CN104950571B

CN104950571B - Photosensitive resin composition for color filter and application thereof

Info

Publication number: CN104950571B
Application number: CN201510109906.1A
Authority: CN
Inventors: 许荣宾
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2014-03-24
Filing date: 2015-03-13
Publication date: 2019-05-10
Anticipated expiration: 2035-03-13
Also published as: CN104950571A; TWI559085B; TW201537296A

Abstract

The invention relates to a photosensitive resin composition for a color filter and application thereof. The photosensitive resin composition comprises a pigment (A), an alkali-soluble resin (B), a compound (C) having an ethylenically unsaturated group, a photoinitiator (D), and an organic solvent (E). The alkali-soluble resin (B) comprises a first alkali-soluble resin (B-1) and a second alkali-soluble resin (B-2). The photosensitive resin composition can improve the voltage holding ratio and the developing resistance of the color filter.

Description

Colored filter photosensitive polymer combination and its application

Technical field

The present invention is a kind of colored filter photosensitive polymer combination in relation to liquid crystal display and its is formed by Colored filter is especially to provide a kind of voltage retention and the good colored filter photosensitive resin composition of resistance to developability Object.

Background technique

Currently, colored filter has been widely used in colour liquid crystal display device, colour facsimile apparatus, colour camera etc. Application field.As the market demand of the imaging equipments such as colour liquid crystal display device increasingly expands, in the production skill of colored filter Also tend to diversification in art.

Colored filter usually can by decoration method, print process, electricity the methods of method or pigment dispersion method, by red, green, blue Etc. pixels be formed on transparent glass substrate be made.In general, to improve the contrast of colored filter, pixel shader interlayer Configurable light shield layer (or black matrix", black matrix).

The processing procedure of above-mentioned pigment dispersion method is that first pigment is dispersed in photocurable resin and forms coloring phototonus tree The resin combination is finally formed pixel shader layer by oil/fat composition.Furthermore, the processing procedure of pigment dispersion method, usually First on the transparent supports such as glass substrate, light shield layer is formed with the metals such as chromium, chromium oxide or photoresist photomask.So Afterwards, which is coated with by the photoresist for being dispersed with red pigment (colourama resist) by rotary coating mode It on transparent support, is exposed by mask, and carry out development treatment after exposure to obtain red pixel.Then, with Red, green, blue etc. can be made respectively in same mode of operation, i.e. recycling coating, exposure, the mode developed on support Three-color pixel.

In recent years, the purposes of colour liquid crystal display device is no longer confined on PC, is also widely used for color TV And on various monitoring screens (especially large-sized color liquid crystal screen), so being wanted for liquid crystal display color saturation Ask higher and higher.Therefore, pigment proportion contained by photosensitive polymer combination is also higher and higher, alkali soluble resin and photonasty The relative usage quantitative change of monomer is few, the crosslinking degree decline after causing exposure, and the bad problem waited of resistance to developability is caused to occur.

In the revealed content of Japanese Unexamined Patent Publication 2004-138950 bulletin, specific alkali soluble resin is used, it can To form the flat pixel shader layer in surface, the colored filter that pattern form, resistance to developability and brightness are excellent in, however this The voltage retention that method easily leads to the photosensitive polymer combination is too low and lead to be easy lacking for image retention when showing picture It falls into and exists.

Therefore, how resistance to developability and voltage retention are promoted simultaneously, to reach the requirement of current industry, for institute of the present invention Belong to the target for making great efforts research in technical field.

Summary of the invention

Therefore, one aspect of the present invention is to provide a kind of colored filter photosensitive polymer combination.This is photosensitive Property resin combination can promote the voltage retention and resistance to developability of colored filter.

It is to utilize colored filter above-mentioned it is another aspect of the invention to provide a kind of method for manufacturing colored filter Mating plate forms pixel layer with photosensitive polymer combination.

Another aspect of the present invention is to provide a kind of colored filter, is made using method above-mentioned.

Another aspect of the invention is to provide a kind of liquid crystal display device, and it includes colored filters above-mentioned.

Above-mentioned aspect according to the present invention proposes a kind of colored filter photosensitive polymer combination, this photonasty tree Oil/fat composition includes pigment (A), alkali soluble resin (B), the compound (C) with ethylene unsaturated group, light initiator (D) And organic solvent (E), analysis states it below.

Photosensitive polymer combination

Pigment (A)

Pigment (A) of the invention can be any combination of inorganic pigment, organic pigment or above-mentioned pigment.

Above-mentioned inorganic pigment can be the metallic compound of metal oxide or metal complex etc..The metal oxide can For the oxide of the metal of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc or antimony etc. and the composite oxides of aforementioned metal.

Above-mentioned organic pigment is to be selected from C.I. 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 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71, 73；C.I. paratonere 1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32, 37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58: 2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112, 113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177, 178,179,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226, 242,243,245,254,255,264,265；C.I. pigment violet 1,19,23,29,32,36,38,39；C.I. pigment blue 1,2, 15,15:3,15:4,15:6,16,22,60,66；C.I. pigment Green 7,36,37；C.I. pigment brown 23,25,28；And C.I. face Expect black 1,7.Organic pigment above-mentioned can the individually a kind of or a variety of uses of mixing.

The average grain diameter of the primary particle of the pigment (A) be 10nm to 200nm, preferably 20nm to 150nm, more preferably 30nm to 130nm.

Total usage amount based on aftermentioned alkali soluble resin (B) is 100 parts by weight, and the usage amount of the pigment (A) is 30 weights Part is measured to 300 parts by weight, preferably 35 parts by weight to 250 parts by weight, more preferably 40 parts by weight to 200 parts by weight.

When necessary, which is selectively included dispersing agent, concrete example, such as: cationic system, anionic system, non- The interfacial agent of ionization series, both sexes, polysiloxane series or fluorine system etc..

The interfacial agent may include, but are not limited to polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether or poly- The polyethylene oxide alkyl ethers class of ethylene oxide oil ether etc.；Polyethylene oxide octyl phenylate or polyethylene oxide nonyl phenylate etc. Polyethylene oxide alkylbenzene ethers interfacial agent；The poly- second of polyethylene glycol dilaurate or polyglycol distearate etc. Diol diesters class interfacial agent；Sorbitan fatty acid ester class interfacial agent；The polyesters interface of fatty acid modification is living Property agent；The polyurethanes interfacial agent of tertiary amine modification；The manufacture of chemical industrial company, SHIN-ETSU HANTOTAI, the quotient of model KP Product；Toray Dow Corning Silicon manufacture, the commodity of model SF-8427；The manufacture of common prosperity society oil chemical industry, The commodity of model Polyflow；Get Ke Mu company (Tochem Products Co., Ltd.) manufacture, the quotient of model F-Top Product；Big Japan's printing ink chemical industry manufacture, the product of model Megafac；Sumitomo 3M manufacture, the product of model Fluorad； Asahi Glass manufacture, the commodity of model Asahi Guard or Surflon.The interfacial agent can be individually a kind of or be mixed a variety of It uses.

Alkali soluble resin (B)

Alkali soluble resin (B) of the invention may include the first alkali soluble resin (B-1) and the second alkali soluble resin (B-2).In addition, alkali soluble resin (B) is selectively included third alkali soluble resin (B-3).

First alkali soluble resin (B-1)

First alkali soluble resin (B-1) is formed by mixture institute combined polymerization, wherein the mixture include have by Hinder the ethylene monomer (b-1-1) of amine structure and the ethylene unsaturated monomer (b-1- with one or more carboxylic acid groups 2)。

In addition, mixture above-mentioned is selectively included ethylene monomer (b-1-1) and tool with the structure of hindered amine There are other copolymerizable ethylene insatiable hungers other than the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups With monomer (b-1-3).

Ethylene monomer (b-1-1) with the structure of hindered amine

Ethylene monomer (b-1-1) with the structure of hindered amine can be for such as shown in following formula (I) with the second of the structure of hindered amine Alkene monomer:

In formula (I), X₁It is 6 that hydrogen atom, carbon number, which are represented, as 1 to 18 straight chained alkyl, branched alkyl or naphthenic base, carbon number Aromatic radical, the aromatic alkyl that carbon number is 7 to 12, acyl group, oxygen radical to 20, or-OX₄；X₄Representing hydrogen atom, carbon number is 1 To the fragrant alkane that 18 straight chained alkyl, branched alkyl or naphthenic base, the aromatic radical that carbon number is 6 to 20 or carbon number are 7 to 12 Base；X₂And X₃It is independently represented each other methyl, ethyl, phenyl or bond forms the aliphatic ring that carbon number is 4 to 12 mutually；" * " generation Table covalent bond.

Work as X₁And X₄Represent carbon number as 1 to 18 straight chained alkyl, branched alkyl or naphthenic base when, X₁And X₄It can be carbon number be 1 To 18 straight chained alkyl or branched alkyl or carbon number be 3 to 8 naphthenic base, concrete example, such as: methyl, ethyl, n-propyl, Isopropyl, normal-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl or cetyl etc..Work as X₁Carbon number is represented as 6 to 20 virtue When perfume base, concrete example can be phenyl, Alpha-Naphthyl or betanaphthyl.Work as X₁And X₄Represent carbon number as 7 to 12 aromatic alkyl when, X₁ And X₄It can be the aromatic radical for the alkyl bond for being 1 to 8 with carbon number, and the carbon number of the aromatic radical is 6 to 10, concrete example can be Benzyl base, phenethyl, α-Jia Ji Benzyl base or 2- phenyl-propane -2- base etc..Work as X₁And X₄Acyl group, carbon number are represented as 2 to 8 alkanoyl Or when aroyl, concrete example can be acetyl or benzoyl base.

X of the invention₁Preferably can be the alkyl or oxygen radical that hydrogen atom, carbon number are 1 to 5, wherein with hydrogen atom, oxygen from It is more preferably by base and methyl.

Secondly, the X in formula (I)₂And X₃It can be bonded the structure to form cycloaliphatic ring, concrete example can be pentamethylene or hexamethylene Deng.X₂And X₃It preferably can be methyl.

It can be for such as following formula (I-1) and (I-2) institute with the ethylene monomer with the structure of hindered amine shown in such as formula (I) The compound for the structure shown:

In formula (I-1) and (I-2), X₅And X₇Separately represent hydrogen atom or methyl；X₆Represent methine or carbon number For 2 to 5 alkylidene；X₈Represent the structure as shown in formula (I)；X₉Representative-CONH-* ,-SO₂-、-SO₂NH-*, wherein " * " generation Table and X₈The covalent bond of bond；X₆Preferably ethylidine or propylidyne are more preferably with ethylidine；The integer that s is 0 to 8, with 0 to 6 It is preferable.

The concrete example of ethylene monomer as shown in formula (I-1) with the structure of hindered amine can be for such as following formula (I-1-1) to (I- Structure shown in 1-7):

In formula (I-1-1) into (I-1-7), X₅It is defined as described above, it does not repeat separately herein.

