acrylate], or each R of the structure as shown in formula (1)1aIt is former for hydrogen Son, R2aSummation for ethylidine and s and t is respectively 0.5,1,5 or 10 compound.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, the compound (C-1) of the unsaturated group containing ethene Usage amount scope be 2 parts by weight to 80 parts by weight, preferably 5 parts by weight to 70 parts by weight, so with 8 parts by weight to 60 parts by weight For more preferably.
It is thus photosensitive if compound (C-1) of the unsaturated group containing ethene is not used in photosensitive polymer combination The resistance to sputter sex expression for the colored filter that property resin combination is formed is bad.
The compound (C-2) of the unsaturated group containing ethene
The alternative chemical combination for including the unsaturated group containing ethene of the compound (C) of the unsaturated group containing ethene of the present invention Thing (C-2).
The compound (C-2) of the unsaturated group containing ethene, which can include, according to 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- amino -3,7- dimethyl monooctyl ester, methacrylic acid -7- ammonia 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- It is ethylhexyl, methacrylic acid -2- ethylhexyls, ethyl diethylene glycol (DEG) acrylate, ethyl diethylene glycol (DEG) methacrylate, tertiary pungent Base acrylamide, t-octyl Methacrylamide, diacetone acrylamide, two acetone Methacrylamides, acrylic acid diformazan ammonia Base ester, dimethylaminoethyl ester, dodecylacrylate, lauryl methacrylate, two ring penta of acrylic acid Alkene 2-ethoxyethyl acetate, methacrylic acid dicyclopentenyl 2-ethoxyethyl acetate, acrylic acid dicyclopentenyl ester, methacrylic acid dicyclopentenyl ester, nitrogen, Nitrogen-dimethacrylamide, nitrogen, nitrogen-dimethylmethacryl amide, acrylic acid tetrachloro phenyl ester, methacrylic acid tetrachloro phenyl ester, Acrylic acid -2- tetrachloros phenoxy ethyl, methacrylic acid -2- tetrachloros phenoxy ethyl, tetrahydrofurfuryl acrylate, methacrylic acid Tetrahydrochysene chaff ester, tetrabromophenyl acrylate, methacrylic acid tetrabromo phenyl ester, acrylic acid -2- tetrabromos phenoxy ethyl, metering system Acid -2- tetrabromos phenoxy ethyl, acrylic acid -2- Trichlorophenoxies ethyl ester, methacrylic acid -2- Trichlorophenoxies ethyl ester, propylene Sour tribromophenyl, methacrylic acid tribromophenyl, acrylic acid -2- tribromophenoxies ethyl ester, methacrylic acid -2- tribromophenoxies Ethyl ester, acrylic acid -2- hydroxyl ethyl esters, 2-hydroxyethyl methacry-late, 2-hydroxypropyl acrylate, Hydroxypropyl methacrylate, Caprolactam, nitrogen-vinyl skin junket alkanone, acrylate, phenoxyethyl methacrylate, acrylic acid Pentachlorophenyl ester, methacrylic acid pentachlorophenyl ester, acrylic acid pentabromo- phenyl ester, methacrylic acid pentabromo- phenyl ester, poly- single acrylic acid second two Alcohol ester, poly- monomethacrylate glycol ester, poly- mono acrylic acid propylene glycol ester, poly- monomethacrylate acid propylene glycol ester, acrylic acid Norbornene ester, or methacrylic acid norbornene ester etc..Wherein, the unsaturated compound with least one ethene unsaturated group can be single It is solely a kind of to use or mix a variety of uses.
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, three (2- ethoxys) isocyanates, three acrylic acid Ester, three (2- ethoxys) isocyanates trimethyl acrylic esters, three (2- ethoxys) isocyanates, three propylene of caprolactone modification Acid esters, three (2- ethoxys) isocyanates trimethyl acrylic esters, three acrylic acid trihydroxy methyl propyl ester, the front three of caprolactone modification Base acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of ethylene oxide (hereinafter referred to as EO) modification, EO are modified Trimethacrylate acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester, the PO of propylene oxide (hereinafter referred to as PO) modification change Trimethacrylate acid trihydroxy methyl propyl ester, triethylene glycol diacrylate, triethylene glycol dimethacrylate, the neopentyl glycol two of matter 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 pentamethacrylate, 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 pentamethacrylate of caprolactone modification, tetrapropylene acid two Trihydroxy methyl propyl ester, two trihydroxy methyl propyl ester of tetramethyl acrylic acid, 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, Bisphenol F dimethylacrylate, phenolic aldehyde polyglycidyl ether acrylate, the phenolic aldehyde polyglycidyl ether methyl of EO modifications 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 Commodity of DPCA-120 etc..Wherein, the unsaturated compound with least two ethene unsaturated groups can individually a kind of use Or a variety of uses of mixing.
It is preferred that the compound (C-2) of the unsaturated group containing ethene is changed selected from three acrylic acid trihydroxy methyl propyl ester, EO Three acrylic acid trihydroxy methyl propyl ester of matter, 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, three propionic acid of glycerine 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 compound (C-2) of the above-mentioned unsaturated group containing ethene individually a kind of can use or mix a variety of uses.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, the compound (C-2) of the unsaturated group containing ethene Usage amount scope be 18 parts by weight to 120 parts by weight, preferably 25 parts by weight to 110 parts by weight, so with 42 parts by weight to 90 Parts by weight is more preferably.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, the compound (C) of the unsaturated group containing ethene Usage amount scope is 20 parts by weight to 200 parts by weight, preferably 30 parts by weight to 180 parts by weight, so with 50 parts by weight to 150 weights Part is measured as more preferably.
Light initiator (D)
The light initiator (D) of the present invention includes light initiator (D-1) and/or light initiator (D-2), following division it.
Light initiator (D-1)
Light initiator (D-1) can include the structure as shown in following formula (2)：
In formula (2), R1bRepresent the organic group containing the cycloalkyl that carbon number is 3 to 20, R2bAnd R3bTable independently of one another Show alkyl or aryl, and R4bRepresent alkyl.
So as to sensitivity is further improved to consider, R1bRepresent that the organic group of cycloalkyl for being 3 to 10 containing carbon number is Preferably, R1bRepresent the organic group for the cycloalkyl for being 5 to 8 containing carbon number for more preferably.
R1bIt can be mixed with the hydrocarbon-based for having divalence to contain to represent the organic group containing the cycloalkyl that carbon number is 3 to 20 The organic group of cycloalkyl, the example of divalence hydrocarbon-based can be alkylidene, and preferably carbon number is 2 to 5 alkylidene, be more preferably time Ethyl.
R1bIt is the organic group containing the cycloalkyl that carbon number is 3 to 20, preferably cycloalkyl alkylidene, is more preferably cyclopenta Ethyl.
In formula (2), further to lift sensitivity to consider, R2bIt can be alkyl or aryl, be preferably alkyl, be more preferably carbon number For 1 to 5 alkyl, and using methyl as again more preferably.
In formula (2), further to lift sensitivity to consider, R3bMore preferably it is that carbon number is for alkyl or aryl, preferably alkyl 1 to 10 alkyl, and using ethyl as again more preferably.
In formula (2), further to lift sensitivity to consider, R4bFor alkyl, preferably carbon number is 1 to 5 alkyl, is more preferably Methyl.
In formula (2), R4bThe position of substitution can be ortho position, meta or para position.To further improve sensitivity to consider, preferably For ortho position.
In the example of the compound represented by formula (2), R1bIt is cycloalkyl ethylidine, R2bIt is methyl, R3bIt is ethyl, R4bIt is Methyl, specific commodity are, for example, TR-PBG-304 of Changzhou strength Co., Ltd. etc..
The concrete example of light initiator (D-1) is such as, but not limited to the structure as shown in following formula (2-1) to formula (2-10) Light initiator.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, and the usage amount scope of light initiator (D-1) is 5 weights Part is measured to 50 parts by weight, preferably 10 parts by weight to 45 parts by weight, so using 15 parts by weight to 40 parts by weight as more preferably.
During using light initiator (D-1), the resistance to of colored filter formed by photosensitive polymer combination splashes crossing property table Now more preferably.
Light initiator (D-2)
Light initiator (D-2) has the structure as shown in following formula (3)：
In formula (3), E1、E2、E3、E4、E5、E6、E7And E8Represent independently of one another hydrogen atom, carbon number as 1 to 20 alkane Base,COE16、OE17, halogen atom, NO2OrOr
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Warp is represented independently of one anotherSubstituted carbon number is 2 to 10 alkenyl；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Common representative-(CH independently of one another2)p-W- (CH2)q-；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is common independently of one another to representA wherein at least E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
E9、E10、E11And E12Each independently represent hydrogen atom, carbon number as 1 to 20 alkyl, the carbon number for 1 to 20 alkyl To be unsubstituted or substitute through an at least group as follows, and an at least group be selected from phenyl, halogen atom, CN, OH, SH, alkoxy, (CO) OH or (CO) O (R that carbon number is 1 to 41), wherein R1Carbon number is represented as 1 to 4 alkyl；Or
E9、E10、E11And E12The phenyl being unsubstituted is represented independently of one another or is substituted through an at least group as follows Phenyl, an at least group be selected from carbon number be 1 to 6 alkyl, halogen atom, CN, OE17、SE18Or NE19E20；Or
E9、E10、E11And E12Halogen atom, CN, OE are represented independently of one another17、SE18、SOE18、SO2E18Or NE19E20, its In such substituent OE17、SE18Or NE19E20It is without or via such group E17、E18、E19And/or E20With one of naphthalene nucleus Carbon atom forms five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Represent independently of one anotherCOE16Or NO2；
W represents O, S, NE26Or singly-bound, p represent 0 to 3 integer, q represents 1 to 3 integer, Z1Represent CO or singly-bound；
E13Carbon number is represented as 1 to 20 alkyl, the carbon number be 1 to 20 alkyl be unsubstituted or through it is as follows extremely Few group substitution, wherein an at least group are selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2OrOr
E13Carbon number is represented as 2 to 20 alkyl, the alkyl which is 2 to 20, which is mixed with, one or more O, S, SO, SO2、 NE26Or CO；Or
E13Carbon number is represented as 2 to 12 alkenyl, the carbon number be 2 to 12 alkenyl be without be mixed with or through be mixed with have it is one or more A O, CO or NE26, wherein the alkene 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 Base is to be unsubstituted or substitute through an at least 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 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 are taken through an at least group as follows Generation, wherein an at least group are to be selected from OE17、SE18、NE19E20、COE16、CN、NO2, halogen The haloalkyl that alkyl that atom, carbon number are 1 to 20, carbon number are 1 to 4, being mixed with has one or more O, S, CO or NE26And carbon number is 2 to 20 alkyl；The phenyl or the naphthyl respectively through carbon number be 3 to 10 cycloalkyl substitution or respectively through be mixed with have one or more O, S, CO or NE26And the cycloalkyl that carbon number is 3 to 10 substitutes；
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 the carbon number that substitutes through an at least group as follows is 1 to 20, and an at least group is choosing From halogen atom, phenyl, the alkyl phenyl or CN that carbon number is 1 to 20；Or
E14Represent phenyl or naphthyl, it is respectively unsubstituted or substitutes through an at least group as follows, and this at least one Group be selected from carbon number be 1 to 6 alkyl, carbon number be 1 to 4 haloalkyl, halogen atom, CN, OE17、SE18And/or NE19E20；Or
E14Represent carbon number as 3 to 20 heteroaryl, carbon number is 1 to 8 alkoxy, benzyloxy or phenoxy group, the benzyloxy And the phenoxy group is to be unsubstituted or substitute through an at least group as follows, and an at least group is to be selected from carbon number as 1 The haloalkyl and/or halogen atom that alkyl, carbon number to 6 are 1 to 4；
E15It is 6 to 20 aromatic radical or carbon number as 3 to 20 heteroaryl to represent carbon number, it is respectively unsubstituted or through following institute Show an at least group substitution, and an at least group be selected from phenyl, halogen atom, carbon number be 1 to 4 haloalkyl, CN, NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2And SO bonds and alkyl and SO that carbon number is 1 to 102Bond and carbon number are 1 Alkyl to 10, be mixed with and have one or more O, S or NE26And the alkyl that carbon number is 2 to 20；Or its respectively through carbon number be 1 to 20 alkane Base substitutes, and wherein the carbon number is that 1 to 20 alkyl is to be unsubstituted or substitute through an at least group as follows, and this is at least One group is 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 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
E15Carbon number is represented as 1 to 20 alkyl, the carbon number be 1 to 20 alkyl be unsubstituted or through it is as follows extremely Few group substitution, and an at least group is selected from halogen atom, OE17、SE18, carbon number be 3 to 8 cycloalkyl, carbon number 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、 Phenyl, the wherein carbon number are 1 to 20 Alkyl be to substitute through phenyl, and the alkyl halide that alkyl that it is 1 to 20 through halogen atom, carbon number that the phenyl, which is, carbon number are 1 to 4 Base, OE17、SE18Or NE19E20Substitution；Or
E15Carbon number is represented as 2 to 20 alkyl, the alkyl which is 2 to 20 is to be mixed with to have one or more O, SO or SO2, The alkyl through being mixed with and carbon number is 2 to 20 is to be unsubstituted or substitute through an at least group as follows, and this at least one Group is selected from halogen atom, OE17、COOE17、CONE19E20, phenyl or through OE17、SE18Or NE19E20Substituted phenyl；Or
E15Carbon number is represented as 2 to 20 alkanoyl or benzoyl, it is unsubstituted or through as follows at least one Group substitutes, and an at least group is to be selected from the alkyl, halogen atom, phenyl, OE that carbon number is 1 to 617、SE18Or NE19E20； Or
E15Representative is unsubstituted or through an at least OE17Substituted naphthoyl or the heteroaryl carbonyl that carbon number is 3 to 14 Base；Or
E15Carbon number is represented as 2 to 12 alkoxy carbonyl, the alkoxy carbonyl which is 2 to 12 is without being mixed with or passing through At least an O is mixed with, wherein this through be mixed with or without be mixed with and carbon number be 2 to 12 alkoxy carbonyl be to be unsubstituted or through at least Monohydroxy substitutes；Or