The concrete example of ethylene monomer as shown in formula (I-2) with the structure of hindered amine can be for such as following formula (I-2-1) to (I- Structure shown in 2-4):

In formula (I-2-1) into (I-2-4), X₇It is defined as described above, it does not repeat separately herein.

It can be 4- methacrylamido -2,2,6,6- that the present invention, which has the ethylene monomer (b-1-1) of the structure of hindered amine, Tetramethyl-piperidines (4-methacrylamido-2,2,6,6-tetramethylpiperidine) or Hitachi's chemical conversion industry Co., Ltd.'s manufacture, model FA-712HM [2,2,6,6- tetramethyl-4-piperidyl methyl acrylates；That is previously described formula (I-1-1), And X₅Represent methyl] or FA-711MM [1,2,2,6,6- pentamethyl-piperidyl methyl acrylate；That is previously described formula (I-1-2), and X₅ Represent methyl].

The aforementioned ethylene monomer (b-1-1) with the structure of hindered amine can the individually a kind of or a variety of uses of mixing.

Based on ethylene monomer (b-1-1) with the structure of hindered amine and aftermentioned with one or more carboxylic acid groups Total usage amount of ethylene unsaturated monomer (b-1-2) and other copolymerizable ethylene unsaturated monomers (b-1-3) is 100 Parts by weight, this has the usage amount of the ethylene monomer (b-1-1) of the structure of hindered amine for 3 parts by weight to 45 parts by weight, preferably 4 Parts by weight are to 40 parts by weight, more preferably 5 parts by weight to 35 parts by weight.

Ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups

There is the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups may include, but are not limited to propylene for this Acid, methacrylic acid (methacrylic acid；MAA), butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2- third Alkene acyl ethyoxyl succinate or 2- methacryloyloxyethyl succinate (2-methacryloyloxyethyl succinate monoester；) etc. HOMS unsaturated monocarboxylic acid compound；Maleic acid, maleic anhydride, fumaric acid, clothing health Unsaturated dicarboxylic acid (acid anhydride) compound of acid, itaconic anhydride, citraconic acid or citraconic anhydride etc.；Insatiable hungers more than three carboxylic acid groups With polybasic carboxylic acid (acid anhydride) compound.The aforementioned ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups can The individually a kind of or a variety of uses of mixing.

Preferably, it is selected from third that this, which has the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups, Olefin(e) acid, methacrylic acid, 2- acryloyloxyethyl succinate or 2- methacryloyloxyethyl succinate.Wherein, with 2- Acryloyloxyethyl succinate or 2- methacryloyloxyethyl succinate are more preferably.

Based on the aforementioned ethylene monomer (b-1-1) with the structure of hindered amine, with one or more carboxylic acid groups' Total usage amount of ethylene unsaturated monomer (b-1-2) and aftermentioned other copolymerizable ethylene unsaturated monomers (b-1-3) For 100 parts by weight, it is 15 weights that this, which has the usage amount of the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups, Part is measured to 55 parts by weight, preferably 20 parts by weight to 50 parts by weight, more preferably 25 parts by weight to 45 parts by weight.

Other copolymerizable ethylene unsaturated monomers (b-1-3)

The ethylene monomer (b-1-1) with the structure of hindered amine and the ethylene with one or more carboxylic acid groups Other copolymerizable ethylene unsaturated monomers (b-1-3) may include, but are not limited to benzene second other than unsaturated monomer (b-1-2) Alkene (styrene；SM), the aromatic vinyl of α-methylstyrene, vinyltoluene, p-chlorostyrene, methoxy styrene etc. Based compound；N-phenylmaleimide (N-phenylmaleimide；PMI), the o- hydroxyphenyl-maleimides of N-, N- The p- hydroxyphenyl-maleimides of m- hydroxyphenyl-maleimides, N-, N- ortho-methyl phenyl maleimide, the m- first of N- The o- methoxyphenyl maleimide of the p- methylphenylmaleimide of base phenyl maleimide, N-, N-, the m- methoxy of N- The maleimation of the p- methoxyphenyl maleimide of base phenyl maleimide, N-, N- N-cyclohexylmaleimide etc. Close object；Methyl acrylate (methyl acrylate；MA), methyl methacrylate, ethyl acrylate, ethyl methacrylate, N-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methyl The secondary butyl ester of n-butyl acrylate, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, propylene Tert-butyl acrylate, Tert-butyl Methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy methacrylate, acrylic acid -2- hydroxyl Base propyl ester, methacrylic acid -2- hydroxy propyl ester, acrylic acid -3- hydroxy propyl ester, methacrylic acid -3- hydroxy propyl ester, acrylic acid - 2- hydroxybutyl, methacrylic acid -2- hydroxybutyl, acrylic acid -3- hydroxybutyl, methacrylic acid -3- hydroxybutyl, propylene Acid -4- hydroxybutyl, methacrylic acid -4- hydroxybutyl, allyl acrylate, allyl methacrylate, acrylic acid benzene first Ester, benzyl methacrylate (benzyl methacrylate；BzMA), phenyl acrylate, phenyl methacrylate, propylene Triethylenetetraminehexaacetic acid glycol methoxyethoxy ester, methacrylic acid triethylene glycol methoxyethoxy ester, lauryl methacrylate, methacrylic acid 14 Arrcostab, methacrylic acid cetyl ester, octadecyl methacrylate, methacrylic acid eicosane base ester, methyl-prop Olefin(e) acid docosane base ester, acrylic acid double cyclopentenyl aoxidize ethyl ester (dicyclopentenyloxyethyl acrylate； ) etc. DCPOA unsaturated carboxylic ester compound；Acrylic acid-N, N- dimethylamino ethyl ester, methacrylic acid-N, N- dimethyl Amino ethyl ester, acrylic acid-N, N- diethylamino propyl ester, methacrylic acid-N, N- dimethylamino propyl ester, acrylic acid-N, N- Dibutylamino propyl ester, N- methacrylic acid iso-butyl amino ethyl ester；Acrylic acid epoxy propyl diester, glycidyl third The unsaturated carboxylic acid glycidyl ester compounds of base ester etc.；The carboxylic acid second of vinyl acetate, vinyl propionate, vinyl butyrate etc. Enester compound；Methoxy ethylene, vinyl ethyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers etc. are no It is saturated ether compound；The nitrilation vinyl compound of acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, cyaniding Asia ethylene etc.；Propylene The insatiable hunger of amide, Methacrylamide, α-chloroacrylamide, N- hydroxyethyl acrylamide, N- hydroxyethyl methacrylamide etc. And amide compound；The aliphatic conjugated diene compound of 1,3- butadiene, isoprene, chlorination butadiene etc..It is aforementioned other Copolymerizable ethylene unsaturated monomer (b-1-3) can the individually a kind of or a variety of uses of mixing.

Preferably, other copolymerizable ethylene unsaturated monomers (b-1-3) are selected from styrene, N- phenyl horse Come acid imide, methyl acrylate, methyl methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid -2- hydroxy methacrylate, third Olefin(e) acid benzene methyl, benzyl methacrylate, acrylic acid double cyclopentenyl aoxidize any mixing of ethyl ester or above compound.

Based on the aforementioned ethylene monomer (b-1-1) with the structure of hindered amine, with one or more carboxylic acid groups' Total usage amount of ethylene unsaturated monomer (b-1-2) and other copolymerizable ethylene unsaturated monomers (b-1-3) is 100 Parts by weight, the usage amount of other copolymerizable ethylene unsaturated monomers (b-1-3) they are 0 parts by weight to 82 parts by weight, compared with Good is 10 parts by weight to 70 parts by weight, more preferably 20 parts by weight to 60 parts by weight.

If alkali soluble resin (B) does not use aforementioned first alkali soluble resin (B-1), obtained panel is when long Between driving under be also easy to produce ion, and reduce voltage retention.

Second alkali soluble resin (B-2)

Second alkali soluble resin (B-2) is to be reacted to obtain by the first mixture, which includes to have at least The epoxide (b-2-1) of two epoxy groups, and there is at least one carboxylic acid group and at least one ethylene unsaturated group Compound (b-2-2).

In addition, first mixture is selectively included compound carboxylic acid anhydride (b-2-3), the compound with epoxy group (b-2-4) or any combination of above-mentioned material.

Epoxide (b-2-1) at least two epoxy groups

It includes such as following formula (II) compound represented, such as that this, which has the epoxide (b-2-1) of at least two epoxy groups, Any mixing of lower formula (III) compound represented or above-mentioned material:

In formula (II), Y₁、Y₂、Y₃And Y₄Separately represent hydrogen atom, halogen atom, carbon number as 1 to 5 alkyl or The aromatic radical or aralkyl that alkoxy or carbon number are 6 to 12.

As aforementioned formula (II) compound represented can be by bisphenol fluorene type compound (bisphenol fluorene) and halogenation Propylene oxide (epihalohydrin) is reacted and is obtained.

The concrete example of above-mentioned bisphenol fluorene type compound can be bis- (4- hydroxy phenyl) fluorenes [9,9-bis (4- of 9,9- Hydroxyphenyl) fluorine], bis- (the 4- hydroxy-3-methyl phenyl) fluorenes (9,9-bis (4-hydroxy-3- of 9,9- Methylphenyl) fluorene), bis- (4- hydroxyl -3- chlorphenyl) fluorenes (9,9-bis (4-hydroxy-3- of 9,9- Chlorophenyl) fluorene), bis- (4- hydroxyl -3- bromophenyl) fluorenes (9,9-bis (4-hydroxy-3- of 9,9- Bromophenyl) fluorene), bis- (4- hydroxyl -3- fluorophenyl) fluorenes (9,9-bis (4-hydroxy-3- of 9,9- Fluorophenyl) fluorene), bis- (the 4- hydroxy 3-methoxybenzene base) fluorenes (9,9-bis (4-hydroxy-3- of 9,9- Methoxyphenyl) fluorene), bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) fluorenes of 9,9- (9,9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene), bis- (4- hydroxyl -3,5- dichlorophenyl) fluorenes of 9,9- (9,9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene), bis- (4- hydroxyl -3,5- dibromo phenyl) fluorenes of 9,9- (9,9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene) or above compound any combination.

The concrete example of aforementioned halogenated epoxy propane (epihalohydrin) may include, but are not limited to the chloro- 1,2- epoxy third of 3- Any combination of alkane (epichlorohydrin) or the bromo- 1,2 epoxy prapane of 3- (epibromohydrin) or above compound.

The concrete example of bisphenol fluorene type compound with epoxy group may include chemical company, Nippon Steel (Nippon steel Chemical Co., Ltd) manufacture, the commodity of model ESF-300；Osaka natural gas companies (Osaka Gas Co., Ltd) system It makes, the commodity of model PG-100 or EG-210；Short message scientific & technical corporation (S.M.S Technology Co., Ltd) manufacture, model For the commodity of SMS-F9PhPG, SMS-F9CrG or SMS-F914PG.