E15Phenyloxycarbonyl is represented, which is to be unsubstituted or substitute through an at least group as follows, And alkyl that it is 1 to 6 selected from carbon number that an at least group, which is, halogen atom, carbon number be 1 to 4 haloalkyl, phenyl, OE17、 SE18Or NE19E20；Or
E15Represent CN, CONE19E20、NO2, carbon number be 1 to 4 haloalkyl, S (O)r-R2And S (O)rThe phenyl of bond, Wherein should be 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 is 1 to 6 alkyl；Or
E15Representative and SO2Phenyl, diphenylphosphino or the two (R of O bonds3)-phosphono, wherein should and SO2O bonds Phenyl is to be unsubstituted or substitute through the alkyl that carbon number is 1 to 12, and R3Carbon number is represented as 1 to 4 alkoxy；
R represents 1 to 2 integer；
E'14Represent to have and be directed to E14One of in definition wherein；
E'15Represent to have and be directed to E15One of in definition wherein；
Z2Represent O, S, SO or SO2；
Z3Represent O, CO, S or singly-bound；
E16It is 6 to 20 aryl or carbon number as 3 to 20 heteroaryl to represent carbon number, it is respectively unsubstituted or through as follows An at least group substitution, and an at least 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 the alkyl that carbon number is 1 to 20, or carbon number are 1 to 20 Alkyl, the wherein carbon number is that 1 to 20 alkyl is to be unsubstituted or substitute through an at least group as follows, and wherein this is extremely A few group is selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 it is miscellaneous Heteroaryloxycarbonyl that aryloxycarbonyl that aryl, carbon number are 6 to 20, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E16Hydrogen atom or carbon number are represented as 1 to 20 alkyl, wherein the carbon number is that 1 to 20 alkyl is to be unsubstituted or pass through At least group substitution as follows, and an at least group 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
E16Carbon number is represented as 2 to 12 alkyl, which 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 Cycloalkyl, wherein R4Carbon number is represented as 1 to 8 alkyl；Or
E16Represent through SE18Substituted phenyl, wherein E18Bond is represented to the COE16The benzene of the attached carbazole part The singly-bound of base or the naphthyl 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 group substitutes, and an at least group is selected from halogen atom, 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) bond phenyl, (CO) OH, (CO) O (R1), carbon number Cycloalkyl, SO for 3 to 202-(R7)、O(R7) or be mixed with through an at least O and cycloalkyl that carbon number is 3 to 20, wherein, R5Represent Carbon number be 1 to 3 alkyl, R6Carbon number is represented as 2 to 4 alkenyl, and R7Carbon number is represented as 1 to 4 haloalkyl；Or
E17Carbon number is represented as 2 to 20 alkyl, and the carbon number be 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
E17Represent carbon number and be bonded the group formed, and the group with carbon number as 3 to 10 cycloalkyl by 1 to 8 alkyl It is without being mixed with or being mixed with through an at least O；Or
E17Benzoyl is represented, which is unsubstituted or substitutes through an at least 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
E17Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through as follows at least one Group substitutes, and the alcoxyl that alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that an at least group, which is, carbon number are 1 to 12 Base, CN, NO2, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amino orWherein R8Carbon number is represented as 1 to 3 alkoxy, and R9Carbon number is represented as 1 to 12 alkyl；Or
E17With withPhenyl or naphthyl ring wherein one A carbon atom forms singly-bound；
E18Represent hydrogen atom, carbon number as 2 to 12 cycloalkyl or phenyl-R as 3 to 20 of alkenyl, carbon number5, the wherein carbon The cycloalkyl and the phenyl-R that alkenyl that number is 2 to 12, the carbon number are 3 to 205Be without be mixed with or be mixed with have one or more O, S、CO、NE26Or COOE17；Or
E18Carbon number is represented as 1 to 20 alkyl, the carbon number be 1 to 20 alkyl be unsubstituted or through following depicted at least One group substitutes, and an at least 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
E18Carbon number is represented as 2 to 20 alkyl, the carbon number be 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, which is to be unsubstituted or substitute through an at least group as follows, and should The alkoxy or carbon number that alkyl that it is 1 to 6 selected from carbon number that an at least group, which is, halogen atom, OH, carbon number are 1 to 4 are 1 to 4 Alkyl sulfenyl；Or
E18Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, its be respectively be unsubstituted or through it is as follows at least One group substitutes, and an at least 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, the alkoxy that carbon number is 1 to 12, CN, NO2, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl amino, (CO) O (R4)、(CO)-R4、(CO)N(R4)2Or
E19And E20Represent independently of one another hydrogen atom, carbon number as 1 to 20 hydroxy alkyl, carbon as 2 to 4 of alkyl, carbon number 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 E20Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through as follows An at least group substitutes, and haloalkyl that it is 1 to 4 selected from halogen atom, carbon number that an at least 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 this five yuan or hexa-atomic saturation or unsaturation ring are unsubstituted or through an at least group as follows Substitution, wherein an at least group be selected from carbon number be 1 to 20 alkyl, carbon number be 1 to 20 alkoxy ,=O, OE17、 SE18、NE21E22、(CO)E23、NO2, halogen atom, carbon number be 1 to 4 haloalkyl, CN, phenyl,Or there are one or more O, S, CO or NE without being mixed with or being mixed with17And the ring that carbon number is 3 to 20 Alkyl；Or
E19And E20It is that heteroaromatic ring system is formed together with attached nitrogen-atoms, which is not It is substituted or substitutes through an at least group as follows, and an at least group is selected from alkyl of the carbon number for 1 to 20, carbon number Alkoxy that haloalkyl, carbon number for 1 to 4 are 1 to 20 ,=O, OE17、SE18、NE21E22、(CO)E23、Halogen atom, NO2, CN, phenyl, or without be mixed with or be mixed with have one or more O, S, CO or NE17And the cycloalkyl that carbon number is 3 to 20；
E21And E22Represent independently of one another hydrogen atom, carbon number as 1 to 20 haloalkyl, carbon as 1 to 4 of alkyl, carbon number Cycloalkyl or phenyl of the number for 3 to 10；
E21And E22Formed together with the nitrogen-atoms bonded with it 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 are 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 have an at least O, CO or NE26And alkyl that carbon number is 2 to 20, without being mixed with or being mixed with there are O, S, CO or NE26And the cycloalkyl that carbon number is 3 to 20； Or
E23Represent phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represent (CO) OE17、CONE19E20、(CO)E17Or have and be directed to E19And E20One of in definition wherein；
E25Represent COOE17、CONE19E20、(CO)E17；Or E25With for E17One of in definition wherein；
E26Represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have an at least O or CO And the alkyl that carbon number is 2 to 20；Or E26Represent phenyl-R1, without being mixed with or being mixed with through an at least O or CO and carbon number is 3 to 8 Cycloalkyl；Or E26Represent (CO) E19；Or E26Represent phenyl, E26It is to be unsubstituted or substitute through an at least group as follows, And alkyl that it is 1 to 20 selected from carbon number that an at least group, which is, halogen atom, carbon number be 1 to 4 haloalkyl, OE17、SE18、 NE19E20OrBut condition has at least one for the light initiator (D-2) of the structure as shown in formula (3)
It should be characterized in that including at least one one-tenth on its carbazole moiety with the light initiator (D-2) of structure shown in formula (3) Ring (annelated) unsaturation ring.In other words, at least a 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, the alkyl that carbon number is 1 to 12, carbon number is 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 for example methyl, ethyl, propyl group, isopropyl, normal-butyl, the second butyl, isobutyl group, the tert-butyl group, amyl group, Hexyl, heptyl, 2,4,4- tri-methyl-amyls, 2- ethylhexyls, octyl group, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, ten Six bases, octadecyl and 20 bases.The alkyl that carbon number is 1 to 6 has the definition identical with the alkyl that above-mentioned carbon number is 1 to 20, and With the corresponding carbon number of highest.
The alkyl that the carbon number for being unsubstituted or being substituted for containing an at least carbon-to-carbon multikey is 1 to 20 is as described later 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 more halogenations, until all hydrogen atoms replace with halogen, and may be, for example, CjHwXy, wherein w+y=2j+1 and X is halogen, preferably fluorine atom.Specific example such as chloromethyl, trichloromethyl, trifluoromethyl Or 2- bromopropyls, in particular trifluoromethyl or trichloromethyl.
The hydroxy alkyl that the carbon number is 2 to 4 means the alkyl that the carbon number through the substitution of one or two oxygen atoms is 2 to 4.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 alkoxyalkyl that the carbon number is 2 to 10 is the alkyl that the carbon number being mixed with through an O is 2 to 10.Carbon number is 2 to 10 The identical definition for the alkyl that alkyl has with foregoing carbon number is 1 to 20, and there is 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 the alkyl that the carbon number of CO is 2 to 20 is for example through O, S, NE26Or between CO Miscellaneous 1 to 9 time, 1 to 5 time, 1 to 3 time, 1 time or 2 times.If being mixed with group there are more than one, it is for identical type or not Together.Two oxygen atoms are separated by least one methylene, preferably at least two methylene (i.e. ethylidine).Such 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。
The cycloalkyl that the cycloalkyl and carbon number that cycloalkyl that the carbon number is 3 to 10, carbon number are 3 to 10 are 3 to 8 can be regarded as Including at least the alkyl of a ring.Specific example such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl and amyl group ring penta Base.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 asAnd other corresponding rings.Other concrete examples may be, for example, (such as) or Etc. structure, and bridging or fused ring system, for example, definition herein also includes Etc. structure, wherein R10Represent alkylidene, R11Represent 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 (such as)、 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 the carbon number of one or more O by 1 to 8 alkyl be 3 to 10 with carbon number cycloalkyl bond formed Group refer to through it is at least one with most 8 carbon atoms it is alkyl-substituted be mixed with as previously defined have one or more O Carbon number be 3 to 10 cycloalkyl.Specific example is such as Deng.
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 for 1 to 12 alkyl has the identical definition for 1 to 20 alkyl such as foregoing carbon number, and has the corresponding carbon number of highest.Carbon number is 1 to 4 alkoxy is straight or branched, such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, the second fourth oxygen Base, isobutoxy or tert-butoxy.The alkoxy that the alkoxy and carbon number that carbon number is 1 to 8 are 1 to 4 be it is identical with aforementioned definitions, And there is 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 has 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, tert. butyl-sulphenyl.
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 the alkenyl, carbon number 2 that for example, carbon number is 2 to 10 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 the alkenyl that the carbon number of CO is 2 to 12 is for example through O, S, NE26Or CO is mixed with 1 To 9 times, 1 to 5 time, 1 to 3 time, 1 time or 2 times.If being mixed with group there are more than one, it is identical type or difference.Two A oxygen atom is separated by least one methylene, preferably at least two methylene (i.e. ethylidine).Alkenyl is straight or branched And as defined above.For example, following construction unit can be formed：- CH=CH-O-CH2CH3,-CH=CH-O-CH=CH2 Deng.
The cycloalkenyl group that the carbon number is 4 to 8 has an at least double bond, and may be, for example, the cycloalkenyl group or carbon number that carbon number is 4 to 6 For 6 to 8 cycloalkenyl group.Specific example such as cyclobutane base, cyclopentenyl, cyclohexenyl group or cyclo-octene base, in particular cyclopentenyl And cyclohexenyl group, it is preferably cyclohexenyl group.
The alkenyloxy group that the carbon number is 3 to 6 is single or multiple unsaturation, and has the one of which of the definition such as foregoing alkenyl, And attachment 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 alkanoyl that the carbon number is 2 to 20 is straight or branched, and may be, for example, carbon number be 2 to 18, carbon number is 2 to 14, The alkanoyl or carbon number that carbon number is 2 to 12, carbon number is 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 identical definition of the alkanoyl that carbon number as the aforementioned is 2 to 20, and has highest Corresponding carbon number.
The carbon number be 2 to 12 alkoxy carbonyl be straight or branched, 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 by At least two methylene (i.e. ethylidine) separate.The alkoxy carbonyl through being mixed with is unsubstituted or is taken through one or more hydroxyls Generation.The aryloxycarbonyl that carbon number is 6 to 20 may be, for example, phenyloxycarbonyl (=phenyl-O- (CO) O-), naphthoxycarbonyl, anthracene Epoxide carbonyl etc..The heteroaryl that it is 5 to 20 with the carbon number of-O-CO- bonds that the Heteroarylcarbonyl that carbon number is 5 to 20, which can be,.
The cycloalkyl that it is 3 to 10 with the carbon number of CO bonds that the naphthene base carbonyl that the carbon number is 3 to 10, which can be, wherein cycloalkyl With defining as hereinbefore, and there is the corresponding carbon number of highest.Being mixed with has one or more O, S, NE26Or the carbon number of CO is 3 to 10 naphthene base carbonyl refers to the cycloalkyl with CO bonds through being mixed with, wherein the cycloalkyl through being mixed with has and foregoing phase Same 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 has the corresponding carbon number of highest.Being mixed with has one or more O, S, NE26Or The cyclo alkoxy carbonyl that the carbon number of CO is 3 to 10 refers to the cycloalkyl with-O- (CO)-bond through being mixed with, wherein through being mixed with Cycloalkyl has definition as hereinbefore.
The alkyl phenyl that the carbon number is 1 to 20 refers to through at least one alkyl-substituted phenyl, the wherein sum total of carbon atom Up to 20.
The aryl that the carbon number is 6 to 20 may be, for example, phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, 1,2- benzos phenanthryl and four Phenyl, connection time triphenyl etc., in particular phenyl or naphthyl, preferably phenyl.Naphthyl is 1- naphthyls or 2- naphthyls.
In the content of light initiator (D-2), the heteroaryl which is 3 to 20 includes monocyclic or multi-loop system, such as Fused ring system.Concrete example is thienyl, benzo [b] thienyl, naphtho- [2,3-b] thienyl, thianthrene group, furyl, hexichol And furyl, benzo piperazine mutter base (benzopyran), xanthyl, thioxanthene base, coffee dislike thiophene base, pyrrole radicals, imidazole radicals, pyrazolyl, Pyrazinyl, pyrimidine radicals, pyridazinyl, indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizine base, isoquinolyl, Quinolyl, phthalazinyl, naphthyridines base, quinoxaline base, quinazolyl, cinnoline base (cinnoline), pteridine radicals, carbazyl, B-carboline Base, phenanthridinyl, acridinyl, perimidinyl, phenanthroline, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furan Xanthones bases, phenoxazine base, 7- phenanthryl, anthraquinone -2- bases (bis- side epoxide -9,10- dihydroanthracene -2- bases of=9,10-), 3- benzos [b] thiophene Base, 5- benzos [b] thienyl, 2- benzos [b] thienyl, 4- dibenzofuran groups, 4,7- dibenzofuran groups, 4- methyl -7- Dibenzofuran group, 2- xanthyls, 8- methyl -2- xanthyls, 3- xanthyls, 2- coffee dislike thiophene base, 2,7- coffee dislikes thiophene base, 2- pyrroles Base, 3- pyrrole radicals, 5- methyl -3- pyrrole radicals, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 2- methyl -4- imidazole radicals, 2- second Base -4- imidazole radicals, 2- ethyl -5- imidazole radicals, 1H-TETRAZOLE -5- bases, 3- pyrazolyls, 1- methyl -3- pyrazolyls, 1- propyl group -4- pyrroles Oxazolyl, 2- pyrazinyls, 5,6- dimethyl -2- pyrazinyls, 2- indolizine base, 2- methyl -3- isoindolyls, 2- methyl isophthalic acids-different Yin Diindyl base, 1- methyl -2- indyls, 1- methyl -3- indyls, 1,5- dimethyl -2- indyls, 1- methyl -3- indazolyls, 2,7- Dimethyl -8- purine radicals, 2- methoxyl group -7- methyl -8- purine radicals, 2- quinolizines base, 3- isoquinolyls, 6- isoquinolyls, 7- are different Quinolyl, 3- methoxyl group -6- isoquinolyls, 2- quinolyls, 6- quinolyls, 7- quinolyls, 2- methoxyl group -3- quinolyls, 2- first Epoxide -6- quinolyls, 6- phthalazinyls, 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- quinazolyls, 2- dimethylamino -6- quinazolyls, 3- cinnoline bases, 6- cinnoline bases, 7- cinnoline bases, 3- methoxyl group -7- cinnoline bases, 2- pteridine radicals, 6- pteridine radicals, 7- pteridine radicals, 6,7- dimethoxy -2- pteridine radicals, 2- carbazyls, 3- carbazyls, 9- methyl -2- carbazyls, 9- methyl -3- carbazyls, B-carboline -3- bases, 1- methyl-ss-carboline -3- bases, 1- first Base-B-carboline -6- bases, 3- phenanthridinyls, 2- acridinyls, 3- acridinyls, 2- perimidinyls, 1- methyl -5- naphthalenes embedding two Pyridyl, 5- phenanthrolines, 6- phenanthrolines, 1- phenazinyl, 2- phenazinyl, 3- isothiazolyls, 4- isothiazolyls, 5- isothiazole Base, 2- phenothiazinyls, 3- phenothiazinyls, 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 Heteroarylcarbonyl that the carbon number is 4 to 20 is to be connected to molecule remainder as defined above via CO groups 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 cannot have than virtue Free position on basic ring is more substituent.
In the position 4 of substituent preferably on the phenyl ring on the benzyl ring or in 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6- configurations.
The group through being mixed with least once 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 substituted at least once 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 substituted through an at least 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, is more preferably fluorine and chlorine.
For example, if E1And E2、E2And E3、E3And E4Or E5And E6、E6And E7、E7And E8It is separatelyThe structure shown in for example with following formula (3-1) to formula (3-9) is then formed, wherein with formula (3-1) Structure is preferable.
The compound of the formula (3) is characterized in that at least one benzyl ring is condensed with carbazole moiety, to form " naphthyl " ring. Namely above-mentioned formula (3-1) to one of the structure of formula (3-9) is according to depicted in formula (3).
If E1And E2、E2And E3、E3And E4Or E5And E6、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 E20Five yuan or hexatomic ring are formed with a carbon atom of naphthyl ring, then is obtained comprising 3 or more rings (including naphthyl Ring) structure.Specific example may be, for example,
Deng.
If E17With withGroup phenyl or naphthyl ring one A carbon atom forms singly-bound, then is formed for example Etc. structure.
If E16It is through SE18Substituted phenyl, wherein E18Represent that bond extremely has COE16Carbazole moiety phenyl or naphthyl The singly-bound of ring, the structure formed may be, for example, If it is, E16It is through SE18Substituted phenyl, wherein group E18Represent key Knot extremely has COE16Carbazole moiety phenyl or naphthyl ring singly-bound, and formed at the same time there is thioxanthene base section and carbazole moiety A phenyl or naphthyl ring.
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 condensed with the saturation or unsaturation ring, then the saturation or unsaturation formed Ring may be, for example, aziridine, pyrroles, thiazole, Pyrrolizidine, oxazole, pyridine, 1,3- diazines, 1,2- diazines, hexahydropyridine or morpholine Or accordingly cyclic (such as)。
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..
The light initiator (D-2) (oxime ester) of structure shown in the formula (3) be by known method preparation, such as by with Make corresponding oxime and carboxylic acid halides under the conditions of lower, particularly chloride or anhydride reaction：Atent solvent (such as：T-butyl methyl ether, Tetrahydrofuran (THF) or dimethylformamide) in, in the presence of alkali (such as triethylamine or pyridine), or basic solvent (such as Pyridine) in.In one embodiment of this invention, as the compound of formula (3-1) be with following formula (i) shown in method prepare, its Middle E7It is oxime ester base groupAnd Z1It is singly-bound.And the compound as shown in formula (3-2) to formula (3-8) is Prepare in the same way, but select suitable oxime to carry out.
In formula (i), E1、E2、E5、E6、E8、E13、E14And E15It is that as defined above, X means halogen atom, in particular Chlorine atom.It is preferred that E14For methyl.
It is known that the above-mentioned reaction as shown in formula (i) for the art has a usually intellectual, and usually -15 DEG C to+ Implement at a temperature of 50 DEG C, preferably implement at a temperature of 0 DEG C to 25 DEG C.
Work as Z1When being CO, corresponding oxime be by with alkyl nitrite (such as 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, detailed preparation method is as shown in 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 (3) as defined above compound, wherein X is halogen atom, And particularly chlorine atom, and E14Definition know as foregoing.
The required oxime as starting material can be by 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 be (such as) in polar solvent (such as dimethylacetylamide (DMA), DMA aqueous solutions, 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 reaction mixture.It is well known that reaction speed has pH dependences, and can connect when starting or during reaction Alkali is added continuously.Also the basic solvents such as pyridine can be used as alkali and/or solvent or cosolvent.Reaction temperature is usually room Temperature is typically about 20 DEG C to 120 DEG C to the reflux temperature of mixture.
Corresponding ketone intermediate be (such as) by document (such as standard chemical teaching material, such as J.March, Advanced Organic Chemistry, the 4th edition, Wiley Interscience, 1992) it is prepared by method described in.In addition, continuously not Reed-Kerafyrm thatch reaction (Friedel-Crafts reaction) can be effectively used for synthetic intermediate.These reactions are to be familiar with Known to skilled person.
Another convenient synthesis of oxime is to use nitrous acid or alkyl nitrite by " activity " methylene nitrosation.Alkaline condition (such as Organic Syntheses coll. (J.Wiley＆Sons, New York, 1988) Section VI rolls up page 199 and the 840th Described in page) (such as Organic Synthesis coll. Vs roll up page 32 and page 373, Section III volume the with acid condition Page 191 and page 513, described in page 202, page 204 and page 363 of vol. ii) be both adapted to prepare and use in the present invention Make the oxime of starting material.Generally nitrous acid is produced from sodium nitrite.Alkyl nitrite can be (such as) methyl nitrite, nitrous Acetoacetic ester, propyl nitrite, butyl nitrite or isoamyl nitrite.
In another embodiment, light initiator (D-2) is free type oxime compound, and with the knot as shown in formula (3A) Structure：
In formula (3A), 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 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 E8It is separately common to representA wherein at least E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
E9、E10、E11And E12Independently represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number be 1 to 20 alkyl be Be unsubstituted or substitute through an at least group as follows, and an at least group be selected from phenyl, halogen atom, CN, OH, SH, alkoxy, (CO) OH or (CO) O (R that carbon number is 1 to 41), wherein R1Carbon number is represented as 1 to 4 alkyl；Or
E9、E10、E11And E12Separately represent the phenyl being unsubstituted or substitute through an at least group as follows Phenyl, an at least group be selected from carbon number be 1 to 6 alkyl, halogen atom, CN, OE17、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 (IA) One carbon atom forms five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Separately representCOE16Or NO2；
W represents O, S, NE26Or singly-bound, p represent 0 to 3 integer, q represents 1 to 3 integer, Z1Represent CO or singly-bound；
E13Carbon number is represented as 1 to 20 alkyl, carbon number be 1 to 20 alkyl be unsubstituted or through it is as follows at least One group substitutes, wherein an above-mentioned at least group is selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20、 NE19E20、PO(OCkH2k+1)2OrOr
E13Carbon number is represented as 2 to 20 alkyl, the alkyl that carbon number is 2 to 20 is to be mixed with to have one or more O, S, SO, SO2、 NE26Or CO；Or
E13Carbon number is represented as 2 to 12 alkenyl, carbon number be 2 to 12 alkenyl be without be mixed with or be mixed with have one or more 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 is It is unsubstituted or substitutes through an at least 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 more O, S, CO or NE26Carbon number be 3 to 10 cycloalkyl；Or
E13Represent phenyl or naphthyl, and it is respectively unsubstituted or substitutes through an at least group as follows, wherein this is extremely A few 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 the alkyl that carbon number is 2 to 20；Or its is each There are one or more O, S, CO or NE through not being mixed with or being mixed with26And carbon number is substituted by 3 to 10 cycloalkyl；
K represents 1 to 10 integer；
E15It is 6 to 20 aromatic radical or carbon number as 3 to 20 heteroaryl to represent carbon number, it is respectively unsubstituted or through following institute Show an at least group substitution, and an at least group be selected from phenyl, halogen atom, carbon number be 1 to 4 haloalkyl, CN, NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2And SO bonds and alkyl and SO that carbon number is 1 to 102Bond and carbon number are 1 Alkyl to 10, be mixed with and have one or more O, S or NE26And the alkyl that carbon number is 2 to 20；Or its respectively through carbon number be 1 to 20 alkane Base substitutes, and wherein carbon number is that 1 to 20 alkyl is to be unsubstituted or substitute through an at least group as follows, and an at least base Group is 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 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
E15Carbon number is represented as 1 to 20 alkyl, carbon number be 1 to 20 alkyl be unsubstituted or through it is as follows at least One group substitutes, and an at least group is selected from halogen atom, 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 carbon number is that 1 to 20 alkyl is Substitute 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
E15Carbon number is represented as 2 to 20 alkyl, the alkyl that carbon number is 2 to 20 is to be mixed with to have one or more O, SO or SO2, warp It is mixed with and alkyl that carbon number is 2 to 20 is to be unsubstituted or substitute through an at least group as follows, and at least a group is Selected from halogen atom, OE17、COOE17、CONE19E20, phenyl or through OE17、SE18Or NE19E20Substituted phenyl；Or
E15Carbon number is represented as 2 to 20 alkanoyl or benzoyl, is unsubstituted or through an at least base as follows Group's substitution, and an at least group is to be selected from the alkyl, halogen atom, phenyl, OE that carbon number is 1 to 617、SE18Or NE19E20；Or
E15Representative is unsubstituted or through an at least OE17Substituted naphthoyl or the heteroaryl carbonyl that carbon number is 3 to 14 Base；Or
E15Carbon number is represented as 2 to 12 alkoxy carbonyl, the alkoxy carbonyl that carbon number is 2 to 12 is without being mixed with or being mixed with Have one or more O, wherein through be mixed with or without be mixed with and carbon number be 2 to 12 alkoxy carbonyl be to be unsubstituted or through at least one Hydroxyl substitutes；Or
E15Phenyloxycarbonyl is represented, phenyloxycarbonyl is to be unsubstituted or substitute through an at least group as follows, and Haloalkyl that alkyl that it is 1 to 6 selected from carbon number that an at least group, which is, halogen atom, carbon number are 1 to 4, phenyl, OE17、SE18 Or NE19E20；Or
E15Represent CN, CONE19E20、NO2, carbon number be 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
E15Representative and SO2Phenyl, diphenylphosphino or the two (R of O bonds3)-phosphono, wherein with SO2The benzene of O bonds Base is to be unsubstituted or substitute through the alkyl that carbon number is 1 to 12, and R3Carbon number is represented as 1 to 4 alkoxy；
R represents 1 to 2 integer；
E'15Represent to have and be directed to E15One of in definition wherein；
Z2Represent O, S, SO or SO2；
Z3Represent O, CO, S or singly-bound；
E16It is 6 to 20 aryl or carbon number as 3 to 20 heteroaryl to represent carbon number, it is respectively unsubstituted or through as follows An at least group substitution, and an at least 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 the alkyl that carbon number is 1 to 20, or the alkane that carbon number is 1 to 20 The alkyl that base, wherein carbon number are 1 to 20 is to be unsubstituted or substitute through an at least group as follows, a wherein at least group It is selected from halogen atom, COOE17、CONE19E20, phenyl, carbon number be 3 to 8 cycloalkyl, carbon number be 3 to 20 heteroaryl, carbon Heteroaryloxycarbonyl that aryloxycarbonyl that number is 6 to 20, carbon number are 3 to 20, OE17、SE18Or NE19E20；Or
E16Hydrogen atom or carbon number are represented as 1 to 20 alkyl, wherein carbon number is that 1 to 20 alkyl is unsubstituted or through such as At least group substitution shown in lower, and an at least group is 3 to 6 selected from halogen atom, 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
E16Carbon number is represented as 2 to 12 alkyl, the alkyl that carbon number is 2 to 12 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 Cycloalkyl, the wherein R4Carbon number is represented as 1 to 8 alkyl；Or
E16Represent through SE18Substituted phenyl, wherein E18Bond is represented to COE16The phenyl or naphthalene of attached carbazole part 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 group substitutes, and an at least group is selected from halogen atom, 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) bond phenyl, (CO) OH, (CO) O (R1), carbon number Cycloalkyl, SO for 3 to 202-(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 R5Generation Alkyl, the R that table carbon number is 1 to 36Carbon number is represented as 2 to 4 alkenyl, and R7Carbon number is represented as 1 to 4 haloalkyl；Or
E17Carbon number is represented as 2 to 20 alkyl, and the alkyl that carbon number is 2 to 20 is to be mixed with to 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
E17Represent carbon number and be bonded the group formed, and above-mentioned base with carbon number as 3 to 10 cycloalkyl by 1 to 8 alkyl Group is without being mixed with or having one or more O through being mixed with；Or
E17Benzoyl is represented, benzoyl is unsubstituted or substitutes through an at least group as follows, and this is 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
E17Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through as follows at least one Group substitutes, and alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that an at least group, which is, carbon number be 1 to 12 alkoxy, CN、NO2, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amino orWherein R8Carbon number is represented as 1 to 3 alkoxy, and R9Carbon number is represented as 1 to 12 alkyl；Or
E17With withOne of carbon atom of phenyl or naphthyl ring form list Key；
E18Represent hydrogen atom, carbon number as 2 to 12 cycloalkyl or phenyl-R as 3 to 20 of alkenyl, carbon number5, wherein carbon number The cycloalkyl and phenyl-R that alkenyl, carbon number for 2 to 12 are 3 to 205Be without be mixed with or be mixed with have one or more O, S, CO, NE26Or COOE17；Or
E18Carbon number is represented as 1 to 20 alkyl, the alkyl that carbon number is 1 to 20 is unsubstituted or through following depicted at least one Group substitutes, and an at least 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
E18Carbon number is represented as 2 to 20 alkyl, the alkyl that carbon number is 2 to 20 is to be mixed with to have one or more O, S, CO, NE26 Or 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 to be unsubstituted or substitute through an at least group as follows, and at least The alkyl that the alkoxy or carbon number that alkyl that it is 1 to 6 selected from carbon number that one group, which is, halogen atom, OH, carbon number are 1 to 4 are 1 to 4 Sulfenyl；Or
E18Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, its is each unsubstituted or through an at least base as follows Group's substitution, and an at least group is to be selected from the haloalkyl, carbon number that halogen atom, the alkyl that carbon number is 1 to 12, carbon number are 1 to 4 Alkoxy, CN, NO for 1 to 122, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, two Phenyl amino, (CO) O (R4)、CO-R4、(CO)N(R4)2Or
E19And E20Separately represent hydrogen atom, carbon number as 1 to 20 hydroxy alkyl, carbon as 2 to 4 of alkyl, carbon number 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 E20Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through as follows An at least group substitutes, and haloalkyl that it is 1 to 4 selected from halogen atom, carbon number that an at least 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 to be unsubstituted or taken through an at least group as follows Generation, wherein at least a group be selected from carbon number be 1 to 20 alkyl, carbon number be 1 to 20 alkoxy ,=O, OE17、SE18、 NE21E22、(CO)E23、NO2, halogen atom, carbon number be 1 to 4 haloalkyl, CN, phenyl,Or without It is mixed with or through at least 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 attached nitrogen-atoms, which is not It is substituted or substitutes through an at least group as follows, and an at least group is selected from alkyl of the carbon number for 1 to 20, carbon number Alkoxy that haloalkyl, carbon number for 1 to 4 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 the ring that carbon number is 3 to 20 Alkyl；
E21And E22Separately represent hydrogen atom, carbon number as 1 to 20 haloalkyl, carbon as 1 to 4 of alkyl, carbon number Cycloalkyl or phenyl of the number for 3 to 10；
E21And E22Formed together with the nitrogen-atoms bonded with it 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 are 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 have an at least O, CO or NE26And alkyl that carbon number is 2 to 20, without being mixed with or being mixed with there are O, S, CO or NE26And the cycloalkyl that carbon number is 3 to 20； Or
E23Represent phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represent (CO) OE17、CONE19E20、(CO)E17Or have and be directed to E19And E20One of in definition wherein；
E25Represent COOE17、CONE19E20、(CO)E17；Or have and be directed to E17One of in definition wherein；
E26Represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have an at least O or CO And the alkyl that carbon number is 2 to 20；Or E26Represent phenyl-R1, without being mixed with or being mixed with, to have one or more O or CO and carbon number be 3 to 8 Cycloalkyl；Or E26Represent (CO) E19；Or E26Represent phenyl, E26It is to be unsubstituted or taken through an at least group as follows Generation, and alkyl that it is 1 to 20 selected from carbon number that an at least group, which is, halogen atom, carbon number be 1 to 4 haloalkyl, OE17、 SE18、NE19E20OrBut condition has at least one for the light initiator (D-2) of the structure as shown in formula (3A) It is a
For group defined in the compound shown in formula (3A), preferably correspond to such as following changes for formula (3) Compound institute definien, simply defined in oxime ester base group (such as) all replace with accordingly free oximido group
Each oxime ester base group can two kinds of configurations (Z) or (E) exist.Isomers can be separated by traditional methods, but Can be used isomer mixture as (such as) light initial substance.Therefore, light initiator (D-2), the chemical combination as shown in formula (3) Thing, the mixture comprising configurational isomer.