In formula (III), the R₁To R₁₄Separately represent hydrogen atom, halogen atom, carbon number as 1 to 8 alkyl or The aromatic radical that carbon number is 6 to 15, and n represents integer of 0 to 10.

As aforementioned formula (III) compound represented can use such as following formula (III-1) in the presence of an alkali metal hydroxide Compound represented is reacted with halogenated epoxy propane:

In formula (III-1), R₁To R₁₄And the definition of n respectively as previously mentioned, do not repeat separately herein.

As the synthetic method of formula (III-1) compound represented be first in the presence of acid catalyst, will be such as following formula (III- 2) compound represented and phenol (phenol) class compound carry out condensation reaction, to be formed such as formula (III-1) compound represented. Then, excessive halogenated epoxy propane is added, so that halogenated epoxy propane carries out dehalogenation with such as formula (III-1) compound represented Change hydrogen reaction (dehydrohalogenation), can be obtained such as formula (III) compound represented:

In formula (III-2), R₃To R₆It is defined as described above, it does not repeat separately herein；R₁₅And R₁₆Separately represent The alkyl or alkoxy that halogen atom or carbon number are 1 to 6.Above-mentioned halogen atom can be chlorine atom or bromine atom.Alkyl compared with Good is methyl, ethyl or tert-butyl.Alkoxy is preferably methoxy or ethoxy.

The concrete example of phenolic compound above-mentioned may include, but are not limited to phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), positive third phenol (n-propylphenol), isobutyl phenol (isobutylphenol), tertiary butyl phenol (t- Butylphenol), octyl phenol (octylphenol), nonyl phenol (nonylphenol), stubble phenol (xylenol), methyl butyl benzene Phenol (methylbutylphenol), di-tert-butylphenol (di-t-butylphenol), phenol ethylene (vinylphenol), propylene Phenol (propenylphenol), acetylene phenol (ethinylphenol), penta phenol of ring (cyclopentylphenol), hexamethylene Base phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc..The phenolic compound can be individually a kind of Or a variety of uses of mixing.

It is 1 mole based on the above-mentioned usage amount such as formula (III-2) compound represented, the usage amount of phenolic compound is 0.5 mole to 20 moles, preferably 2 moles to 15 moles.

The concrete example of acid catalyst may include hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid (p-toluenesulfonic acid), grass Acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous aluminum chloride (aluminium chloride ) or the compound of zinc chloride (zinc chloride) etc. anhydrous.Acid catalyst is preferably p-methyl benzenesulfonic acid, sulfuric acid, salt Any mixing of acid or above compound.

Though the usage amount of above-mentioned acid catalyst is without particular limitation.But based on above-mentioned such as formula (III-2) compound represented Usage amount be 100 weight percent, the usage amount of acid catalyst is preferably 0.1 weight percent to 30 weight percent.

Above-mentioned condensation reaction can be solvent-free or in presence of organic solvent carry out.The concrete example of the organic solvent It may include, but are not limited to toluene (toluene), dimethylbenzene (xylene) or methyl iso-butyl ketone (MIBK) (methyl isobutyl ) etc. ketone organic solvent.Above-mentioned organic solvent can the individually a kind of or a variety of uses of mixing.

Total usage amount based on such as formula (III-2) compound represented and phenols is 100 weight percent, organic solvent Usage amount is 50 weight percent to 300 weight percent, preferably 100 weight percent to 250 weight percent.In addition, The operation temperature of above-mentioned condensation reaction is 40 DEG C to 180 DEG C, and the operating time of condensation reaction is 1 hour to 8 hours.

After completing above-mentioned condensation reaction, it can be neutralized or washing process.The neutralisation treatment is after reacting The pH value of solution be adjusted to 3 to 7, preferably 5 to 7.Neutralizer can be used to carry out in the washing process, and the neutralizer is alkali Property substance, concrete example, such as: sodium hydroxide (sodium hydroxide) or potassium hydroxide (potassium hydroxide) Deng alkali metal hydroxide；Calcium hydroxide (calcium hydroxide) or magnesium hydroxide (magnesium hydroxide) Deng alkaline-earth metal hydroxide；Secondary second triamine (diethylene triamine), three times second tetramine (triethylenetetramine), the organic amine of aniline (aniline) or phenylenediamine (phenylene diamine) etc.；Ammonia (ammonia), any combination of sodium dihydrogen phosphate (sodium dihydrogen phosphate) or above compound.It is above-mentioned Neutralizer can the individually a kind of or a variety of uses of mixing.Prior art method progress can be used in above-mentioned washing process, such as is reacting The aqueous solution containing neutralizer is added in solution afterwards, and extraction is repeated.

After carrying out neutralisation treatment or washing process above-mentioned, the unreacted phenols of distillation and molten can be handled by heating under reduced pressure Agent, and be concentrated.In this way, can obtain such as formula (III-1) compound represented.

The concrete example of above-mentioned halogenated epoxy propane may include, but are not limited to the bromo- 1,2- ring of epichlorohydrin, 3- Any combination of Ethylene Oxide or above compound.Before carrying out above-mentioned de-hydrogen halide, it can add in advance or Yu Fanying The alkali metal hydroxide of sodium hydroxide, potassium hydroxide etc. is added in the process.The operation temperature of above-mentioned de-hydrogen halide can It is 20 DEG C to 120 DEG C, and its operating time can be 1 hour to 10 hours.

In one embodiment, added alkali metal hydroxide also can be its aqueous solution in above-mentioned de-hydrogen halide. In this embodiment, while above-mentioned alkali metal hydroxide aqueous solution being continuously added in de-hydrogen halide system, Can be under decompression or normal pressure, continuous still water outlet and halogenated epoxy propane use removing water, and can connect halogenated epoxy propane It is back in reaction system continuously.

Before above-mentioned de-hydrogen halide carries out, tetramethyl-ammonium chloride (tetramethyl ammonium can be also added Chloride), tetramethylammonium bromide (tetramethyl ammonium bromide) or trimethyl benzyl ammonia chloride The quarternary ammonium salt of (trimethyl benzyl ammonium chloride) etc. is as catalyst, and at 50 DEG C to 150 DEG C Under, it reacts 1 hour to 5 hours, alkali metal hydroxide or its aqueous solution is added.Then, at a temperature of 20 DEG C to 120 DEG C, Reaction 1 hour to 10 hours, to carry out de-hydrogen halide.

It is 1 equivalent based on the above-mentioned hydroxyl total yield as in formula (III-1) compound represented, halogenated epoxy propane makes Dosage is 1 equivalent to 20 equivalents, preferably 2 equivalents to 10 equivalents.Based on the above-mentioned hydroxyl as in formula (III-1) compound represented Base total yield is 1 equivalent, and the usage amount of the alkali metal hydroxide added in aforementioned de-hydrogen halide is worked as 0.8 equivalent to 15 Amount, preferably 0.9 equivalent to 11 equivalents.

In order to go on smoothly above-mentioned de-hydrogen halide, the alcohols solvent of methanol or ethyl alcohol etc. can be also added.In addition, Dimethyl sulfone (dimethyl sulfone) or dimethyl sulfoxide (dimethyl sulfoxide) etc. also can be used in de-hydrogen halide The polar solvent of aprotic (aprotic) reacted.In the case of using an alcohol solvent, it is based on halogenated epoxy third Total usage amount of alkane is 100 weight percent, and the usage amount of alcohols is 2 weight percent to 20 weight percent, preferably 4 weights Percentage is measured to 15 weight percent.Using the polar solvent of aprotic, based on the total of halogenated epoxy propane Usage amount is 100 weight percent, and the usage amount of the polar solvent of aprotic is 5 weight percent to 100 weight percent, Preferably 10 weight percent are to 90 weight percent.

After completing de-hydrogen halide, washing process is optionally carried out.Then, in the way of vacuum distillation, example It is such as to remove halogenated epoxy in the environment of 110 DEG C to 250 DEG C and pressure less than 1.3kPa [10 millimetress of mercury (mmHg)] in temperature The polar solvent of propane, alcohols and aprotic.

It, can be by toluene or methyl iso-butyl ketone (MIBK) in order to avoid obtained epoxy resin has the halogen of hydrolyzable (methyl isobutyl ketone) equal solvent and the alkali metal hydroxide aqueous solutions such as sodium hydroxide or potassium hydroxide add In solution after to de-hydrogen halide, and de-hydrogen halide is carried out again.In de-hydrogen halide, based on above-mentioned such as formula (III-1) the hydroxyl total yield in compound represented is 1 equivalent, the usage amount of alkali metal hydroxide be 0.01 mole extremely 0.3 mole, preferably 0.05 mole to 0.2 mole.The operation temperature of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, and is grasped Making the time is 0.5 hour to 2 hours.

After completing de-hydrogen halide, salt be by filtering and washing and etc. removal.In addition, utilizing vacuum distillation Mode remove the solvent of toluene or methyl iso-butyl ketone (MIBK) etc., can be obtained such as formula (III) compound represented.It is above-mentioned such as formula (III) concrete example of compound represented may include, but are not limited to Japanese chemical drug corporation and make, model NC-3000, NC- The commodity of 3000H, NC-3000S and NC-3000P.

Compound (b-2-2) at least one carboxylic acid group Yu at least one ethylene unsaturated group

The concrete example of compound (b-2-2) at least one carboxylic acid group and at least one ethylene unsaturated group is choosing From in the group as composed by following (1) to (3): (1) acrylic acid, methacrylic acid, 2- methylacryoyloxyethyl succinic acid (2-methacryloyloxyethylbutanedioic acid), 2- methacryl oxygen-butyl succinic acid, 2- metering system Acyloxyethyl adipic acid, 2- methacryl oxygen-butyl adipic acid, 2- methylacryoyloxyethyl hexahydrophthalic acid, 2- first Base acrylyl oxy-ethyl maleic acid, 2- methacryloxypropyl maleic acid, 2- methacryl oxygen-butyl maleic acid, 2- methyl Acryloxypropyl succinic acid, 2- methacryloxypropyl adipic acid, 2- methacryloxypropyl tetrahydrophthalic acid, 2- methacryloxypropyl phthalic acid, 2- methacryl oxygen-butyl phthalic acid or 2- methacryl oxygen-butyl Hydrogen phthalic acid；(2) compound obtained by being reacted as (methyl) acrylate with hydroxyl with dicarboxylic acid compound, Middle dicarboxylic acid compound includes adipic acid, succinic acid, maleic acid or phthalic acid；And (3) by (methyl) with hydroxyl Half ester compound obtained by acrylate is reacted with aftermentioned compound carboxylic acid anhydride (b-2-3), wherein (methyl) with hydroxyl Acrylate includes 2- hydroxyethylmethacry,ate [(2-hydroxyethyl) acrylate], 2- hydroxy ethyl methyl acrylic acid Ester [(2-hydroxyethyl) methacrylate], 2- acrylate [(2-hydroxypropyl) Acrylate], 2- hydroxy propyl methacrylate [(2-hydroxypropyl) methacrylate], 4- hydroxybutyl third Olefin(e) acid ester [(4-hydroxybutyl) acrylate], 4- hydroxybutyl methacrylate [(4-hydroxybutyl) Methacrylate] or pentaerythritol acrylate trimethyl etc..