In a preferred embodiment, light initiator (D) includes the light initiator (D-2) of the structure as shown in formula (3), its Middle 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 representA wherein at least E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
Z1Represent CO or singly-bound；
E13Carbon number is represented as 1 to 20 alkyl, carbon number be 1 to 20 alkyl be unsubstituted or through it is as follows at least One group substitutes, and an at least group is selected from halogen atom, OE17、SE18、COOE17、CONE19E20Or PO (OCkH2k+1)2；Or
E13Carbon number is represented as 2 to 20 alkyl, 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；
E15Phenyl, naphthyl, carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through as follows at least one Group substitutes, and an at least group is selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, OE17、SE18, be mixed with There is the alkyl that an at least O or S and carbon number are 2 to 20, or it respectively substitutes through the alkyl that one or more carbon numbers are 1 to 20, the carbon Number is to be unsubstituted or substitute through an at least group as follows for 1 to 20 alkyl, and an at least 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, the Heteroaryloxycarbonyl that carbon number is 4 to 20, OE17、SE18、NE19E20Or PO (OCkH2k+1)2；Or
E15Carbon number is represented as 1 to 20 alkyl, it is to be unsubstituted or substitute through an at least group as follows, and extremely A few 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 in definition wherein；
E'15Represent to have and be directed to E15One of in definition wherein；
E16Phenyl is represented, it is to be unsubstituted or substitute through an at least group as follows, and an at least group is choosing From OE17、SE18、NE19E20, be mixed with least O, S or NE26And the alkyl that carbon number is 2 to 20；Or
E16Phenyl is represented, is to substitute through the alkyl that an at least carbon number is 1 to 20, wherein carbon number is that 1 to 20 alkyl is not It is substituted or substitutes through an at least group as follows, and an at least group is selected from halogen atom, COOE17、CONE19E20、 Aryloxycarbonyl that heteroaryl that cycloalkyl that phenyl, carbon number are 3 to 8, carbon number are 3 to 20, carbon number are 6 to 20, carbon number be 4 to 20 Heteroaryloxycarbonyl, OE17、SE18Or NE19E20；Or
E16Carbon number is represented as 1 to 20 alkyl, E16It is to be unsubstituted or substitute through an at least group as follows, and An at least 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)；
E17Carbon number is represented as 1 to 20 alkyl, it is to be unsubstituted or substitute through an at least group as follows, and extremely A few group is selected from halogen atom, OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1), carbon number be 3 to 20 cycloalkyl, its The cycloalkyl that middle carbon number is 3 to 20 is not to be mixed with or be mixed with an at least O；Or
E17Carbon number is represented as 2 to 20 alkyl, the alkyl that carbon number is 2 to 20 is to be mixed with an at least O；
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 or warpSubstitution, but condition has extremely for the light initiator (D-2) of the structure as shown in formula (3) It is one few
It must pay attention to the compound of formula as defined above (3), wherein E1、E2、E3、E4、E5、E6、E7And E8Independently 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 the alkyl or the phenyl substituted through a following at least group that carbon number is 1 to 20, wherein at least a group can For OE17Or the alkyl that carbon number is 1 to 20；
E16It is phenyl, phenyl is that a wherein at least group can be OE through following at least group substitution17Or carbon number is 1 To 20 alkyl；
E17It is that the carbon number for being unsubstituted or substituting through an at least halogen atom is 1 or 20 alkyl or is mixed with and has an at least oxygen The carbon number of atom is 1 to 20 alkyl, but there are at least one in compound of the condition for the structural formula as shown in formula (3)
In one more preferably embodiment, light initiator (E) includes the light initiator (D-2) of the structure as shown in formula (3), its Middle E1、E2、E3、E4、E5、E6、E7And E8Independently represent hydrogen atom；Or
E1And E2、E3And E4Or E5And E6It is separately common to representAn and 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；
E13Carbon number is represented as 1 to 20 alkyl, it is to be unsubstituted or substitute through an at least group as follows, and extremely A few group is selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2；Or
E13Carbon number is represented as 2 to 20 alkyl, it is to be mixed with an at least O；Or
E13Represent phenyl；
K represents integer 2；
E14Carbon number is represented as 1 to 20 alkyl or thienyl；
E15Phenyl or naphthyl is represented, and it is respectively unsubstituted or through an at least OE17Or the alkyl that carbon number is 1 to 20 substitutes； Or
E15Thienyl, hydrogen atom or carbon number are represented as 1 to 20 alkyl, wherein carbon number is that 1 to 20 alkyl is without taking In generation, substitutes through an at least group as follows, and an at least group is to be selected from OE17、SE18, carbon number be 3 to 8 cycloalkyl, NE19E20Or COOE17；Or
E15Carbon number is represented as 2 to 20 alkyl, and the alkyl that carbon number is 2 to 20 is mixed with and has SO2；
E16Phenyl or naphthyl is represented, it is respectively unsubstituted or substitutes through an at least group as follows, and an at least base Group is to be selected from OE17、SE18、NE19E20Or the alkyl that carbon number is 1 to 20；Or
E16Represent thienyl；
E17Represent hydrogen atom, carbon number as 1 to 8 alkanoyl or carbon number as 1 to 20 alkyl, carbon number be 1 to 20 alkyl To be unsubstituted or substitute through an at least group as follows, and an at least group be selected from halogen atom, O (CO)- (R1)、O(CO)-(R6), or it is mixed with the cycloalkyl that an at least O and carbon number are 3 to 20；Or
E17Carbon number is represented as 2 to 20 alkyl, and the alkyl that carbon number is 2 to 20 is mixed with an at least O；
E18Represent carbon number as 3 to 20 cycloalkyl, carbon number as 1 to 20 alkyl, its be unsubstituted or through an at least OH, O(CO)-(R6) or (CO) OE17Substitution；Or
E18Phenyl is represented, it is to be unsubstituted or substitute through an at least halogen atom；
E19And E20Be separately represent carbon number as 1 to 8 alkanoyl or carbon number as 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 (D-2) of structure shown in formula (3) has at least one
The formula (3-1) that is as defined above of specific example of the light initiator (D-2) of the present invention to formula (3-7) chemical combination Thing, formula (3-1), formula (3-2), formula (3-3), especially formula (3-1) or formula (3-3) or formula (3-1), formula (3-3) or formula (3-4), especially The compound of its formula (3-1) 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.Preferably Ground, E2RepresentCOE16OrOr E2And E1It is jointlySo 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 substituted through an at least group as follows, and an at least group is selected from the alkane that carbon number is 1 to 6 Base, 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 E20Formed with a carbon atom of the naphthalene nucleus in formula (3) 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 substituted through an at least group as follows, and an at least group is to be selected from carbon number as 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 representOr 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 substituted through an at least group as follows, and an at least group is selected from the alkane that carbon number is 1 to 6 Base, 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 E20Five yuan are formed with a carbon atom of the naphthalene nucleus in formula (3) Ring or hexatomic ring.
In addition, in an example, E9、E10、E11And E12Independently represent hydrogen atom, carbon number as 1 to 20 alkyl, not The phenyl being substituted or the phenyl substituted through an at least group as follows, at least a group are selected from the alkane that carbon number is 1 to 6 Base, halogen atom, OE17Or SE18；Or E9、E10、E11And E12Independently represent halogen atom, OE17、SE18、NE19E20Or COE16。
Alternatively, in an example, E9、E10、E11And E12Independently represent hydrogen atom, carbon number as 1 to 20 alkyl, not The phenyl being substituted or the phenyl substituted through an at least group as follows, at least a group are selected from the alkane that carbon number is 1 to 6 Base, 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 for example to represent carbon number as 1 to 20 alkyl, it is to be unsubstituted or taken through an at least group as follows Generation, wherein an above-mentioned at least group is selected from halogen atom, COOE17Or CONE19E20；Or
E13Carbon number is represented as 2 to 20 alkyl, the alkyl that carbon number is 2 to 20 is to be mixed with to have one or more O, S, SO, SO2、 NE26Or CO；
E13Carbon number is represented as 2 to 12 alkenyl, the alkenyl that carbon number is 2 to 12 is not to be mixed with or be mixed with to have one or more O, CO Or NE26；Or
E13Carbon number is represented as 3 to 10 cycloalkyl, cycloalkyl is not to be mixed with or be mixed with to have one or more O, S, CO or NE26； Or
E13Phenyl or naphthyl is represented, and it is respectively to be unsubstituted or substituting through an at least group as follows, wherein extremely A few group is to be selected from OE17、SE18、NE19E20、COE16、NO2, halogen atom, carbon number for 1 to 20 alkyl, the haloalkyl that carbon number is 1 to 4, are mixed with and alkyl that carbon number is 2 to 20 through an at least O；Or carbon number is represented as 1 To 20 alkyl, it is to be unsubstituted or substitute through an at least group as follows, wherein an above-mentioned at least group is choosing From halogen atom, E17、COOE17、OE17、SE18、CONE19E20Or PO (OCkH2k+1)2；Or carbon number is represented as 2 to 20 alkyl, its It is to be mixed with to have one or more O.
In addition, E13Carbon number is represented as 1 to 20 alkyl, it is to be unsubstituted or taken through an at least group as follows Generation, wherein an above-mentioned at least group is selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20Or PO (OCkH2k+1)2；Or carbon number is represented as 2 to 20 alkyl, the alkyl that carbon number is 2 to 20 is to be mixed with to have an O；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 group substitution shown, a wherein at least 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, be mixed with the carbon for having one or more O Number is 2 to 20 alkyl.
In another embodiment, E13Carbon number is represented as 1 to 20 alkyl, its be unsubstituted or through it is as follows at least One group substitutes, wherein an above-mentioned at least group is selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2；Or generation The alkyl that table, which is mixed with, one or more O and carbon number is 2 to 20；Or represent carbon number as 2 to 12 alkenyl, carbon number as 3 to 10 ring Alkyl, phenyl or naphthyl.
Alternatively, E13Such as carbon number can be represented as 1 to 20 alkyl, it is unsubstituted or through an at least base as follows Group's substitution, wherein an above-mentioned at least group is selected from halogen atom, E17、OE17、SE18Or PO (OCkH2k+1)2；Or represent at least The alkyl that one O is mixed with and carbon number is 2 to 20；Or represent phenyl, carbon number as 2 to 12 alkenyl or carbon number as 3 to 10 cycloalkyl.
Alternatively, E13Can represent carbon number as 1 to 20 alkyl, phenyl, carbon number as 2 to 12 alkenyl or carbon number as 3 to 10 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 E13Carbon number can be represented as the alkyl that 1 to 20 alkyl, especially carbon number are 1 to 8, such as 2- ethylhexyls；
E14Can for example represent hydrogen atom, carbon number as 3 to 8 cycloalkyl, carbon number as 2 to 5 alkenyl, carbon number is 1 to 20 Alkoxy or the alkyl that carbon number is 1 to 20, it is to be unsubstituted or substitute through an at least halogen atom or phenyl；Or
E14Phenyl or naphthyl is represented, it is respectively to be unsubstituted or substitute through an at least group as follows, and at least one Group be selected from carbon number be 1 to 6 alkyl, carbon number be 1 to 4 haloalkyl, halogen atom, OE17、SE18And/or NE19E20； Or
E14Carbon number is represented as 3 to 5 heteroaryl, such as thienyl, or represent carbon number as 1 to 8 alkoxy, Benzyl epoxides or Phenoxy group.
Alternatively, E14Carbon number can for example be represented as 1 to 20 alkyl, and the alkyl that carbon number is 1 to 20 is through an at least halogen Atom or phenyl substitutes；Or
E14Represent carbon number as 3 to 5 heteroaryl (such as thienyl) or represent be unsubstituted or through it is as follows at least One group substitution phenyl, and an at least group be selected from carbon number be 1 to 6 alkyl, carbon number be 1 to 4 haloalkyl, halogen Atom, OE17、SE18And/or NE19E20；Or
E14Carbon number is represented as 1 to 8 alkoxy, Benzyl epoxides or phenoxy group.
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 substitutes；Or
E14It is phenyl, and phenyl is unsubstituted or substitutes through the alkyl that an at least carbon number is 1 to 6.
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, is more preferably the alkyl that carbon number is 1 to 8.
E15May be, for example, the aryl that carbon number is 6 to 20 or the heteroaryl that carbon number is 5 to 20, it is respectively unsubstituted or through as follows Shown at least group substitution, and an at least group be selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, CN、NO2、OE17、SE18、NE19E20, carbon number be 1 to 20 alkyl；Or
E15It is hydrogen atom, the cycloalkyl that carbon number is 3 to 8, wherein carbon number is that 3 to 8 cycloalkyl is without being mixed with or being mixed with There are one or more O, CO or NE26；Or
E15It is the alkyl that carbon number is 1 to 20, the alkyl that carbon number is 1 to 20 is unsubstituted or through an at least base as follows Group's substitution, and an at least group is selected from halogen atom, OE17, carbon number be 3 to 8 cycloalkyl, carbon number be 5 to 20 heteroaryl Heteroaryloxy-carbonyl that phenyloxycarbonyl that base, carbon number are 8 to 20, carbon number are 5 to 20, NE19E20、COOE17、CONE19E20、 PO(OCkH2k+1)2、Phenyl or the phenyl substituted through following group, above-mentioned group are former selected from halogen Son, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 haloalkyl, OE17Or NE19E20；Or
E15It is the alkyl that carbon number is 2 to 20, and the alkyl that carbon number is 2 to 20 is mixed with and has at least 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 substitutes through the alkyl that carbon number is 1 to 12；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 substitute through an at least group as follows, And an at least group is to be selected from OE17、SE17, carbon number be 3 to 8 cycloalkyl, NE19E20Or COOE17；Or
E15It is the alkyl that carbon number is 2 to 20, and the alkyl that carbon number is 2 to 20 is mixed with and has an at least O or SO2。
In the compound as shown in formula (3), E15May be, for example, hydrogen atom, phenyl, naphthyl, it is respectively unsubstituted or through carbon Number substitutes for 1 to 8 alkyl；Or
E15It is thienyl, the alkyl that carbon number is 1 to 20, it is unsubstituted or substitutes through an at least group as follows, And an at least group is to be selected from OE17、SE17, carbon number be 3 to 8 cycloalkyl, NE19E20Or COOE17；Or
E15It is the alkyl that carbon number is 2 to 20, and the alkyl that carbon number is 2 to 20 is mixed with and has an at least O or SO2。
E15In particular (such as) carbon number be 3 to 8 cycloalkyl or carbon number be 1 to 20 alkyl, preferably carbon number be 1 to 20 Alkyl, be more preferably carbon number be 1 to 12 alkyl.
E'14And E'15Preferably respectively have as described above for E14And E15One of which in defining.
Z2Be (such as) O, S or SO, such as O or S, in particular O.
E16May be, for example, aryl (especially phenyl or naphthyl, especially phenyl) that carbon number is 6 to 20 or carbon number be 5 to 20 it is miscellaneous Aryl (especially thienyl), it is respectively unsubstituted or substitutes through an at least group as follows, and at least a group is to be selected from In phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, CN, NO2、OE17、SE18、NE19E20Or it is mixed with the carbon number of an at least O For 1 to 20 alkyl；Or its respectively through an at least carbon number be 1 to 20 alkyl substitute, carbon number be 1 to 20 alkyl be unsubstituted or Substitute through an at least group as follows, and an at least group is selected from halogen atom, COOE17、CONE19E20, phenyl, Aryloxycarbonyl that heteroaryl that cycloalkyl that carbon number is 3 to 8, carbon number are 5 to 20, carbon number are 6 to 20, carbon number are 5 to 20 Heteroaryloxycarbonyl, OE17、SE18Or NE19E20；Or
E16It is hydrogen atom, the alkyl that carbon number is 1 to 20, and the alkyl that carbon number is 1 to 20 is unsubstituted or through as follows An at least group substitution, and an at least group be selected from halogen atom, phenyl, OH, SH, carbon number be 3 to 6 alkenyloxy group, 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 the alkyl that carbon number is 2 to 12 is mixed with and has an at least 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 At least group substitution shown in lower, and an at least group is selected from phenyl, halogen atom, the alkyl halide that carbon number is 1 to 4 Base, OE17、SE18、NE19E20Or the alkyl that carbon number is 1 to 20；Or
E16It is the alkyl that carbon number is 1 to 20, the alkyl that carbon number is 1 to 20 is unsubstituted or through an at least base as follows Group's substitution, and an at least 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 the alkyl that carbon number is 2 to 12 is to be mixed with to have an at least 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, it is respectively unsubstituted or through as follows at least one Group substitutes, and an at least 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 (such as) phenyl, phenyl is unsubstituted or substitutes through an at least 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 E16Be (such as) phenyl or naphthyl, it is respectively unsubstituted or is taken through the alkyl that an at least carbon number is 1 to 20 Generation.
E16In particular phenyl, and phenyl substitutes through the alkyl that an at least carbon number is 1 to 20.
E17May be, for example, hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, it is unsubstituted or through as follows An at least group substitutes, and an at least group is 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 be 3 to 20 cycloalkyl or be mixed with the carbon number for having an at least O For 3 to 20 cycloalkyl；Or
E17It is the alkyl that carbon number is 2 to 20, and the alkyl that carbon number is 2 to 20 is mixed with and has an at least 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 an at least O without being mixed with or being mixed with；Or
E17It is benzoyl, and benzoyl is to be unsubstituted or substitute through an at least group as follows, and at least The alkoxy substitution 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 the heteroaryl that phenyl, naphthyl or carbon number are 5 to 20, it is respectively unsubstituted or through an at least base as follows Group's substitution, and alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that an at least group, which is, carbon number be 1 to 12 alkoxy, CN、NO2, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amino or
In another embodiment, E17Be (such as) hydrogen atom, phenyl-R5, carbon number be 1 to 20 alkyl, it is without taking In generation, substitutes through an at least group as follows, and an at least group is selected from halogen atom, O (CO)-(R1)、O(CO)- (R6) or be mixed with have an at least 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 the carbon number of a few O is 2 to 20, the cycloalkyl for being 3 to 20 without being mixed with or being mixed with the carbon number for having an at least O；Or
E17It is benzoyl, benzoyl is to be unsubstituted or substitute through an at least group as follows, and at least one The alkoxy that alkyl, halogen atom, OH or the carbon number that it is 1 to 6 selected from carbon number that group, which is, are 1 to 3；Or
E17It is phenyl or naphthyl, it is respectively unsubstituted or substitutes through an at least group as follows, and an at least group Be be 1 to 12 selected from halogen atom, carbon number alkyl or carbon number be 1 to 12 alkoxy.
E17Also for (such as) hydrogen atom, phenyl-R5, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 20 alkyl, it is It is unsubstituted or substitutes through an at least group as follows, and it selected from halogen atom, carbon number is 3 to 20 that an at least group, which is, Cycloalkyl, O (CO)-(R1)、O(CO)-(R6) or be mixed with the alkyl that the carbon number for having an at least O is 2 to 20, or E17It is that carbon number is 2 to 20 alkyl, it, which is mixed with, an at least 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 group substitution as follows, and an at least group is to be selected from O (CO)-(R1)、O(CO)-(R6) or be mixed with and have at least The carbon number of one O is 2 to 20 alkyl, or E17It is the alkyl that carbon number is 2 to 20, it, which is mixed with, an at least O.
E18Be (such as) carbon number be 3 to 20 cycloalkyl, it has an at least 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 substitutes through an at least 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 O, S, CO, NE26Or COOE17；Or
E18It is the alkanoyl that carbon number is 2 to 8 or the enoyl- that carbon number is 3 to 6, benzoyl；Or
E18It is the heteroaryl that phenyl, naphthyl or carbon number are 3 to 20, it is respectively unsubstituted or through an at least base as follows Group's substitution, and an at least group is to be selected from the haloalkyl, carbon that halogen atom, the alkyl that carbon number is 1 to 12, carbon number are 1 to 4 Number is 1 to 12 alkoxy or NO2。
In another embodiment, E18Be (such as) carbon number be 3 to 20 cycloalkyl, carbon number be 1 to 20 alkyl, it is not It is substituted or substitutes through an at least group as follows, and an at least 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 an at least halogen atom or carbon number are 1 to 12, especially Halogen atom substitutes.
E18Be (such as) 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 be 2 to 8 alkanoyl, benzoyl, phenyl or naphthyl.
For example, E18It is the alkyl that carbon number is 1 to 20, it substitutes through an at least 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 takes through an at least halogen atom Generation.
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 Alkyl, the cycloalkyl that carbon number is 3 to 20, phenyl-R5, phenyl or naphthyl, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 8 alkane Acyloxy, the enoyl- or benzoyl that carbon number is 3 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；Or
E19And E20It is that heteroaromatic ring system is formed together with the nitrogen-atoms being bonded, heteroaromatic ring system is without taking In generation, substitutes through an at least group as follows, and an at least group is to be selected from the alkyl, carbon number 1 that carbon number is 1 to 20 To 4 haloalkyl 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 be 3 to 20 cycloalkyl, phenyl-R5, carbon number be 1 to 8 alkanoyl, carbon number be 1 to 8 alkanoyl Epoxide, the enoyl- or benzoyl that carbon number is 3 to 12；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 Alkyl, the cycloalkyl that carbon number is 3 to 20, phenyl-R5, 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 to form morpholine ring with the nitrogen-atoms being bonded.
For example, E21And E22Be separately hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 halo Alkyl, the cycloalkyl that carbon number is 3 to 10 or phenyl；Or
E21And E22It is to form morpholine ring with the nitrogen-atoms being bonded.E21And E22Especially it is separately hydrogen atom or carbon Number is 1 to 20 alkyl.
E23Be (such as) hydrogen atom, OH, phenyl or carbon number be 1 to 20 alkyl.E23In particular hydrogen atom, OH or carbon number For 1 to 4 alkyl.
E24Be preferably configured to such as E19And E20Defined one of which.E25Be preferably configured to such as E17Defined One of which.
E26Be (such as) 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, an at least O or CO；Or
E26It is phenyl-R1, carbon number be 3 to 8 cycloalkyl, and carbon number be 3 to 8 cycloalkyl be without being mixed with or being mixed with one Or multiple O or CO；Or
E26It is (CO) E19Or phenyl, and phenyl is to be unsubstituted or substitute through a following at least group, at least a group can Haloalkyl that the alkyl for being 1 to 20 for carbon number, halogen atom, carbon number are 1 to 4, OE17、SE18、NE19E20；Or
E26Represent (such as) hydrogen atom, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 haloalkyl；It is phenyl-R1、 Cycloalkyl, (CO) E that carbon number is 3 to 819Or phenyl, and phenyl is to be unsubstituted or taken through the alkyl that an at least carbon number is 1 to 20 Generation.In addition, E26Be (such as) 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 (D-2) of the foregoing structure with as shown in formula (3) is such as, but not limited to as follows The light initiator of structure shown in formula (3-10) to formula (3-95).
Usage amount based on alkali soluble resin (B) is 100 parts by weight, and the usage amount scope of light initiator (D-2) is 5 weights Part is measured to 50 parts by weight, preferably 10 parts by weight to 45 parts by weight, so using 15 parts by weight to 40 parts by weight as more preferably.
Light initiator (D-3)
The light initiator (D) of the present invention can further include light initiator (D-3).
Light initiator (D-3) can be selected from acetophenone based compound (acetophenone), diimidazole based compound (biimidazole), acyl oxime compound (acyl oxime) or these a combination.
Above-mentioned acetophenone based 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 based compound is to 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 ) -4,4 ', phenyl 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-click Azoles -3- substituents] -, 1- (oxygen-acetyl oxime) [ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazole-3-yl]-, 1- (O-acetyl oxime), such as the name of an article of Ciba Specialty Chemicals is CGI-242 person, shown in its structure such as following formula (6-1)], 1- [4- (phenyl) phenyl]-octane -1,2- diketone -2- (O- benzoyls Base oxime) [1- [4- (phenylthio) phenyl]-octane-1,2-dione 2- (O-benzoyloxime), such as Ciba The commodity of the trade name CGI-124 of Specialty Chemicals manufactures, shown in its structure such as following formula (6-2)], 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-acetyl oxime), such as rising sun electrification company system, shown in its structure such as following formula (6-3)].
It is preferred that light initiator (D-3) is 2- methyl isophthalic acids-(4- methylthiophenyis) -2- morpholino -1- acetone, 2- benzyls Base -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 a combination.
It is preferred that light initiator (D-3) 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), acetyl group (acetyl) Deng α-diketone (α-diketone) class compound；Keto-alcohol (acyloin) class compound of diphenylhydroxyethanone (benzoin) etc.； Diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether), hexichol second Keto-alcohol ether (acyloin ether) class compound of alcohol ketone isopropyl ether (benzoin isopropyl ether) etc.；2,4,6- tri- Methyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide), it is double- (2,6- dimethoxys benzoyl) -2,4,4- trimethylpentyl phosphine oxides [bis- (2,6-dimethoxy-benzoyl) -2,4, 4-trimethyl-phenyl-phosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) class compound； Quinone (quinone) class compound of anthraquinone (anthraquinone), 1,4- naphthoquinones (1,4-naphthoquinone) etc.；Benzoyl Methyl chloride (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl-phenylsulfone), three (trichlorines Methyl)-s- triazines [tris (trichloromethyl)-s-triazine] etc. halide；And di-t-butyl peroxidating The peroxide of thing (di-tertbutylperoxide) etc..Wherein, with benzophenone (benzophenone) class compound compared with It is good, especially with 4,4 '-bis- (diethylamine) benzophenone are optimal.