Compound carboxylic acid anhydride (b-2-3)

Compound carboxylic acid anhydride (b-2-3) can be selected from the group as composed by aftermentioned (1) and (2): (1) succinic anhydride (butanedioic anhydride), maleic anhydride (maleic anhydride), itaconic anhydride (Itaconic Anhydride), phthalic anhydride (phthalic anhydride), tetrabydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic anhydride), Methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene tetrabydrophthalic anhydride (methyl Endo-methylene tetrahydro phthalic anhydride), chlorendic anhydride (chlorendic anhydride), The binary of glutaric anhydride or inclined three benzoyl oxide (1,3-dioxoisobenzofuran-5-carboxylic anhydride) etc. Compound carboxylic acid anhydride；And (2) benzophenone tetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride；BTDA), the quaternary compound carboxylic acid anhydride of double pyromellitic dianhydride or double phenylate tetracarboxylic acid dianhydrides etc..

Compound (b-2-4) with epoxy group

Compound (b-2-4) with epoxy group can be selected from glycidyl methacrylate, 3,4- expoxycyclohexyl Methacrylate, the glycidyl ether compound with unsaturated group, with the unsaturated compound of epoxy group or above-mentionedization Close any combination of object.

The above-mentioned glycidyl ether compound with unsaturated group may include the manufacture of Chang Lai chemical conversion industry Co., Ltd., model For Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, The commodity of Denacol EX-171 or Denacol EX-192 etc..

Second alkali soluble resin (B-2) can be epoxide (b-2-1) and tool at least two epoxy groups There is the compound (b-2-2) of at least one carboxylic acid group and at least one ethylene unsaturated group to carry out polymerization reaction and is formed by tool There is the reaction product of hydroxyl, wherein the epoxide (b-2-1) at least two epoxy groups includes as shown in formula (II) Compound, such as any mixing of formula (III) compound represented or above-mentioned material.Then, compound carboxylic acid anhydride (b-2-3) is added Into reaction solution, to carry out polymerization reaction.The total yield number of the hydroxyl of reaction product based on above-mentioned hydroxyl is 1 equivalent, The equivalents of anhydride group possessed by compound carboxylic acid anhydride (b-2-3) is 0.4 equivalent to 1 equivalent, and preferably 0.75 equivalent to 1 is worked as Amount.When using multiple compound carboxylic acid anhydrides (b-2-3), these compound carboxylic acid anhydrides can sequentially add in reaction or add simultaneously Add.When using dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride as compound carboxylic acid anhydride (b-2-3), binary carboxylic The molar ratio of anhydride compound and quaternary compound carboxylic acid anhydride are 1/99 to 90/10, preferably 5/95 to 80/20.Above-mentioned reaction Operation temperature can be 50 DEG C to 130 DEG C.

Second alkali soluble resin (B-2) can for at least two epoxy groups epoxide (b-2-1) with have The compound (b-2-2) of at least one carboxylic acid group and at least one ethylene unsaturated group carries out reaction and is formed by with hydroxyl Reaction product, wherein the epoxide (b-2-1) at least two epoxy groups can be for as shown in formula (II) and formula (III) Compound.Then, by addition compound carboxylic acid anhydride (b-2-3), the compound (b-2-4) with epoxy group or both Be incorporated into reaction solution, to carry out polymerization reaction.Based on the epoxy group in such as formula (II) and formula (III) compound represented Total yield number be 1 equivalent, the above-mentioned compound (b-2- at least one carboxylic acid group and at least one ethylene unsaturated group 2) acid value equivalents is 0.8 equivalent to 1.5 equivalents, preferably 0.9 equivalent to 1.1 equivalents.Based on above-mentioned anti-with hydroxyl The total usage amount for answering the hydroxyl of product is 100 molar percentages, and the usage amount of compound carboxylic acid anhydride (b-2-3) is 10 Mole percents Than to 100 molar percentages, preferably 20 molar percentages to 100 molar percentages, more preferably 30 molar percentages to 100 rub That percentage.

When preparing above-mentioned the second alkali soluble resin (B-2), in order to shorten the reaction time, alkaline chemical combination can be generally added Object is into reaction solution, using as catalysts.The catalysts may include, but are not limited to triphenylphosphine (triphenyl Phosphine), antimony triphenyl (triphenyl stibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethylammonium chloride) or zephiran chloride triethyl group Ammonium (benzyltriethylammonium chloride) etc..The catalysts can individually a kind of or mixing be a variety of uses.

Based on the above-mentioned epoxide (b-2-1) at least two epoxy groups and at least one carboxylic acid group and extremely Total usage amount of the compound (b-2-2) of a few ethylene unsaturated group is 100 parts by weight, the usage amount of the catalysts For 0.01 parts by weight to 10 parts by weight, preferably 0.3 parts by weight to 5 parts by weight.

Secondly, in order to control the degree of polymerization, reaction can add polymerization inhibitor (polymerization inhibitor) extremely In reaction solution.Polymerization inhibitor may include 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.Polymerization inhibitor can the individually a kind of or a variety of uses of mixing.

Based on the above-mentioned epoxide (b-2-1) at least two epoxy groups and at least one carboxylic acid group and extremely Total usage amount of the compound (b-2-2) of a few ethylene unsaturated group is 100 parts by weight, the usage amount of the polymerization inhibitor For 0.01 parts by weight to 10 parts by weight, preferably 0.1 parts by weight to 5 parts by weight.

When preparing the second alkali soluble resin (B-2), polymerization solvent is optionally used.Polymerization solvent It may include the alcohols solvent of ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, 2- butanol, hexanol or ethylene glycol etc.；Methyl ethyl ketone or ring The ketones solvent of hexanone etc.；The aromatic hydrocarbon solvent of toluene or dimethylbenzene etc.；It matches Luo plain (cellosolve) or butyl matches Luo The match Luo element class solvent of plain (butyl cellosolve) etc.；Card must appropriate (carbitol) or butyl card must appropriate (butyl ) etc. carbitol card must appropriate class solvent；Propylene glycol monomethyl ether (propylene glycol monomethyl ether) etc. Propylene glycol alkyl ether solvent；More the third the two of dipropylene glycol monomethyl ether [di (propylene glycol) methyl ether] etc. Alcohol alkyl ether [poly (propylene glycol) alkyl ether] class solvent；Ethyl acetate, butyl acetate, ethylene glycol list Ethyl ether acetate ester (ethylene glycol monoethyl ether acetate) or propylene glycol monomethyl ether acetate The acetates solvent of (propylene glycol methyl ether acetate) etc.；Ethyl lactate (ethyl ) or lactic acid alkyl ester (alkyl lactate) class solvent of butyl lactate (butyl lactate) etc. lactate；Or dialkyl group two Alcohol ethers solvent.The polymerization solvent can individually a kind of or mixing be a variety of uses.

The acid value of second alkali soluble resin (B-2) is 50 milligrams KOH/ grams to 200 milligrams KOH/ grams, preferably 60 milligrams KOH/ grams to 150 milligrams KOH/ grams.

When alkali soluble resin (B) does not use the second alkali soluble resin (B-2), obtained colored filter sense The defect that photosensitive resin composition has resistance to developability bad.

When the weight ratio of aforementioned first alkali soluble resin (B-1) and the second alkali soluble resin (B-2) be 10/90 to When 90/10, obtained colored filter photosensitive polymer combination has preferable resistance to developability.

Third alkali soluble resin (B-3)

Third alkali soluble resin (B-3) is formed by mixture institute combined polymerization, and wherein the mixture includes to have one A or more than one carboxylic acid group ethylene unsaturated monomer (b-3-1) and it is aforementioned have one or more carboxylic acid groups Ethylene unsaturated monomer (b-3-1) other than other copolymerizable ethylene unsaturated monomers (b-3-2).

Ethylene unsaturated monomer (b-3-1) with one or more carboxylic acid groups

There is ethylene unsaturated monomer (b-3-1) of one or more carboxylic acid groups to be the same as aforementioned having one for this A or more than one carboxylic acid group ethylene unsaturated monomer (b-1-2) is identical, therefore does not repeat separately herein.

Other copolymerizable ethylene unsaturated monomers (b-3-2)

Other copolymerizable ethylene unsaturated monomers (b-3-2), which are the same as aforementioned this, has the structure of hindered amine Ethylene monomer (b-1-1) is other in addition with the ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups Copolymerizable ethylene unsaturated monomer (b-1-3), does not repeat separately herein.

Compound (C) with ethylene unsaturated group

The compound (C) with ethylene unsaturated group refers to the unsaturation at least one ethylene unsaturated group The unsaturated compound of compound or the ethylene unsaturated group with 2 or 2 or more.

There is the unsaturated compound of at least one ethylene unsaturated group may include, but are not limited to acrylamide, propylene for this Morpholide, metering system morpholide, acrylic acid -7- amino -3,7- dimethyl monooctyl ester, methacrylic acid -7- amino -3,7- diformazan Base monooctyl ester, isobutoxymethyl acrylamide, isobutoxymethyl Methacrylamide, isobomyl acrylate base 2-ethoxyethyl acetate, first Base isobomyl acrylate base 2-ethoxyethyl acetate, isobornyl acrylate, isobornyl methacrylate, acrylic acid-2-ethyl caproite, first Base acrylic acid-2-ethyl caproite, ethyl diethylene glycol (DEG) acrylate, ethyl diethylene glycol (DEG) methacrylate, t-octyl acrylamide, T-octyl Methacrylamide, diacetone acrylamide, diacetone Methacrylamide, acrylate ester, methyl-prop Olefin(e) acid dimethylamino ester, dodecylacrylate, lauryl methacrylate, acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, first Base acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, acrylic acid dicyclopentenyl ester, methacrylic acid dicyclopentenyl ester, N, N- dimethyl allene acyl Amine, N, N- dimethylmethacryl amide, acrylic acid tetrachloro phenyl ester, methacrylic acid tetrachloro phenyl ester, acrylic acid -2- tetrachlorobenzene oxygen Base ethyl ester, methacrylic acid -2- tetrachloro phenoxy ethyl, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylic acid four Bromobenzene ester, methacrylic acid tetrabromo phenyl ester, acrylic acid -2- tetrabromo phenoxy ethyl, methacrylic acid -2- tetrabromo phenoxy group second Ester, acrylic acid -2- Trichlorophenoxy ethyl ester, methacrylic acid -2- Trichlorophenoxy ethyl ester, tribromophenyl acrylate, methyl-prop Olefin(e) acid tribromophenyl, acrylic acid -2- tribromophenoxy ethyl ester, methacrylic acid -2- tribromophenoxy ethyl ester, acrylic acid -2- hydroxyl Ethyl ester, 2-hydroxyethyl methacry-late, 2-hydroxypropyl acrylate, Hydroxypropyl methacrylate, caprolactam, N- vinyl skin junket alkanone, phenoxyethyl acrylate, phenoxyethyl methacrylate, Pentachlorophenyl Acrylate, methyl-prop Olefin(e) acid pentachlorophenyl ester, acrylic acid pentabromo- phenyl ester, methacrylic acid pentabromo- phenyl ester, poly- single acrylic acid glycol ester, poly- monomethyl third Olefin(e) acid glycol ester, poly- mono acrylic acid propylene glycol ester, poly- monomethacrylate acid propylene glycol ester, acrylic acid norbornene ester or metering system Sour norbornene ester etc..