Above-mentioned smooth initiator (D-3) can the individually a kind of or a variety of uses of mixing.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, and the usage amount scope of light initiator (D-3) is 0 weight Part is measured to 90 parts by weight, preferably 0 parts by weight to 70 parts by weight, so using 0 parts by weight to 50 parts by weight as more preferably.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, and the usage amount scope of light initiator (D) is 10 weights Part is measured to 100 parts by weight, preferably 20 parts by weight to 90 parts by weight, so using 30 parts by weight to 80 parts by weight as more preferably.
Solvent (E)
Solvent (E) need to select to can dissolve pigment (A), alkali soluble resin (B), the compound of the unsaturated group containing ethene (C) and light initiator (D), and the appropriate evaporative that not react to each other and have with above-mentioned composition is needed.
Solvent (E) can be identical with preparing solvent used in alkali soluble resin (B), and details are not described herein.It is it is preferred that molten Agent (E) is to be selected from propylene glycol methyl ether acetate, cyclohexanone or 3- ethoxyl ethyl propionates.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, and the usage amount scope of solvent (E) is 500 parts by weight To 5,000 parts by weight, preferably 800 parts by weight to 4,500 parts by weight, so with 1,000 parts by weight to 4,000 parts by weight for more It is good.
Dyestuff (F)
The photosensitive polymer combination of the present invention is selectively included dyestuff (F).Dyestuff (F) is that collocation pigment (A) makes With having the dyestuff (F) that special spectrum may be selected in usual skill in the technical field of the invention.Dyestuff (F) is for example but unlimited In azo dyes, azo metal misfit thing dyestuff, anthraquinone dye, bipseudoindoxyl dye, thioindigo color, phthalocyanine dye, diphenyl-methane dye Material, kiton colors, xanthene dye, thiazine dye, the dye of positive ion, cyanine dyes, nitro dye, quinoline dye, naphthoquinones dye Material, oxazine dye etc..
In one embodiment, dyestuff (F) be selected from C.I. solvent reds 2, C.I. solvent red 24s, C.I. solvent reds 27, C.I. solvent red 49, C.I. solvent reds 52, C.I. solvent reds 57, C.I. solvent red 8s 9, C.I. solvent reds 111, C.I. solvent reds 114th, 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 is 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 is 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 are 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 list The solely a kind of or a variety of uses of mixing.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, the usage amount scope of dyestuff (F) for 0 parts by weight extremely 50 parts by weight, preferably 0 parts by weight to 40 parts by weight, so using 0 parts by weight to 30 parts by weight as more preferably.
Additive (G)
Photosensitive polymer combination alternative includes additive (G), such as, but not limited to：Filler, alkali-soluble tree High-molecular compound, adherence accelerating agent, antioxidant, ultra-violet absorber, anti-agglutinant beyond fat (B) etc..
Additive (G) is such as, but not limited to the fillers such as glass, aluminium；Polyvinyl alcohol, polyalkylene glycol monoalkyl ether, poly- fluorine third High-molecular compound beyond the alkali soluble resins such as olefin(e) acid alkyl ester (B)；Vinyltrimethoxysilane, vinyl triethoxyl Silane, vinyl three (2- methoxyethoxies) silane, nitrogen-(2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, Nitrogen-(2- amino-ethyls) -3- TSL 8330s, 3-aminopropyltriethoxysilane, 3- epoxy prapanol propyl group Trimethoxy silane, 3- epoxy prapanol hydroxypropyl methyls dimethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silicon Alkane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- metacryloxy propyl trimethoxy silicon The adherence accelerating agents such as alkane, 3- mercaptopropyl trimethoxy silanes；2,2- thiobis (4- methyl-6-tert-butylphenols), 2,6- The antioxidants such as di-t-butyl phenol；2- (the 3- tert-butyl group -5- methyl -2- hydroxy phenyls) -5- chlorphenyls change nitrogen, alkoxy benzene The ultra-violet absorbers such as ketone；And the anti-agglutinant such as Sodium Polyacrylate.Above-mentioned additive (G) can be individually a kind of or mixes a variety of make With.
Usage amount based on alkali soluble resin (B) is 100 parts by weight, and the usage amount scope of additive (G) is 0.1 weight Part is to 10 parts by weight, preferably 0.3 parts by weight to 7 parts by weight, so using 0.5 parts by weight to 4 parts by weight as more preferably.
The preparation method and colored filter of colored filter
The manufacture method of colored filter, is to comprise the following steps：On a substrate, by foregoing photosensitive resin composition Thing forms a pixel layer.
Colored filter is as obtained by the manufacture method of the above-mentioned colored filter.
The manufacture method of colored filter is mainly by revolution coating, cast coat, ink-jet application (ink-jet) or roller The coating methods such as formula coating, the photosensitive resin combination for being mixed into solution state is coated on substrate.After coating, first In a manner of being dried under reduced pressure, most solvent is removed, then solvent is removed in a manner of pre-baked (pre-bake) and is formed pre-baked Film.Wherein, be dried under reduced pressure and pre-baked condition, according to the species of each composition, compounding ratio and it is different, in general, it is 0 to be dried under reduced pressure Carried out 1 second to 60 seconds under to the pressure of 200mmHg, pre-baked carried out 1 minute to 15 points at a temperature of 70 DEG C to 110 DEG C Clock.After pre-baked, pre-baked film is exposed under specified mask (mask), developer solution 15 is impregnated at a temperature of 23 ± 2 DEG C Second developed to 5 minutes, remove should not part and form pattern.The light used is exposed, with the purple of g lines, h lines, i lines etc. Outside line is preferred, and ultraviolet device can be (super) high-pressure mercury-vapor lamp or metal halid lamp.
The concrete example of aforesaid base plate can be such as, but not limited to：For the alkali-free glass of liquid crystal display device, soda-lime glass, hard Matter glass (Pai Lesi glass), quartz glass, soda-lime glass and in nesa coating accompanying on these glass；Or for solid The photo-electric conversion device substrate of body camera etc. is (such as：Silicon substrate) etc..These substrates are usually to be initially formed each pixel of isolation The black matrix" (black matrix) of dyed layer.
The concrete example of developer solution：Sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus, silicic acid Sodium, sodium methyl silicate, ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole Cough up, the alkaline aqueous solution that the alkali compounds such as piperidines or 1,8- diazabicylo-(5,4,0) -7- hendecenes is formed, the alkalescence The concentration range of aqueous solution is generally 0.001 to 10 weight %, preferably 0.005 to 5 weight %, is more preferably 0.01 to 1 weight Measure %.
During the developer solution formed using aforementioned base aqueous solution, usually cleaned again with water after development, secondly with pressure Contracting air or compressed nitrogen air-dry pattern.
The substrate with photo-hardening film layer after air-drying, using heating units such as hot plate or baking ovens, is in temperature range Heat 1 to 15 minute, the volatile ingredient in film is removed, and make unreacted ethene in film at 100 DEG C to 280 DEG C Property unsaturated double-bond carry out thermmohardening reaction.Photosensitive polymer combination using assorted (mainly including three color of red, green, blue) exists In predetermined pixel with same step repetitive operation three times, you can obtain the pixel shader layer of three color of red, green, blue.
Secondly, on pixel shader layer, ITO (tin indium oxide) evaporations are formed under vacuum with 220 DEG C to 250 DEG C temperature Film, if necessary, after etching and wiring are implemented to ITO evaporation films, is coated liquid crystal orienting film polyimides, and then burns till, i.e., Can be as the colored filter of liquid crystal display.
Furthermore the foregoing liquid crystal orienting film used, is the orientation for limiting liquid crystal molecule, and is not particularly limited herein, 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 tool usually intellectual, and the non-emphasis for the present invention, therefore do not repeat separately.
Liquid crystal display element
Liquid crystal display element includes a colored filter as described above.
Liquid crystal display element, mainly by colored filter (CF) base obtained by above-mentioned method for manufacturing colored filtering substrate Plate, and thin film transistor (TFT) (thin film transistor are set；TFT drive substrate) is formed.First, above-mentioned 2 Gap (structure cell interval is intervened between plate base；Cell gap) to make oppositely disposed, the surrounding position of 2 plate bases is bonded with sealing agent Afterwards, the filling injection liquid crystal in the gap that substrate surface and sealing agent are distinguished, then seal injection hole and form liquid crystal crystalline substance Born of the same parents (cell).Then, on the outer surface of liquid crystal cell, that is, other sides of each substrate of composition liquid crystal cell, patch Close polarizer and liquid crystal display element is made.
As for the foregoing liquid crystal used, that is, liquid-crystal compounds or liquid-crystal composition, herein and it is not particularly limited, can makes With any type liquid-crystal compounds and liquid-crystal composition.
Compared with prior art, using the present invention above-mentioned photosensitive polymer combination obtained by colored filter, tool There is good resistance to sputter.
Embodiment
Prepare the first alkali soluble resin (B-1)
Synthesis example B-1-1
By fluorenes ring oxygen compound (model ESF-300, the Nippon Steel's chemistry system of 100 parts by weight；Epoxide equivalent 231), 30 weights Measure the acrylic acid of part, the benzyltriethylammonium chloride of 0.3 parts by weight, the DBPC 2,6 ditertiary butyl p cresol and 130 weights of 0.1 parts by weight Measure part propylene glycol methyl ether acetate continuously added to 500mL four-hole boiling flask in, and pan feeding speed control 25 parts by weight/point Clock, in the range of temperature is maintained 100 DEG C to 110 DEG C, reaction 15 it is small when after, you can acquisition 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 In, while the tetrabydrophthalic anhydride of 6 parts by weight and the benzophenone tetracarboxylic dianhydride of 13 parts by weight are added, and be heated to 110 DEG C to 115 DEG C, when reaction 2 is small after, you can acquisitions acid value is 98.0mgKOH/g, and number average molecular weight is 1,623 First alkali soluble resin (B-1-1).
Synthesis example B-1-2
By fluorenes ring oxygen compound (model ESF-300, the Nippon Steel's chemistry system of 100 parts by weight；Epoxide equivalent 231), 30 weights Measure the acrylic acid of part, the benzyltriethylammonium chloride of 0.3 parts by weight, the DBPC 2,6 ditertiary butyl p cresol and 130 weights of 0.1 parts by weight Measure part propylene glycol methyl ether acetate continuously added to 500mL four-hole boiling flask in, and pan feeding speed control 25 parts by weight/point Clock, in the range of temperature is maintained 100 DEG C to 110 DEG C, reaction 15 it is small when after, you can acquisition 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 In, while the benzophenone tetracarboxylic dianhydride of 13 parts by weight is added, when reaction 2 is small at 90 DEG C to 95 DEG C, then, add 6 weights Measure part tetrabydrophthalic anhydride, and at 90 DEG C to 95 DEG C reaction 4 it is small when, you can acquisition acid value is 99.0mgKOH/g, and Number average molecular weight is 2,162 the first alkali soluble resin (B-1-2).
Synthesis example B-1-3
By epoxide (model NC-3000, Japanese chemical drug (strain) system of 400 parts by weight；Epoxide equivalent 288), 102 weights Measure the acrylic acid of part, the methoxyl group phenol (methoxyphenol) of 0.3 parts by weight, the triphenylphosphine and 264 parts by weight of 5 parts by weight Propylene glycol methyl ether acetate be placed in reaction bulb, temperature is maintained 95 DEG C, when reaction 9 is small after, you can obtaining acid value is The intermediate product of 2.2mgKOH/g.Then, the tetrabydrophthalic anhydride (tetrahydrophthalic of 151 parts by weight is added Anhydride), when reaction 4 is small at 95 DEG C, you can acquisition acid value is 102mgKOH/g, and number average molecular weight is 2,589 The first alkali soluble resin (B-1-3).
Synthesis example B-1-4
By epoxide (model NC-3000, Japanese chemical drug (strain) system of 200 parts by weight；Epoxide equivalent 288), 60 weights Measure the acrylic acid of part, the methoxyl group phenol (methoxyphenol) of 0.15 parts by weight, the triphenylphosphine and 200 weight of 2.5 parts by weight Part propylene glycol methyl ether acetate be placed in reaction bulb, temperature is maintained 95 DEG C, when reaction 9 is small after, you can obtaining acid value is The intermediate product of 2.5mgKOH/g.Then, the tetrabydrophthalic anhydride (tetrahydrophthalic of 70 parts by weight is added Anhydride) and 15 parts by weight 3,4- epoxycyclohexyl-methyl methacrylates, at 95 DEG C react 4 it is small when, you can obtain It is 105mgKOH/g to obtain acid value, and the first alkali soluble resin (B-1-4) that number average molecular weight is 3,410.
Prepare the second alkali soluble resin (B-2)
Synthesis example B-2-1
Blender, thermometer, condenser pipe and nitrogen inlet are set on one or four cervical vertebra bottles, 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 3,4- epoxycyclohexyl-methyls methacrylate (ECMMA) of 15 parts by weight, the o- vinyl benzene of 10 parts by weight Methyl glycidyl ethers (referred to as VBGE), and the 2 of 4.5 parts by weight, the double -2- methylbutyronitriles of 2 '-azo (referred to as AMBN) are molten Above-mentioned four cervical vertebras bottle is instilled dropwise in the propylene glycol methyl ether acetate of 100 parts by weight, and by this mixed solution is interior when 2 is small In.After when 100 DEG C of reactions 6.5 are small, the acrylic acid (referred to as AA) of 5 parts by weight is added in the four cervical vertebra bottles full of nitrogen, And temperature is risen to 110 DEG C.React 6 it is small when after, you can the second alkali soluble resin (B-2-1) of synthesis example B-2-1 is made.
Synthesis example B-2-2 to B-2-6
Synthesis example B-2-2 to B-2-6 is to prepare the second alkali soluble resin with the step identical with synthesis example B-2-1 (B-2), difference be in：Change reaction temperature, polymerization time, the species and usage amount of composition, its actual conditions is stated in detail in table 1。
Prepare the compound of unsaturated group containing ethene (C-1)
Synthesis example (C-1-1)
With agitating device, return duct, thermometer conical flask in, add 286.3g (1.0mol) (RS) -1,1 ' - Union -2-naphthol, the ethylene carbonate of 264.2g (3.0mol), the toluene of the potassium carbonate of 41.5g (0.3mol) and 2000ml, When reaction 12 is small at 110 DEG C.After reaction, gained reaction solution is cleaned through washing with 1%NaOH aqueous solutions.Then, washed Untill washing water is in neutrality.Using spin concentration instrument, solvent is distilled off in the solution after washing under reduced pressure, can obtain The 2mol reacting ethylene oxide things of (RS) -1,1 '-union -2-naphthol of 300.0g.