The aforementioned unsaturated compound at least one ethylene unsaturated group can the individually a kind of or a variety of uses of mixing.

This has the unsaturated compound of 2 or 2 or more ethylene unsaturated groups including but not limited to ethylene glycol dipropyl Olefin(e) acid ester, ethylene glycol dimethacrylate, diacrylate dicyclopentenyl ester, dimethacrylate dicyclopentenyl ester, triethylene glycol Diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, three (2- ethoxy) isocyanates diacrylates Ester, three (2- ethoxy) isocyanates dimethylacrylates, three (2- ethoxy) isocyanurate triacrylates, three (2- hydroxyls Ethyl) isocyanates trimethyl acrylic ester, caprolactone modification three (2- ethoxy) isocyanurate triacrylates, caprolactone Three (2- ethoxy) isocyanates trimethyl acrylic esters, the three acrylic acid trihydroxy methyl propyl ester, trimethacrylate acid three of modification The trimethacrylate that methylol propyl ester, three acrylic acid trihydroxy methyl propyl ester of ethylene oxide (hereinafter referred to as EO) modification, EO are modified The trimethyl that sour trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of propylene oxide (hereinafter referred to as PO) modification, PO are modified Acrylic acid trihydroxy methyl propyl ester, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentylglycol diacrylate, Neopentylglycol dimethacrylate, 1,4 butanediol diacrylate, 1,4- butanediol dimethylacrylate, 1,6- oneself two Alcohol diacrylate, 1,6-HD dimethylacrylate, pentaerythritol triacrylate, pentaerythrite trimethacrylate acid Ester, pentaerythritol tetraacrylate, pentaerythritol tetramethylacrylate, polyester diacrylate, polyester dimethacrylate Ester, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate；DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol 5 third Olefin(e) acid ester, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethyl acrylic acid Ester, the dipentaerythritol hexaacrylate 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 The bisphenol-A that trihydroxy methyl propyl ester, two trihydroxy methyl propyl ester of tetramethyl acrylic acid, the bisphenol a diacrylate of EO modification, EO are modified The hydrogen that dimethylacrylate, the bisphenol a diacrylate of PO modification, the bisphenol a dimethacrylate of PO modification, EO are modified Change the hydrogenated bisphenol A diacrylate that bisphenol a diacrylate, the hydrogenated bisphenol A dimethylacrylate of EO modification, PO are modified The Bisphenol F diacrylate that ester, the hydrogenated bisphenol A dimethylacrylate of PO modification, the glycerin tripropionate of PO modification, EO are modified Bisphenol F dimethylacrylate, the phenolic aldehyde polyglycidyl ether acrylate, phenolic aldehyde polyglycidyl ether methyl that ester, EO are modified Acrylate, or Japanese Toagosei Co., Ltd's manufacture, the commodity etc. of model TO-1382.

The compound (C) with ethylene unsaturated group preferably changes selected from three acrylic acid trihydroxy methyl propyl ester, EO Three acrylic acid trihydroxy methyl propyl ester, the pentaerythritol triacrylate, season penta that three acrylic acid trihydroxy methyl propyl ester, the PO of matter are modified Tetra-acrylate, dipentaerythritol hexaacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol tetrapropylene acid Three propionic acid of glycerol that ester, the dipentaerythritol hexaacrylate of caprolactone modification, the sour two trihydroxy methyl propyl ester of tetrapropylene, PO are modified Any combination of ester or above-mentioned material.

Total usage amount based on aforementioned alkali soluble resin (B) is 100 parts by weight, this has the change of ethylene unsaturated group The usage amount for closing object (C) is 60 parts by weight to 600 parts by weight, preferably 80 parts by weight to 500 parts by weight, more preferably 100 weight Part to 400 parts by weight.

Light initiator (D)

Light initiator (D) of the invention can be O- acyl group oxime (oxime) compound, triazine (triazine) compound, benzene Ethane ketone (acetophenone) compound, diimidazole (biimidazole) compound or benzophenone (benzophenone) Compound etc..The light initiator (D) can the individually a kind of or a variety of uses of mixing.

The O- acyl group oxime compound may include, but are not limited to 1- [4- (phenyl) phenyl]-heptane -1,2- diketone -2- (O- benzoyl group oxime), 1- [4- (phenyl) phenyl]-octane -1,2- diketone -2- (O- benzoyl group oxime), 1- [4- (benzoyl group) Phenyl]-heptane -1,2- diketone -2- (O- benzoyl group oxime), 1- [9- ethyl -6- (2- methyl benzoyl group) -9H- carbazole -3- base] - Ethane ketone -1- (O- acetyl group oxime), 1- [9- ethyl -6- (3- methyl benzoyl group) -9H- carbazole -3- base]-ethane ketone 1- (O- second Acyl group oxime), 1- [9- ethyl -6- benzoyl group -9H- carbazole -3- base]-ethane ketone 1- (O- acetyl group oxime), ethane ketone -1- [9- second Base -6- (2- methyl -4- tetrahydrofuran base benzoyl group) -9H- carbazole -3- base] -1- (O- acetyl group oxime), ethane ketone -1- [9- second Base -6- (2- methyl -5- THP trtrahydropyranyl benzoyl group) -9H- carbazole -3- base] -1- (O- acetyl group oxime), ethane ketone -1- [9- second Base -6- (2- methyl -4- tetrahydrofuran base methoxybenzene acyl group) -9H- carbazole -3- base] -1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -5- tetrahydrofuran base methoxybenzene acyl group) -9H- carbazole -3- base] -1- (O- acetyl group oxime), ethane Ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) benzoyl group } -9H- carbazole -3- base] - 1- (O- acetyl group oxime) or ethane ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) first Oxygroup benzoyl group } -9H- carbazole -3- base] -1- (O- acetyl group oxime) etc..O- acyl group oxime compound above-mentioned can be individually a kind of or mixed Close a variety of uses.

The triaizine compounds may include, but are not limited to bis- (trichloromethyl) -6- (p- methoxyl group) styryl-s- three of 2,4- Piperazine [2,4-Bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine], 2,4- bis- (trichloromethyls) - 6- (the p- dimethylaminophenyl -1,3- butadienyl of 1-)-s- triazine [2,4-Bis (trichloromethyl) -6- (1-p- Dimethylaminophenyl-1,3-butadienyl)-s-triazine] or the p- methoxy of 2- trichloromethyl -4- amino -6- Base styryl-s- triazine [2-trichloromethyl-4-amino-6- (p-methoxy) styryl-s-triazine] Deng.Triaizine compounds above-mentioned can the individually a kind of or a variety of uses of mixing.

The vinylbenzene ketone compound may include, but are not limited to dimethylamine vinylbenzene ketone, α, α '-dimethoxy azoxy Vinylbenzene ketone, 2,2 '-dimethyl-2- phenyl vinylbenzene ketone, p- methoxybenzene ethane ketone, 2- methyl-1-(4- methyl thio benzene Base) -2- morpholine -1- acetone or 2- benzyl -2-N, TMSDMA N dimethylamine -1- (4- morpholinyl phenyl) -1- butanone etc..Vinylbenzene ketone above-mentioned Compound can the individually a kind of or a variety of uses of mixing.

The diimidazole compound may include, but are not limited to 2,2 '-bis- (o- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl, two miaow Azoles, 2,2 '-bis- (ortho-fluorophenyl base) -4,4 ', 5,5 '-tetraphenyl diimidazoles, 2,2 '-bis- (ortho-methyl phenyl) -4,4 ', 5,5 ' - Tetraphenyl diimidazole, 2,2 '-bis- (o- methoxyphenyl) -4,4 ', 5,5 '-tetraphenyl diimidazoles, 2,2 '-bis- (o- ethylo benzenes Base) -4,4 ', 5,5 '-tetraphenyl diimidazoles, 2,2 '-bis- (p- methoxyphenyl) -4,4 ', 5,5 '-tetraphenyl diimidazoles, 2, 2 '-bis- (2,2 ', 4,4 '-tetramethoxy phenyl) -4,4 ', 5,5 '-tetraphenyl diimidazoles, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl diimidazoles or 2,2 '-bis- (2,4 dichloro benzene base) -4,4 ', 5,5 '-tetraphenyl diimidazoles etc..Two miaow above-mentioned Azole compounds can the individually a kind of or a variety of uses of mixing.

The benzophenone cpd may include, but are not limited to thioxanthones, 2,4- diethyl thioxanthone, thioxanthones -4- sulfone, two Benzophenone, 4,4 '-bis- (dimethylamine) benzophenone or 4,4 '-bis- (diethylamine) benzophenone etc..Benzophenone chemical combination above-mentioned Object can the individually a kind of or a variety of uses of mixing.

The light initiator (D) preferably can be 1- [4- (phenyl) phenyl]-octane -1,2- diketone -2- (O- benzoyl group Oxime), 1- [9- ethyl -6- (2- methyl benzoyl group) -9H- carbazole -3- base]-ethane ketone -1- (O- acetyl group oxime), ethane ketone -1- [9- ethyl -6- (2- methyl -4- tetrahydrofuran base methoxybenzene acyl group) -9H- carbazole -3- base] -1- (O- acetyl group oxime), ethane Ketone -1- [9- ethyl -6- { 2- methyl -4- (2,2- dimethyl -1,3- dioxolane base) methoxybenzene acyl group } -9H- carbazole - 3- yl] bis- (trichloromethyl) -6- (p- methoxyl group) styryl-s- triazines of -1- (O- acetyl group oxime), 2,4-, 2- benzyl -2- N, TMSDMA N dimethylamine -1- (4- morpholinyl phenyl) -1- butanone, 2,2 '-bis- (2,4 dichloro benzene base) -4,4 ', 5,5 '-tetraphenyl diimidazoles It is [2,2 '-bis (2,4-dichlorophenyl) -4,4 ', 5,5 '-tetraphenyl-1,2 '-biimidazole], 4,4 '-bis- Any combination of (diethylamine) benzophenone or above-mentioned material.

Under the physical property for not influencing photosensitive polymer combination, photosensitive polymer combination of the invention can be added further Initiator other than the light initiator (D).The concrete example of the initiator, such as: α-diketone (α-diketone) compound, keto-alcohol (acyloin) compound, keto-alcohol ether (acyloin ether) compound, acyl phosphine oxide (acylphosphineoxide) are changed Close object, quinone (quinone) compound, the compound with halogen or peroxide etc..

It is compound etc. that the α-dione compounds, which may include, but are not limited to benzil (benzil) or acetyl group (acetyl),. α-dione compounds above-mentioned can the individually a kind of or a variety of uses of mixing.

The keto-alcohol compound may include, but are not limited to diphenylhydroxyethanone (benzoin) etc..Keto-alcohol compound above-mentioned can be single The solely a kind of or a variety of uses of mixing.

The keto-alcohol ether compound may include, but are not limited to diphenylhydroxyethanone methyl ether (benzoin methylether), hexichol Ethyl alcohol ketone ether (benzoin ethylether) or diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc.. Keto-alcohol ether compound above-mentioned can the individually a kind of or a variety of uses of mixing.

The acyl phosphine oxide compound may include, but are not limited to 2,4,6- trimethyl benzoyl diphenyl phosphine oxide (2,4,6- Trimethyl-benzoyl diphenylphosphineoxide) or double-(2,6- dimethoxy benzoyl) -2,4,4- trimethyl Phenylphosphine oxide [bis- (2,6-dimethoxy-benzoyl) -2,4,4-trimethylbenzyl Phosphineoxide] etc..Acyl phosphine oxide compound above-mentioned can the individually a kind of or a variety of uses of mixing.

The quinones may include, but are not limited to anthraquinone (anthraquinone), 1,4- naphthoquinones (1,4- Naphthoquinone) etc..Quinones above-mentioned can the individually a kind of or a variety of uses of mixing.

The compound with halogen may include, but are not limited to chloroacetophenone (phenacyl chloride), tribromo first Base benzene sulfone (tribromomethyl phenylsulfone) or three (trichloromethyl)-s- triazine [tris (trichloromethyl)-s-triazine] etc..The aforementioned compound with halogen can the individually a kind of or a variety of uses of mixing.

The peroxide may include, but are not limited to di-t-butyl peroxide (di-tertbutylperoxide) etc..Before The peroxide stated can the individually a kind of or a variety of uses of mixing.

Total usage amount based on aforementioned alkali soluble resin (B) is 100 parts by weight, and the usage amount of the light initiator (D) is 10 parts by weight to 100 parts by weight, preferably 15 parts by weight are to 90 parts by weight, more preferably 20 parts by weight to 80 parts by weight.

Organic solvent (E)

Organic solvent (E) of the invention may include, but are not limited to ethylene glycol monomethyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, two Glycol ether, diethylene glycol (DEG) positive propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol monomethyl ether, propylene glycol second Ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol positive propyl ether, dipropylene glycol n-butyl ether, two (poly-) alkylene glycol mono alkane ether solvent of contracting tripropylene glycol methyl ether or tripropylene glycol ether etc.；Ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol ether acetate, propylene glycol methyl ether acetate (propylene glycol methyl ether acetate； ) or (poly-) alkylene glycol mono alkane ether acetate class solvent of propylene-glycol ethyl ether acetate etc. PGMEA；Diethylene glycol dimethyl ether, two Other ether solvents of glycol ethyl methyl ether, diethyl carbitol or tetrahydrofuran etc.；First and second alkanones, cyclohexanone, 2-HEPTANONE or 3- The ketones solvent of heptanone etc.；The lactic acid alkane esters solvent of 2 hydroxy propanoic acid methyl esters or 2 hydroxy propanoic acid ethyl ester etc.；2- hydroxyl -2- first Base methyl propionate, 2- hydroxy-2-methyl ethyl propionate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxy-c Sour methyl esters, 3- ethoxyl ethyl propionate (ethyl3-ethoxypropionate；EEP), ethoxy ethyl acetate, hydroxyacetic acid Ethyl ester, 2- hydroxy-3-methyl methyl butyrate, 3- methyl -3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl propionic acid Ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, acetic acid isoamyl Ester, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, methyl pyruvate, pyruvic acid second Other esters solvents of ester, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate or 2- methoxyl group ethyl butyrate etc.； The aromatic hydrocarbons class solvent of toluene or dimethylbenzene etc.；N-Methyl pyrrolidone, N,N-dimethylformamide or N, N- The amide solvents such as dimethyl acetamide.

The organic solvent (E) preferably can be propylene glycol methyl ether acetate or 3- ethoxyl ethyl propionate.

Total usage amount based on aforementioned alkali soluble resin (B) is 100 parts by weight, and the usage amount of the organic solvent (E) is 500 parts by weight to 5000 parts by weight, preferably 800 parts by weight to 4,500 parts by weight；More preferably 1,000 parts by weight are to 4,000 weights Measure part.

Dyestuff (F)

Colored filter of the invention is selectively included dyestuff (F) with photosensitive polymer combination, and the dyestuff (F) Orchil with the structure as shown in following formula (IV):

In formula (IV), Z₁To Z₄It is independently represented each other hydrogen atom ,-Z₆, carbon number be 6 to 10 aromatic hydroxy group or through halogen Plain atom ,-Z₆、-OH、-OZ₆、-SO₃ ^-、-SO₃H、-SO₃M、-COOH、-COOZ₆、-SO₃Z₆、-SO₂NHZ₈Or-SO₂NZ₈Z₉It is taken The aromatic hydroxy group for being 6 to 10 for carbon number；Z₅Representative-SO₃ ^-、-SO₃H、-SO₃M、-COOH、-COOZ₆、-SO₃Z₆、-SO₂NHZ₈Or- SO₂NZ₈Z₉；A represents halogen atom；A represents the integer that 0 or 1 and b represents 0 to 5.When b represents 2 to 5, multiple Z₅To be identical or It is not identical.Z above-mentioned₆、Z₈、Z₉Distinguish with M as described below.

Z above-mentioned₆Represent carbon number as 1 to 10 alkyl or through carbon number replaced halogen atom as 1 to 10 alkyl, wherein Alkyl that the carbon number is 1 to 10 or this through carbon number replaced halogen atom be 1 to 10 alkyl in-CH₂Be it is unsubstituted or It can be by-O-, carbonyl or-NZ₇It is replaced.The Z₇Represent carbon number as 1 to 10 alkyl or through halogen atom replace carbon number be 1 to 10 Alkyl.

Z above-mentioned₈And Z₉Carbon number is independently represented each other as 1 to 10 straight chained alkyl, branched alkyl or naphthenic base, or- Q.The Q represent carbon number as 6 to 10 aromatic hydroxy group, carbon number as 5 to 10 heteroaryl perfume base.Furthermore Q can also be represented through halogen original Son ,-Z₆、-OH、-OZ₆、-NO₂,-CH=CH₂Or-CH=CH-Z₆The aromatic hydroxy group that replaced carbon number is 6 to 10, or through halogen Plain atom ,-Z₆、-OH、-OZ₆、-NO₂,-CH=CH₂Or-CH=CH-Z₆The heteroaryl perfume base that replaced carbon number is 5 to 10, wherein Z₆It is defined as described above, it does not repeat separately herein.

Additive (G)

For the physical property and the property changed demand for meeting colored filter segment, photosensitive polymer combination alternative of the invention Ground includes additive (G), such as: high-molecular compound, adherence promotor other than filler, aforementioned alkali soluble resin (B), Antioxidant, ultraviolet absorbing agent or anti-agglutinant etc..

The additive (G) may include, but are not limited to the filler of glass or aluminium etc.；Polyvinyl alcohol, polyalkylene glycol monoalkyl ether Or the high-molecular compound other than the alkali soluble resins such as poly- perfluoroalkyl acrylate alkyl ester (B)；Vinyltrimethoxysilane, vinyl Triethoxysilane, vinyl three (2- methoxyethoxy) silane, N- (2- amino-ethyl) -3- amino propyl methyl dimethoxy Silane, N- (2- amino-ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane, 3- epoxy prapanol Propyl trimethoxy silicane, 3- epoxy prapanol hydroxypropyl methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy Base silane, 3- chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silane, 3- metacryloxy propyl trimethoxy The adherence promotor of base silane or 3- mercaptopropyl trimethoxy silane etc.；2,2- thiobis (4- methyl-6-tert butyl benzene Phenol) or the antioxidants such as 2,6- di-t-butyl phenol；2- (3- tert-butyl -5- methyl -2- hydroxy phenyl) -5- chlorphenyl changes nitrogen Or the ultraviolet absorbing agent of alkoxy benzophenone etc.；The anti-agglutinant of Sodium Polyacrylate etc..

The preparation of photosensitive polymer combination

The preparation method of colored filter of the invention photosensitive polymer combination is can by above-mentioned pigment (A), alkali Soluble resin (B), the compound (C) with ethylene unsaturated group, light initiator (D) and organic solvent (E) are placed in stirring It is stirred in device, it is made to be uniformly mixed into solution state, also optionally added dyestuff (F) when necessary or filler, alkali can High-molecular compound, adherence promotor, antioxidant, ultraviolet absorbing agent or anti-agglutinant etc. other than soluble resin (B) Additive (G).

Total usage amount based on alkali soluble resin (B) is 100 parts by weight, the usage amount of pigment (A) be 30 parts by weight extremely 300 parts by weight, the usage amount of the compound (C) with ethylene unsaturated group are 60 parts by weight to 600 parts by weight, light initiator (D) usage amount is 10 parts by weight to 100 parts by weight, and the usage amount of organic solvent (E) is 500 parts by weight to 5000 weight Part.

The preparation of colored filter

The preparation of colored filter of the invention is to form picture using aforementioned colored filter photosensitive polymer combination Plain layer, and colored filter is made using the method.

The preparation of colored filter of the invention is mainly by revolution coating, cast coat, ink-jet application (ink-jet) Or the coating methods such as print roll coating, the aforementioned colored filter for being mixed into solution state is coated on photosensitive polymer combination On substrate.After coating, first in a manner of being dried under reduced pressure, most solvent is removed, and in a manner of pre-baked (pre-bake) It removes solvent and forms a pre-baked film.Wherein, be dried under reduced pressure and pre-baked condition, according to the type of each composition, be formulated ratio and It is different.Be dried under reduced pressure and carried out 1 second to 60 seconds usually under 0 to 200mmHg pressure, and it is pre-baked be usually at 70 DEG C extremely It is carried out 1 minute to 15 minutes at a temperature of 110 DEG C.Then, which is placed under specified mask (mask) and is exposed, Light used in middle exposure is preferred with the ultraviolet light of g line, h line, i line etc., and ultraviolet device can be (super) high-pressure mercury-vapor lamp Or metal halid lamp.Then, at a temperature of 23 ± 2 DEG C by the pre-baked film after exposure be impregnated in developer solution 15 seconds to 5 minutes into Row development, with remove should not part and form pattern, and formed have photo-hardening film layer substrate.