Then, in the conical flask with agitating device, return duct, thermometer and water separation device, 187.2g is added The 2mol reacting ethylene oxides thing of above-mentioned (RS)-the 1,1 '-union -2-naphthol of (0.5mol), the acrylic acid of 86.5g (2.4mol), The p-methyl benzenesulfonic acid of 0.95g, the quinhydrones of 0.85g, the toluene of 915g, the hexamethylene of 390g, in 95 DEG C to 105 DEG C of reaction temperature In, generation water is removed with solvent azeotropic distillation, simultaneously reacted.After reaction, neutralized using 25%NaOH aqueous solutions, Afterwards, cleaned 3 times using the 15 mass % saline solutions of 200g.Finally, with vacuum distillation removes solvent and obtains following formula (1-1) The compound of unsaturated group containing ethene (C-1-1).
Synthesis example (C-1-2)
With agitating device, return duct, thermometer conical flask in, add 286.3g (1.0mol) (RS) -1,1 ' - The toluene of union -2-naphthol, the carbonic acid of 306.3g (3.0mol) secondary propyl ester, the potassium carbonate of 41.5g (0.3mol) and 2000ml, When reaction 12 is small at 110 DEG C.After reaction, gained reaction solution is cleaned through washing with 1%NaOH aqueous solutions.Then, washed Untill washing water is in neutrality.Using spin concentration instrument, solvent is distilled off in the solution after washing under reduced pressure, can obtain The 2mol propylene oxide reactants of (RS) -1,1 '-union -2-naphthol of 322.0g.
Then, in the conical flask with agitating device, return duct, thermometer and water separation device, 201.2g is added The 2mol propylene oxide reactant of above-mentioned (RS)-the 1,1 '-union -2-naphthol of (0.5mol), the acrylic acid of 86.5g (2.4mol), The p-methyl benzenesulfonic acid of 0.95g, the quinhydrones of 0.88g, the toluene of 985g, the hexamethylene of 420g, in 95 DEG C to 105 DEG C of reaction temperature In, generation water is removed with solvent azeotropic distillation, simultaneously reacted.After reaction, neutralized using 25%NaOH aqueous solutions, Afterwards, cleaned 3 times using the 15 mass % saline solutions of 300g.Finally, with vacuum distillation removes solvent and obtains following formula (1-2) The compound of unsaturated group containing ethene (C-1-2).
Synthesis example (C-1-3)
In autoclave (autoclave), (RS) -1 of 286.3g (1.0mol), 1 '-union -2-naphthol, 114.5g are added Toluene and 0.5g potassium carbonate, and the air in autoclave is replaced into nitrogen.Afterwards, in 120 DEG C to 140 DEG C temperature and Under the reaction pressure of below 0.2MPa, instill 23.7g (0.54mol) ethylene oxide, and react 6 it is small when.After reaction, depressurizing In environment, by unreacted ethylene oxide and toluene distillation, you can (RS) -1 of 302.2g is made, 1 '-union -2-naphthol 0.5mol reacting ethylene oxide things.
Then, in the conical flask with agitating device, return duct, thermometer and water separation device, 154.2g is added 0.5mol reacting ethylene oxides thing, the propylene of 21.6g (0.3mol) of above-mentioned (RS)-the 1,1 '-union -2-naphthol of (0.5mol) Acid, the p-methyl benzenesulfonic acid of 0.95g, the quinhydrones of 0.85g, the toluene of 1130g, the hexamethylene of 485g, in 95 DEG C to 105 of reaction temperature In DEG C, generation water is removed with solvent azeotropic distillation, simultaneously reacted.After reaction, using in 25%NaOH aqueous solutions With afterwards, cleaned 3 times using the 15 mass % saline solutions of 300g.Finally, with vacuum distillation removes solvent and obtains containing ethene Unsaturated group compound (C-1-3).
Through1H-NMR confirmations, each R of foregoing gained unsaturated group containing ethene compound (C-1-3)1aFor hydrogen atom, R2aFor ethylidine, and s+t is 0.5.
Synthesis example (C-1-4)
Synthesis example (C-1-4) is carried out in a manner of identical with synthesis example (C-1-3).Unlike, synthesis example (C-1-4) It is that the usage amount of ethylene oxide is changed into 47.4g (1.1mol).Through1H-NMR confirmations, gained unsaturated group containing ethene chemical combination Each R of thing (C-1-4)1aFor hydrogen atom, R2aFor ethylidine, and s+t is 1.Synthesis example (C-1-5)
Synthesis example (C-1-5) is carried out in a manner of identical with synthesis example (C-1-3).Unlike, synthesis example (C-1-5) It is that the usage amount of ethylene oxide is changed into 236.8g (5.4mol).Through1H-NMR confirmations, gained unsaturated group containing ethene Each R of compound (C-1-5)1aFor hydrogen atom, R2aFor ethylidine, and s+t is 5.
Synthesis example (C-1-6)
Synthesis example (C-1-6) is carried out in a manner of identical with synthesis example (C-1-3).Unlike, synthesis example (C-1-6) It is that the usage amount of ethylene oxide is changed into 473.5g (10.8mol).Through1H-NMR confirmations, gained unsaturated group containing ethene Each R of compound (C-1-6)1aFor hydrogen atom, R2aFor ethylidine, and s+t is 10.
Prepare photosensitive polymer combination
Embodiment 1
By the second alkali soluble resin (B-2-1) of the synthesis example B-2-1 of 100 parts by weight, the C.I. paratoneres of 5 parts by weight 254 (hereinafter referred to as A-1), the compound (C-1-1) of the unsaturated group containing ethene of 2 parts by weight, the EO of 18 parts by weight are modified Trimethacrylate acid trihydroxy methyl propyl ester (C-2-1), 10 parts by weight 1- [4- (phenyl) phenyl]-octane -1,2- diketone - 2- (O- benzoyl groups oxime) (hereinafter referred to as D-3-1), after adding the 3- ethoxyl ethyl propionates (hereinafter referred to as E-1) of 500 parts by weight, With swing-out stirrer, dissolved mixing, you can modulation and photosensitive polymer combination, the photosensitive polymer combination with Following properties evaluations modes are evaluated, and acquired results are as shown in table 2.
Embodiment 2 to 18 and comparative example 1 to 6
Embodiment 2 to 18 and comparative example 1 to 6 are come with the step identical with the photosensitive polymer combination of embodiment 1 Prepare, it is to change the species of raw material in photosensitive polymer combination and make that difference, which is in embodiment 2 to 18 and comparative example 1 to 6, The result of dosage, its actual conditions prepared and properties evaluations is stated in detail in table 2 and table 3.
Evaluation method
Resistance to sputter
Photosensitive polymer combination obtained by embodiment and comparative example is changed with the colourity before and after sputter, is thereby assessed Its resistance to sputter.By the photosensitive polymer combination obtained by embodiment and comparative example in a manner of rotary coating, ruler is coated on On the very little glass substrate for 100mm × 100mm.Then, it is dried under reduced pressure, its pressure is 100mmHg and the time is 30 seconds. Then, pre-baked processing procedure is carried out, its temperature is 80 DEG C and the time is 2 minutes, forms the pre-baked film that a thickness is 2.5 μm.Carry out After pre-baked processing procedure, using energy as 60mJ/cm2Ultraviolet light (exposure machine Canon PLA-501F) irradiate the pre-baked film, and will Pre-baked film after exposure is impregnated in 23 DEG C of developer solution.After 1 minute, which is cleaned with pure water, and with 230 DEG C into Baked after row 30 minutes, i.e., form pixel shader layer on the glass substrate.
Then, the colourity (L*, a*, b*) of pixel shader layer is measured with colorimeter (great Zhong electronics corporations system, model MCPD), Then sputter forms a film resistance value and is for 14.6 Ω/sq, thickness on the pixel shader layerIto thin film, sputter Temperature is 220 DEG C, the colored filter is made.
Afterwards, the colourity of above-mentioned colored filter is measured with the colorimeter, and colourity change (Δ is calculated with formula (7) Eab*), obtained colourity change (Δ Eab*) is smaller, represents that resistance to sputter is better, and commented according to following evaluation criteria Valency：
Δ Eab*=[(Δ L)2+(Δa)2+(Δb)2]1/2Formula (7)
◎：Δ Eab* ＜ 1；
○：1≤Δ Eab* ＜ 3；
△：3≤Δ Eab* ＜ 5；
╳：5≦ΔEab*.
According to the evaluation result of table 2, when the photosensitive polymer combination of the present invention includes containing second shown in formula (1) During alkene unsaturated group compound (C-1), the colored filter formed using above-mentioned photosensitive polymer combination is had well Resistance to sputter.Furthermore when photosensitive polymer combination further includes light initiator (D-1), it can further lift above-mentioned colour The resistance to sputter of optical filter.
On the other hand, according to the evaluation result of table 3, if insatiable hunger containing ethene is not used in photosensitive polymer combination With based compound (C-1), even if addition light initiator (D-1), obtained colored filter can not be still set to reach good resistance to Sputter.
Using the present invention photosensitive polymer combination, colored filter and its manufacture method and its application, by using The specific compound of unsaturated group containing ethene (C-1) shown in formula (1), can make the coloured silk formed by photosensitive polymer combination Colo(u)r filter, has good resistance to sputter.
Although the present invention is disclosed above with several embodiments, so it is not limited to the present invention, belonging to the present invention Any tool usually intellectual in technical field, without departing from the spirit and scope of the present invention, when can make various changes with Retouching, therefore protection scope of the present invention is when subject to appended claims institute defender.
Table 1
MAA methacrylic acids
HOMs 2- methacryloyloxyethyl succinates
AA acrylic acid
N-PMI N-phenylmaleimides
HEMA 2-hydroxyethyl methacrylates
BzMA benzyl methacrylates
ECMMA 3,4- epoxycyclohexyl-methyl methacrylate
MGMA methacrylic acid 2- methyl polyglycidyls
The o- vinyl benzene methyl glycidyl ethers of VBGE
AMBN 2, the double -2- methylbutyronitriles of 2 '-azo
ADVN 2,2 '-azo-two-(2,4 dimethyl-penten cyanogen)
PGMEA propylene glycol methyl ether acetates
EEP 3- ethoxyl ethyl propionates
Table 2
Table 3
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.1. paratonere 17
The trimethacrylate acid trihydroxy methyl propyl ester of C-2-1 E0 modifications
C-2-2 dipentaerythritol acrylates
The dipentaerythritol acrylate of the own Inner esters modifications of C-2-3
The compound of D-1-1 formulas (2-1)
The compound of D-1-2 formulas (2-2)
The compound of D-1-3 formulas (2-6)
The compound of D-2-1 formulas (3-10)
The compound of D-2-2 formulas (3-17)
The compound of D-2-3 formulas (3-36)
D-3-1 1- [4- (phenyl) phenyl]-octane -1,2- diketone -2- (0- benzoyl groups oxime)
D-3-2 2,2 '-bis- (2,4- dichlorophenyl) -4,4 ', 5,5 '-tetraphenyl diimidazole (2,2 '-bis (2,4- Dichloro phenyl) -4,4 ', 5,5 '-tetraphenyl-biimidazole)
D-3-3 4,4 '-bis- (diethylaminos) benzophenone (4,4 '-bis (diethylamino) benzophenone)
D-3-4 2- benzyl -2- nitrogen, nitrogen-diformazan ammonia -1- (4- morphlinophenyls) -1- butanone (2-benzyl-2-N, N- dimethylamino-1-(4-morpholinophenyl)-1-butanone)
E-1 3- ethoxyl ethyl propionates
E-2 propylene glycol methyl ether acetates
E-3 cyclohexanone
F-1 C.I. acid reds 52
F-2 C.I. acid reds 289
F-3 C.I. solvent reds 52
G-1 3- epoxy prapanol propyl trimethoxy silicanes
G-2 2,6- di-t-butyl phenol

Claims (12)

1. a kind of photosensitive polymer combination, it is characterised in that include：
Pigment (A)；
Alkali soluble resin (B)；
The compound (C) of the unsaturated group containing ethene, includes the change of the unsaturated group containing ethene of structure as shown in following formula (1) Compound (C-1)：
In formula (1), R1aThe alkyl for being 1 to 4 for identical or each different hydrogen atoms or carbon number；R2aFor identical or respective difference Carbon number be 1 to 4 alkyl；And s and t each representative unit repeat mean values, and a summation of s and t for 0.4 to 12；
Light initiator (D)；And
Solvent (E).
2. photosensitive polymer combination as claimed in claim 1, wherein the light initiator (D), which include, has knot shown in formula (2) The light initiator (D-1) of structure：
In formula (2), R1bRepresent the organic group containing the cycloalkyl that carbon number is 3 to 20, R2bAnd R3bAlkane is represented independently of one another Base or aryl, and R4bRepresent alkyl.