The concrete example of aforesaid base plate, such as: alkali-free glass, soda-lime glass, the hard glass (group for liquid crystal display device Strangle this glass), quartz glass, in adhering to transparent conductive film person, or the photoelectricity for solid-state image sensor etc. on these glass Converting means substrate (such as: silicon substrate).These substrates are usually to be initially formed the black matrix" that each pixel shader layer is isolated (black matrix)。

Furthermore the concrete example of developer solution, such as: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, carbonic acid Hydrogen potassium, sodium metasilicate, sodium methyl silicate, ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide The alkaline water that the alkali compounds such as ammonium, choline, pyrroles, piperidines or 1,8- diazabicylo-(5,4,0) -7- hendecene are constituted Solution, concentration are generally 0.001 weight percent to 10 weight percent, preferably 0.005 weight percent to 5 weight hundred Divide ratio, more preferably 0.01 weight percent to 1 weight percent.

It when the developer solution constituted using aforementioned base aqueous solution, is cleaned usually after development with water, and with compression Air or compressed nitrogen air-dry pattern.

After air-drying the substrate with photo-hardening film layer, using heating devices such as hot plate or baking ovens, temperature 100 to The substrate is heated at 280 DEG C 1 to 15 minute, to remove the volatile component in film, and make unreacted ethylene in film Unsaturated double-bond carries out thermmohardening reaction.Using the photosensitive polymer combination of assorted (main includes three color of red, green, blue) pre- In fixed pixel three times with same step repetitive operation, the photo-hardening pixel shader layer of three color of red, green, blue can be obtained.

Secondly, forming ITO (indium oxide under vacuum on pixel shader layer above-mentioned with 220 DEG C to 250 DEG C of temperature Tin) evaporation film.When necessary, ITO evaporation film is etched and is routed, and coating of liquid crystalline alignment film polyimides, and then burnt Cheng Zhi can be prepared by the colored filter of liquid crystal display.

The preparation of liquid crystal display device

Liquid crystal display device of the invention includes colored filter above-mentioned.

Liquid crystal display device of the invention is mainly the colored filter substrate as obtained by preceding method and is provided with thin Film transistor (Thin Film Transistor；TFT drive substrate) is constituted, wherein between intervening between above-mentioned 2 plate base Gap (structure cell interval；Cell gap) make it is oppositely disposed, and with sealing agent be bonded 2 plate bases surrounding position.Then, in 2 chip bases Filling injection liquid crystal in the gap that the surface of plate and sealing agent are distinguished, and injection hole is sealed, to form liquid crystal cell (cell).Then, in the outer surface of liquid crystal cell, that is, on other sides of each substrate of composition liquid crystal cell, fitting is inclined Tabula rasa, liquid crystal display device is made.

Illustrate application of the invention following with several embodiments, however, it is not to limit the invention, the present invention Has usually intellectual in technical field, without departing from the spirit and scope of the present invention, when can be used for a variety of modifications and variations.

Specific embodiment

Prepare the first alkali soluble resin (B-1)

It is the first alkali soluble resin that synthesis example B-1-1 to B-1-8 is prepared according to table 1 below.

Synthesis example B-1-1

By the 1,2,2,6,6- pentamethyl of 3 parts by weight-piperidyl methyl acrylate (hereinafter referred to as FA-711MM), 45 weights Measure the 2- methacryloyloxyethyl succinate (hereinafter referred to as HOMS) of part, the double cyclopentenyl acrylate of 12 parts by weight The benzyl methacrylic acid of the styrene (hereinafter referred to as SM) of (hereinafter referred to as FA-511A), 20 parts by weight, 5 parts by weight Ester (hereinafter referred to as BzMA), the methyl methacrylate (hereinafter referred to as MMA) of 15 parts by weight, 4 parts by weight 2,2 '-azos The 3- ethoxyl ethyl propionate (hereinafter referred to as EEP) of double -2- methylbutyronitriles (hereinafter referred to as AMBN) and 200 parts by weight is continuous It is added in the four-hole boiling flask of 500mL, and temperature is maintained 100 DEG C in 25 parts by weight/minute by pan feeding speed control.Reaction 6 After hour, the first alkali soluble resin (B-1-1) can be obtained.

Synthesis example B-1-2 to B-1-8

Synthesis example B-1-2 to B-1-8 is using identical as the production method of the first alkali soluble resin of synthesis example B-1-1 Preparation method, the difference is that synthesis example B-1-2 to B-1-8 be change the first alkali soluble resin in raw material type with Usage amount and polymerizing condition, and its formula and polymerizing condition are as shown in table 1, do not repeat separately herein.

Prepare the second alkali soluble resin (B-2)

Synthesis example B-2-1

Firstly, by the fluorenes ring oxygen compound of 100 parts by weight, (chemical company, Nippon Steel is manufactured, the quotient of model ESF-300 Product, and its epoxide equivalent be 231), the acrylic acid of 30 parts by weight, the benzyltriethylammonium chloride of 0.3 parts by weight, 0.1 parts by weight DBPC 2,6 ditertiary butyl p cresol and the propylene glycol monomethyl ether acetates of 130 parts by weight be added with continous way addition manner to 500 In the four-neck flask of milliliter.Pan feeding speed control is in 25 parts by weight/minute, and the temperature of reaction process maintains 100 DEG C extremely 110℃.After reaction 15 hours, the pale yellow transparent mixed liquor that solid constituent concentration is 50 weight percent can be obtained.

Then, the above-mentioned mixed liquor of 100 parts by weight is added in the ethylene glycol ether acetate of 25 parts by weight, is added simultaneously Add the tetrabydrophthalic anhydride of 6 parts by weight and the benzophenone tetracarboxylic dianhydride of 13 parts by weight, and is heated to 110 DEG C to 115 ℃.After reaction 2 hours, the second alkali soluble resin (B-2-1), acid value 98mgKOH/g, and weight average point can be prepared by Son amount is 2205.

Synthesis example B-2-2

By the fluorenes ring oxygen compounds of 100 parts by weight (manufacture of chemical company, Nippon Steel, the commodity of model ESF-300, and its Epoxide equivalent be 231), the 2,6- bis- of the acrylic acid of 30 parts by weight, the benzyltriethylammonium chloride of 0.3 parts by weight, 0.1 parts by weight The propylene glycol monomethyl ether acetate of Butylated Hydroxytoluene and 130 parts by weight is continuously added in 500 milliliters of four-neck flask.Pan feeding Speed control is in 25 parts by weight/minute, and the temperature of reaction process maintains 100 DEG C to 110 DEG C.After reaction 15 hours Obtain the pale yellow transparent mixed liquor that solid component concentration is 50 weight percent.

Then, by the molten ethylene glycol ether acetate for adding to 25 parts by weight of the above-mentioned mixed liquor of 100 parts by weight, add simultaneously Add the benzophenone tetracarboxylic dianhydride of 13 parts by weight, and is heated to 90 DEG C to 95 DEG C.After reaction 2 hours, the four of 6 parts by weight are added Hydrogen phthalic anhydride, and reacted 4 hours at 90 DEG C to 95 DEG C, it can be prepared by the second alkali soluble resin (B-2-2), acid Valence is 99.0mgKOH/g, and weight average molecular weight is 2630.

Synthesis example B-2-3

By the epoxide of 400 parts by weight, (Japanese chemical drug corporation is made, the commodity of model NC-3000, and its epoxy Equivalent be 288), the triphen of the methoxyl group phenol (methoxyphenol) of the acrylic acid of 102 parts by weight, 0.3 parts by weight, 5 parts by weight The propylene glycol monomethyl ether acetate of base phosphine and 264 parts by weight adds in reaction flask, and temperature is maintained 95 DEG C.Reaction 9 hours Afterwards, intermediate product, acid value 2.2mgKOH/g be can be obtained.Then, the tetrabydrophthalic anhydride of 151 parts by weight is added (tetrahydrophthalic anhydride), and reacted 4 hours at 95 DEG C, it can be prepared by the second alkali soluble resin (B-2-3), acid value 102mgKOH/g, and weight average molecular weight is 3200.

It prepares third alkali soluble resin (B-3)

It is the third alkali soluble resin that synthesis example B-3-1 to B-3-4 is prepared according to table 2 below.

Synthesis example B-3-1

Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter, and import nitrogen.In the environment of nitrogen, (hereinafter referred to as by the 2- methacryloyloxyethyl succinate of 45 parts by weight Styrene for HOMS), the double cyclopentenyl acrylate (hereinafter referred to as FA-511A) of 15 parts by weight, 20 parts by weight is (following Referred to as SM), the benzyl methacrylate (hereinafter referred to as BzMA) of 5 parts by weight, 15 parts by weight methyl methacrylate Ester (hereinafter referred to as MMA) and the 3- ethoxyl ethyl propionate (hereinafter referred to as EEP) of 200 parts by weight are continuously added to four cervical vertebras In bottle, and it is uniformly mixed.Then, the temperature of oil bath is promoted to 100 DEG C, and by the double -2- methyl of the 2 of 4 parts by weight, 2 '-azos Butyronitrile (hereinafter referred to as AMBN) is dissolved in 3- ethoxyl ethyl propionate, is divided equally into the weight of five equal portions, and in 1 hour It is added in four cervical vertebra bottles.Reaction temperature in polymerization process is to maintain 100 DEG C, and react 6 hours.Then, from four cervical vertebra bottles Middle taking-up polymerizate, and solvent is removed to get third alkali soluble resin (B-3-1) is arrived.

Synthesis example B-3-2 to B-3-4

Synthesis example B-3-2 to B-3-4 is using identical as the production method of third alkali soluble resin of synthesis example B-3-1 Preparation method, the difference is that synthesis example B-3-2 to B-3-4 be change third alkali soluble resin in raw material type with Usage amount and polymerizing condition, and its formula and polymerizing condition are as shown in table 2, do not repeat separately herein.

Prepare photosensitive polymer combination

It is the photosensitive polymer combination that embodiment 1 to 11 and comparative example 1 to 6 are prepared according to table 3 and table 4 below.

Embodiment 1

By the pigment of 30 parts by weight (A-1, the wherein ratio of C.I.Pigment R254 and C.I.Pigment Yellow139 Example for 80/20), the first alkali soluble resin (hereinafter referred to as B-1-1) obtained by the aforementioned synthesis example B-1-1 of 10 parts by weight, The two of second alkali soluble resin (hereinafter referred to as B-2-1) obtained by the aforementioned synthesis example B-2-1 of 90 parts by weight, 40 parts by weight 2- methyl-1-(the 4- methyl of six acrylate of pentaerythrite (manufacture of East Asia Synesis Company, hereinafter referred to as C-1), 3 parts by weight Thio-phenyl) -2- morpholino -1- acetone (hereinafter referred to as D-1), 3 parts by weight 2,2 '-bis- (2,4 dichloro benzene dustpans) -4,4 ', 4,4 '-bis- (diethylamine) benzophenone (hereinafter referred to as D- of 5,5 '-tetraphenyl diimidazoles (be referred to as D-2) and 4 parts by weight 3) it, adds in the 3- ethoxyl ethyl propionate (hereinafter referred to as E-1) of 500 parts by weight, is dissolved and mixed with swing-out stirrer, i.e., The colored filter photosensitive polymer combination of embodiment 1 can be made.Resulting colored filter photosensitive resin composition Object is evaluated with following each evaluation method, and acquired results are as shown in table 3, wherein the detection of resistance to developability and voltage retention Method repeats after holding.

Embodiment 2 to 11 and comparative example 1 to 6

Embodiment 2 to 11 and comparative example 1 to 6 are the production method phases using the photosensitive polymer combination with embodiment 1 Same preparation method, the difference is that embodiment 2 to 11 and comparative example 1 to 6 are to change raw material in photosensitive polymer combination Type and usage amount, and its formula and evaluation result are not repeated separately herein respectively as shown in table 3 and table 4.

Evaluation method

1. resistance to developability

The colored filter of solution state is coated in a manner of rotary coating with photosensitive polymer combination having a size of On the glass substrate of 100mm × 100mm, and it is dried under reduced pressure under the pressure of about 100mmHg about 30 seconds.Then, Yu Wen Pre-baked 2 minutes at 80 DEG C of degree, use to form 2.5 μm of film thickness of pre-baked film.Then, with colorimeter (great Zhong electronics corporation manufacture, Model MCPD) measure its coloration (L*, a*, b*).

Later, with ultraviolet photoetching machine (Canon manufacture, model PLA-501F) the above-mentioned pre-baked film of irradiation, wherein The luminous intensity of ultraviolet photoetching machine is set as 100mJ/cm².Then, pre-baked film is impregnated in developer solution 1 minute of 23 DEG C.With After pure water is cleaned, its coloration is measured again, calculates coloration variation (Δ Eab*) using lower formula (V), and carry out according to following benchmark Evaluation indicates that resistance to developability is better wherein obtained coloration variation (Δ Eab*) is smaller:

ΔEab^*=[(Δ L)²+(Δa)²+(Δb)²]^1/2Formula (V)

◎: Δ Eab* < 2.

Zero: 2≤Δ Eab* < 4.

△: 4≤Δ Eab* < 6.

╳: 6≤Δ Eab*.

2. voltage retention

Form the SiO to prevent sodium ion from dissolving out₂Film, and further in vapor deposition predetermined pattern on soda-lime glass substrate Indium tin oxide (Inidium Tin Oxide；ITO) electrode.By sense obtained by previous embodiment 1 to 11 and comparative example 1 to 6 Photosensitive resin composition is coated on above-mentioned glass substrate in a manner of rotary coating.Then, it is carried out with 100 DEG C of temperature pre-baked 1 minute, to form the pre-baked film that film thickness is 2.0 μm.Then, not coverage mask, and with 700J/m²Light irradiation it is above-mentioned pre- Roasting film.It is 23 DEG C that film leaching after exposure, which is placed in temperature, and concentration is formed by the potassium hydroxide of 0.04 weight percent Developer solution in.After 1 minute, with milli-Q water and air-dry.Then, after with 230 DEG C of temperature to the film after development It is 30 minutes roasting, and form hardened coating film.

Then, aforementioned hardened coating film is bonded using sealing agent to be formed by pixel substrate and the ITO of predetermined pattern has been deposited Electrode, and the bead that partial size is 1.8mm is placed between the two.By liquid crystal material (Merck & Co., Inc.'s manufacture, model The liquid crystal material of MLC6608) gap between aforementioned sealing agent, pixel substrate and ITO electrode is injected, to form liquid crystal cell.

Then, obtained liquid crystal cell is placed in 60 DEG C of thermostat, and with liquid crystal voltage conservation rate analyzer Device (Toyo Co., Ltd.'s manufacture, the instrument of model VHR-1A type) measures the voltage retention of obtained liquid crystal cell.It surveys The square wave that the voltage of amount is 5.5 volts, and it is 60Hz that it, which measures frequency,.

Voltage retention above-mentioned is to represent a numerical value, and this numerical value is that (liquid crystal cell is after 16.7 milliseconds for representative The voltage that potential difference/liquid crystal cell is applied in 0 millisecond).It is obtained when the voltage retention of liquid crystal cell is no more than 90% Liquid crystal cell in holding voltage can not be stablized in 16.7 milliseconds, and the liquid crystal molecule in liquid crystal cell is made to be easy to produce ghost Defect.Voltage retention measured by previous embodiment 1 to 11 and comparative example 1 to 6 is evaluated according to following benchmark:

◎: 95% < voltage holding Shuai≤100%.

Zero: 90% < voltage holding Shuai≤95%.

△: 80% < voltage holding Shuai≤90%.

╳: voltage holding Shuai≤80%.

By the result of table 3 and table 4 it is found that when the alkali soluble resin (B) in photosensitive polymer combination of the invention wraps When containing the first alkali soluble resin (B-1), obtained photosensitive polymer combination has preferable voltage retention.Secondly, When alkali soluble resin (B) includes the second alkali soluble resin (B-2), obtained photosensitive polymer combination has preferable Resistance to developability.

Furthermore when the first alkali soluble resin (B-1) and the second alkali soluble resin (B- in alkali soluble resin (B) 2) when weight ratio is 10/90 to 90/10, obtained photosensitive polymer combination has more preferably resistance to developability.

Need to supplement, though the present invention with specific compound, form, reaction condition, processing procedure, analysis method or specific instrument Device illustrates colored filter photosensitive polymer combination and its application of the invention as illustrating, only technology belonging to the present invention Any tool usually intellectual in field is it is found that the present invention is not limited thereto, without departing from the spirit and scope of the present invention, originally The colored filter photosensitive polymer combination of invention and its application also can be used other compounds, composition, reaction condition, Processing procedure, analysis method or instrument carry out.

Although the present invention is disclosed above with embodiment, however, it is not to limit the invention, the skill belonging to the present invention Any tool usually intellectual in art field, without departing from the spirit and scope of the present invention, when various change and profit can be made Decorations, therefore protection scope of the present invention is subject to the range defined depending on appended claims.

Table 3

Abbreviation Chinese

A-1 C.I.Pigment R254/C.I.Pigment Y139=80/20

A-2 C.I.Pigment G36/C.I.Pigment Y150=60/40

A-3 C.I.Pigment B15:6

C-1 dipentaerythritol hexaacrylate (East Asia is synthetically produced)

Tri- acrylic acid trihydroxy methyl propyl ester of C-2

C-3 TO-1382 (Japanese Toagosei Co., Ltd's manufacture)

D-1 2- methyl-1-(4- methylthiophenyi)-2- morpholino-1- acetone

D-2 2,2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl diimidazoles

D-3 4,4 '-bis- (diethylamino) benzophenone

D-4 1- [4- (phenyl) phenyl]-octane -1,2- diketone 2- (O- benzoyl group oxime)

E-1 3- ethoxyl ethyl propionate

E-2 propylene glycol methyl ether acetate

F-1 3- mercaptopropyl trimethoxy silane

F-2 2,2- thiobis (4- methyl-6-tert-butylphenol)

Table 4

Abbreviation Chinese

A-1 C.I.Pigment R254/C.I.Pigment Y139=80/20

A-2 C.I.Pigment G36/C.I.Pigment Y150=60/40

A-3 C.I.Pigment B15:6

C-1 dipentaerythritol hexaacrylate (East Asia is synthetically produced)

Tri- acrylic acid trihydroxy methyl propyl ester of C-2

C-3 TO-1382 (Japanese Toagosei Co., Ltd's manufacture)

D-1 2- methyl-1-(4- methylthiophenyi)-2- morpholino-1- acetone

D-2 2,2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl diimidazoles

D-3 4,4 '-bis- (diethylamino) benzophenone

D-4 1- [4- (phenyl) phenyl]-octane -1,2-=diketone 2- (O- benzoyl group oxime)

E-1 3- ethoxyl ethyl propionate

E-2 propylene glycol methyl ether acetate

F-1 3- mercaptopropyl trimethoxy silane

F-2 2,2- thiobis (4- methyl-6-tert-butylphenol)

Claims

1. a kind of colored filter photosensitive polymer combination, includes:

Pigment (A)；

Alkali soluble resin (B) includes:

First alkali soluble resin (B-1) has the structure of hindered amine as shown in following formula (I):

In formula (I), X₁It is 6 to 20 that hydrogen atom, carbon number, which are represented, as 1 to 18 straight chained alkyl, branched alkyl or naphthenic base, carbon number Aromatic radical, the aromatic alkyl that carbon number is 7 to 12, acyl group, oxygen radical, or-OX₄；X₄Represent hydrogen atom, carbon number is 1 to 18 Straight chained alkyl, branched alkyl or naphthenic base, the aromatic radical that carbon number is 6 to 20 or carbon number be 7 to 12 aromatic alkyl；X₂ And X₃It is independently represented each other methyl, ethyl, phenyl or bond forms the aliphatic ring that carbon number is 4 to 12 mutually；* it represents covalent Key；And

Second alkali soluble resin (B-2) is reacted by the first mixture and is obtained, and wherein first mixture includes to have at least The epoxide (b-2-1) of two epoxy groups, and there is at least one carboxylic acid group and at least one ethylene unsaturated group Compound (b-2-2), the wherein weight ratio of first alkali soluble resin (B-1) and second alkali soluble resin (B-2) It is 10/90 to 90/10；

Compound (C) with ethylene unsaturated group；

Light initiator (D)；And

Organic solvent (E).

2. colored filter photosensitive polymer combination as described in claim 1, total based on the alkali soluble resin (B) Usage amount is 100 parts by weight, and the usage amount of the pigment (A) is 30 parts by weight to 300 parts by weight, this has ethylene unsaturated group The usage amount of compound (C) be 40 parts by weight to 400 parts by weight, the usage amount of the light initiator (D) is 10 parts by weight to 100 Parts by weight, and the usage amount of the organic solvent (E) is 500 parts by weight to 5000 parts by weight.

3. colored filter photosensitive polymer combination as described in claim 1, wherein this has at least two epoxy groups Epoxide (b-2-1) include such as following formula (II) compound represented, such as following formula (III) compound represented or above-mentioned two The combination of person:

In formula (II), Y₁、Y₂、Y₃And Y₄Represent hydrogen atom, halogen atom, carbon number separately as 1 to 5 alkyl or alcoxyl The aromatic radical or aralkyl that base or carbon number are 6 to 12；In formula (III), R₁To R₁₄Separately represent hydrogen atom, halogen The aromatic radical that the alkyl or carbon number that plain atom, carbon number are 1 to 8 are 6 to 15, and n represents integer of 0 to 10.

4. a kind of method for manufacturing colored filter is to utilize colorized optical filtering according to any one of claims 1 to 3 Piece forms a pixel layer with photosensitive polymer combination.

5. a kind of colored filter is made by method as claimed in claim 4.

6. a kind of liquid crystal display device includes colored filter as claimed in claim 5.