3. photosensitive polymer combination as claimed in claim 1, wherein the light initiator (D), which include, has knot shown in formula (3) The light initiator (D-2) of structure：
In formula (3), E1、E2、E3、E4、E5、E6、E7And E8Represent independently of one another 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 E8Warp is represented independently of one another Substituted carbon number is 2 to 10 alkenyl；Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Common representative-(CH independently of one another2)p-W-(CH2)q-； Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8It is common independently of one another to representA wherein at least E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8For
E9、E10、E11And E12Hydrogen atom, carbon number each independently are represented as 1 to 20 alkyl, which is not for 1 to 20 alkyl Be substituted or substitute through an at least group as follows, and an at least group be selected from phenyl, halogen atom, CN, OH, SH, alkoxy, (CO) OH or (CO) O (R that carbon number is 1 to 41), wherein R1Carbon number is represented as 1 to 4 alkyl；Or
E9、E10、E11And E12The phenyl being unsubstituted or the benzene substituted through an at least group as follows are represented independently of one another Base, the alkyl, halogen atom, CN, OE that it is 1 to 6 selected from carbon number which, which is,17、SE18Or NE19E20；Or
E9、E10、E11And E12Halogen atom, CN, OE are represented independently of one another17、SE18、SOE18、SO2E18Or NE19E20, wherein should Deng substituent OE17、SE18Or NE19E20It is without or via such group E17、E18、E19And/or E20With a carbon original of naphthalene nucleus Son forms five-membered ring or hexatomic ring；Or
E9、E10、E11And E12Represent independently of one anotherCOE16Or NO2；
W represents O, S, NE26Or singly-bound, p represent 0 to 3 integer, q represents 1 to 3 integer, Z1Represent CO or singly-bound；
E13Carbon number is represented as 1 to 20 alkyl, the alkyl which is 1 to 20 is unsubstituted or through as follows at least one Group substitutes, and wherein an at least group is selected from halogen atom, E17、COOE17、OE17、SE18、CONE19E20、NE19E20、PO (OCkH2k+1)2OrOr
E13Carbon number is represented as 2 to 20 alkyl, the alkyl which is 2 to 20, which is mixed with, one or more O, S, SO, SO2、NE26Or CO；Or
E13Carbon number is represented as 2 to 12 alkenyl, the carbon number be 2 to 12 alkenyl be without be mixed with or through be mixed with have one or more 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 is It is unsubstituted or substitutes through an at least 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 substitute through an at least group as follows, Wherein an at least group is to be selected from OE17、SE18、NE19E20、COE16、CN、NO2, halogen it is former Son, carbon number be 1 to 20 alkyl, carbon number be 1 to 4 haloalkyl, being mixed with has one or more O, S, CO or NE26And carbon number is 2 To 20 alkyl；The phenyl or the naphthyl respectively through carbon number be 3 to 10 cycloalkyl substitution or respectively through be mixed with have one or more O, S, CO or NE26And the cycloalkyl that carbon number is 3 to 10 substitutes；
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 the carbon number that substitutes through an at least group as follows is 1 to 20, and an at least group is to be selected from halogen Plain 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 substitutes through an at least group as follows, and an at least group Be selected from carbon number be 1 to 6 alkyl, carbon number be 1 to 4 haloalkyl, 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 should Phenoxy group is to be unsubstituted or substitute through an at least group as follows, and an at least group is 1 to 6 selected from carbon number Alkyl, the haloalkyl and/or halogen atom that carbon number is 1 to 4；
E15It is 6 to 20 aromatic radical or carbon number as 3 to 20 heteroaryl to represent carbon number, it is respectively unsubstituted or through as follows An at least group substitutes, and an at least group is selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, CN, NO2、 OE17、SE18、NE19E20、PO(OCkH2k+1)2And SO bonds and alkyl and SO that carbon number is 1 to 102Bond and carbon number are 1 to 10 Alkyl, be mixed with and have one or more O, S or NE26And the alkyl that carbon number is 2 to 20；Or it respectively takes through the alkyl that carbon number is 1 to 20 The alkyl that generation, the wherein carbon number are 1 to 20 is to be unsubstituted or substitute through an at least group as follows, and an at least base Group is 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 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
E15Carbon number is represented as 1 to 20 alkyl, the alkyl which is 1 to 20 is unsubstituted or through as follows at least one Group substitutes, and an at least group is selected from halogen atom, 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、Phenyl, the wherein carbon number are 1 to 20 Alkyl be to substitute through phenyl, and the alkyl halide that alkyl that it is 1 to 20 through halogen atom, carbon number that the phenyl, which is, carbon number are 1 to 4 Base, OE17、SE18Or NE19E20Substitution；Or
E15Carbon number is represented as 2 to 20 alkyl, the alkyl which is 2 to 20 is to be mixed with to have one or more O, SO or SO2, the warp It is mixed with and alkyl that carbon number is 2 to 20 is to be unsubstituted or substitute through an at least group as follows, and an at least group It is selected from halogen atom, OE17、COOE17、CONE19E20, phenyl or through OE17、SE18Or NE19E20Substituted phenyl；Or
E15Carbon number is represented as 2 to 20 alkanoyl or benzoyl, it is unsubstituted or through an at least group as follows Substitution, and an at least group is to be selected from the alkyl, halogen atom, phenyl, OE that carbon number is 1 to 617、SE18Or NE19E20；Or
E15Representative is unsubstituted or through an at least OE17Substituted naphthoyl or the Heteroarylcarbonyl that carbon number is 3 to 14；Or
E15Carbon number is represented as 2 to 12 alkoxy carbonyl, the alkoxy carbonyl which is 2 to 12 is without being mixed with or through at least One O is mixed with, wherein this through be mixed with or without be mixed with and carbon number be 2 to 12 alkoxy carbonyl be to be unsubstituted or through an at least hydroxyl Base substitutes；Or
E15Phenyloxycarbonyl is represented, which is to be unsubstituted or substitute through an at least group as follows, and should Haloalkyl that alkyl that it is 1 to 6 selected from carbon number that an at least group, which is, halogen atom, carbon number are 1 to 4, phenyl, OE17、SE18 Or NE19E20；Or
E15Represent CN, CONE19E20、NO2, carbon number be 1 to 4 haloalkyl, S (O)r-R2And S (O)rThe phenyl of bond, wherein Should be with S (O)rThe phenyl of bond be unsubstituted or through carbon number be 1 to 12 alkyl or SO2-R2Substitution, and R2Carbon number is represented as 1 To 6 alkyl；Or
E15Representative and SO2Phenyl, diphenylphosphino or the two (R of O bonds3)-phosphono, wherein should and SO2The phenyl of O bonds It is to be unsubstituted or substitute through the alkyl that carbon number is 1 to 12, and R3Carbon number is represented as 1 to 4 alkoxy；
R represents 1 to 2 integer；
E'14Represent to have and be directed to E14One of in definition wherein；
E'15Represent to have and be directed to E15One of in definition wherein；
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 Few group substitution, and an at least group is selected from phenyl, halogen atom, the haloalkyl that carbon number is 1 to 4, CN, NO2、 OE17、SE18、NE19E20, be mixed with and have one or more O, S or NE26And the alkyl that carbon number is 1 to 20, or the alkane that carbon number is 1 to 20 The alkyl that base, the wherein carbon number are 1 to 20 is to be unsubstituted or substitute through an at least group as follows, wherein this at least one Group is 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 3 to 20, OE17、SE18Or NE19E20；Or
E16Hydrogen atom or carbon number are represented as 1 to 20 alkyl, wherein the carbon number is that 1 to 20 alkyl is unsubstituted or through as follows Shown at least group substitution, and an at least group is 3 to 6 selected from halogen atom, 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
E16Carbon number is represented as 2 to 12 alkyl, which 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 R4Carbon number is represented as 1 to 8 alkyl；Or
E16Represent through SE18Substituted phenyl, wherein E18Bond is represented to the COE16The phenyl of the attached carbazole part or The singly-bound of the 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 an at least base as follows Group's substitution, and an at least group is selected from halogen atom, 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) bond phenyl, (CO) OH, (CO) O (R1), carbon number Cycloalkyl, SO for 3 to 202-(R7)、O(R7) or be mixed with through an at least O and cycloalkyl that carbon number is 3 to 20, wherein, R5Represent Carbon number be 1 to 3 alkyl, R6Carbon number is represented as 2 to 4 alkenyl, and R7Carbon number is represented as 1 to 4 haloalkyl；Or
E17Carbon number is represented as 2 to 20 alkyl, and the alkyl that the carbon number is 2 to 20 is to be mixed with to 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, it is that have one or more O, S, CO without being mixed with or being mixed with Or NE26；Or
E17Represent carbon number and be bonded the group formed with carbon number as 3 to 10 cycloalkyl by 1 to 8 alkyl, and the group is not Through being mixed with or being mixed with through an at least O；Or
E17Represent benzoyl, which is unsubstituted or substitutes through an at least group as follows, and this at least one The alkoxy that alkyl, halogen atom, OH or the carbon number that it is 1 to 6 selected from carbon number that group, which is, are 1 to 3；Or
E17Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through an at least group as follows Substitution, and alkyl that it is 1 to 12 selected from halogen atom, OH, carbon number that an at least group, which is, carbon number be 1 to 12 alkoxy, CN、NO2, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2, diphenyl-amino orWherein R8Carbon number is represented as 1 to 3 alkoxy, and R9Carbon number is represented as 1 to 12 alkyl；Or
E17With withPhenyl or
One of carbon atom of naphthyl ring forms singly-bound；
E18Represent hydrogen atom, carbon number as 2 to 12 cycloalkyl or phenyl-R as 3 to 20 of alkenyl, carbon number5, the wherein carbon number is 2 Cycloalkyl and the phenyl-R that alkenyl, the carbon number to 12 are 3 to 205Be without be mixed with or be mixed with have one or more O, S, CO, NE26Or COOE17；Or
E18Carbon number is represented as 1 to 20 alkyl, the alkyl which is 1 to 20 is unsubstituted or through an at least base as follows Group's substitution, and an at least 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
E18Carbon number is represented as 2 to 20 alkyl, the alkyl which is 2 to 20 is to be mixed with to 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 alkene acyl Base；Or
E18Benzoyl is represented, which is to be unsubstituted or substitute through an at least group as follows, and this is at least The alkyl that the alkoxy or carbon number that alkyl that it is 1 to 6 selected from carbon number that one group, which is, halogen atom, OH, carbon number are 1 to 4 are 1 to 4 Sulfenyl；Or
E18Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is unsubstituted or through an at least base as follows Group's substitution, and an at least group is to be selected from the haloalkyl, carbon that halogen atom, the alkyl that carbon number is 1 to 12, carbon number are 1 to 4 Alkoxy, CN, the NO of number for 1 to 122, phenyl-R8, phenoxy group, carbon number be 1 to 12 alkyl sulfenyl, phenylsulfartyl, N (R9)2、 Diphenyl amino, (CO) O (R4)、(CO)-R4、(CO)N(R4)2Or
E19And E20Represent independently of one another hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 2 to 4 hydroxy alkyl, carbon number is 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 E20Phenyl, naphthyl or carbon number are represented as 3 to 20 heteroaryl, it is respectively unsubstituted or through as follows at least one Group substitutes, and an at least group is to be selected from the alcoxyl that halogen atom, the haloalkyl that carbon number is 1 to 4, carbon number are 1 to 20 The alkoxy that alkyl, benzoyl or the carbon number that base, carbon number 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 this five yuan or hexa-atomic saturation or unsaturation ring are to be unsubstituted or taken through an at least group as follows Generation, wherein an at least group be selected from carbon number be 1 to 20 alkyl, carbon number be 1 to 20 alkoxy ,=O, OE17、SE18、 NE21E22、(CO)E23、NO2, halogen atom, carbon number be 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 the cycloalkyl that carbon number is 3 to 20；Or
E19And E20It is that heteroaromatic ring system is formed together with attached nitrogen-atoms, which is to be unsubstituted Or substitute through an at least group as follows, and alkyl that it is 1 to 20 selected from carbon number that an at least group, which is, carbon number are 1 to 4 Haloalkyl, carbon number be 1 to 20 alkoxy ,=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 the ring that carbon number is 3 to 20 Alkyl；
E21And E22Represent independently of one another hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, carbon number is 3 Cycloalkyl or phenyl to 10；
E21And E22Formed together with the nitrogen-atoms bonded with it 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 are 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 have at least O, CO or NE26And alkyl that carbon number is 2 to 20, without being mixed with or being mixed with there are O, S, CO or NE26And the cycloalkyl that carbon number is 3 to 20；Or
E23Represent phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represent (CO) OE17、CONE19E20、(CO)E17Or have and be directed to E19And E20One of in definition wherein；
E25Represent COOE17、CONE19E20、(CO)E17；Or E25With for E17One of in definition wherein；
E26Represent hydrogen atom, carbon number as 1 to 20 alkyl, carbon number as 1 to 4 haloalkyl, be mixed with and have at least an O or CO and carbon Number is 2 to 20 alkyl；Or E26Represent phenyl-R1, without be mixed with or be mixed with through an at least O or CO and carbon number be 3 to 8 cycloalkanes Base；Or E26Represent (CO) E19；Or E26Represent phenyl, E26It is to be unsubstituted or substitute through an at least group as follows, and should Haloalkyl that alkyl that it is 1 to 20 selected from carbon number that an at least group, which is, halogen atom, carbon number are 1 to 4, OE17、SE18、 NE19E20OrBut condition has at least one for the light initiator (D-2) of the structure as shown in formula (3)
4. photosensitive polymer combination as claimed in claim 1, the wherein alkali soluble resin (B) include the first alkali-soluble Resin (B-1), first alkali soluble resin (B-1) are and the mixture bags as obtained by a mixture carries out polymerisation Containing the epoxide (b-1-1) with least two epoxy groups and with least one carboxylic acid group and at least one ethene not The compound (b-1-2) of saturation base.
5. photosensitive polymer combination as claimed in claim 4, wherein should the epoxide with least two epoxy groups (b-1-1) there is the structure as shown in formula (4) or formula (5)：
In formula (4), R1c、R2c、R3cAnd R4cHydrogen atom, halogen atom, the alkyl that carbon number is 1 to 5, carbon are represented independently of one another The aralkyl that the aromatic radical or carbon number that alkoxy that number is 1 to 5, carbon number are 6 to 12 are 6 to 12；And
In formula (5), R5cTo R18cThe alkyl or carbon number that expression hydrogen atom, halogen atom, carbon number are 1 to 8 independently of one another are 6 To 15 aromatic radical；And g represents 0 to 10 integer.
6. photosensitive polymer combination as claimed in claim 1, wherein the usage amount based on the alkali soluble resin (B) is 100 parts by weight, the usage amount scope of the pigment (A) is 5 parts by weight to 300 parts by weight, this contains the chemical combination of ethene unsaturated group The usage amount scope of thing (C) is 20 parts by weight to 200 parts by weight, the usage amount scope of the light initiator (D) for 10 parts by weight extremely 100 parts by weight, and the usage amount scope of the solvent (E) is 500 parts by weight to 5,000 parts by weight.
7. photosensitive polymer combination as claimed in claim 1, wherein the usage amount based on the alkali soluble resin (B) is 100 parts by weight, the usage amount scope of the compound (C-1) for containing ethene unsaturated group of structure shown in the formula (1) is 2 weight Part to 80 parts by weight.
8. photosensitive polymer combination as claimed in claim 2, wherein the usage amount based on the alkali soluble resin (B) is 100 parts by weight, the usage amount scope of the light initiator (D-1) is 5 parts by weight to 50 parts by weight.
9. photosensitive polymer combination as claimed in claim 3, wherein the usage amount based on the alkali soluble resin (B) is 100 parts by weight, the usage amount scope of the light initiator (D-2) is 5 parts by weight to 50 parts by weight.
10. a kind of manufacture method of colored filter, it is characterised in that it is used according to any one of claim 1 to 9 Photosensitive polymer combination forms pixel layer.
11. a kind of colored filter, it is characterised in that it is as obtained by manufacture method according to claim 10.
12. a kind of liquid crystal display device, it is characterised in that it is to include colored filter as claimed in claim 11.
CN201711057616.2A 2016-11-01 2017-11-01 Photosensitive resin composition, color filter, method for manufacturing the same, and application thereof Pending CN108020989A (en)

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