CN105487336A

CN105487336A - Resin composition, black matrix, optical filter and its manufacturing method, and display device

Info

Publication number: CN105487336A
Application number: CN201510597816.1A
Authority: CN
Inventors: 廖豪伟; 周泓佳
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2014-10-01
Filing date: 2015-09-18
Publication date: 2016-04-13
Also published as: TW201614001A; TWI563030B

Abstract

The invention provides a resin composition capable of forming a black matrix with good adhesion and good hardness, a black matrix, an optical filter and a manufacturing method thereof, and a display device. The photosensitive resin composition comprises an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), a multi-branched polymer (D), a solvent (E), and a black pigment (F). The alkali-soluble resin (a) includes a first alkali-soluble resin (a-1) represented by formula (1). The multi-branched polymer (D) is formed by reacting a multi-mercapto compound with a multi-functional (meth) acrylate.

Description

Resin combination, black matrix", optical filter and method for making thereof and display device

Technical field

The present invention relates to a kind of black matrix" photosensitive polymer combination, black matrix", colored filter and manufacture method thereof and liquid crystal indicator.

Background technology

In recent years; along with liquid crystal indicator technology miscellaneous is flourish; and in order to the contrast that improves current liquid crystal indicator and display quality, usually black matrix" (BlackMatrix) can be placed in the striped (Stripe) of colored filter in liquid crystal indicator and point (Dot) gap.The contrast (ContrastRatio) caused by light leak (LightLeakage) between above-mentioned black matrix" can prevent because of pixel declines and degradation problem under excitation (ColorPurity).

Generally speaking, the material that uses of black matrix" is all based on the vapor-deposited film containing chromium or chromium oxide etc.But, during using above-mentioned vapor-deposited film as the material of black matrix", exist and manufacture journey complexity and the shortcomings such as material expensive.In order to head it off, previously proposed to have to utilize photosensitive polymer combination to form the technology of black matrix" by the mode of light lithography (PhotoLithographic).

Along with the light-proofness for black matrix" requires day by day to improve, one of its solution is exactly the use amount increasing black pigment, improves the light-proofness of black matrix" by this.For example, Japanese Patent Laid-Open 2006-259716 publication discloses a kind of black matrix" photosensitive polymer combination, and it comprises the black pigment of high use amount, alkali soluble resin, photopolymerization initiator, the reactive monomer with two functional groups and organic solvent.It should be noted that the reactive monomer with two functional groups can improve the reaction between compound, to form meticulous pattern (FinePattern).By this, in photosensitive polymer combination, when in the mode promoting black pigment use amount with while increasing light-proofness, still can keep the sensitivity of photosensitive polymer combination.

In addition, Japanese Patent Laid-Open 2008-268854 publication discloses a kind of photosensitive polymer combination of black matrix".Above-mentioned photosensitive polymer combination comprises the black pigment of the alkali soluble resin having carboxylic acid group and have unsaturated group, the photo polymerization monomer with ethene unsaturated group, photopolymerization initiator and high use amount.In above-mentioned black matrix" photosensitive polymer combination, by the resolution using specific alkali soluble resin to improve the photosensitive polymer combination of high use amount black pigment.

Although the photosensitive polymer combination that improve black pigment use amount in prior art can increase light-proofness.But adherence and the hardness of the black matrix" formed with above-mentioned existing photosensitive polymer combination are not good.

Therefore, how to provide a kind of black matrix" photosensitive polymer combination forming adherence and all good black matrix" of hardness, desire most ardently the problem of solution for current those skilled in the art in fact.

Summary of the invention

In view of this, the invention provides a kind of black matrix" photosensitive polymer combination, black matrix", colored filter and manufacture method thereof and liquid crystal indicator, it can improve the adherence of above-mentioned black matrix" and the not good problem of hardness.

The invention provides a kind of black matrix" photosensitive polymer combination, it comprises alkali soluble resin (A), has the compound (B) of ethene unsaturated group, light initiator (C), multibranched polymers (D), solvent (E) and black pigment (F).

In detail, alkali soluble resin (A) comprises the first alkali soluble resin (A-1) represented by formula (1).

In formula (1), A represents phenylene or has substituent phenylene, wherein above-mentioned substituting group to be carbon number be 1 to 5 alkyl, halogen atom or phenyl; B represents-CO-,-SO ₂-,-C (CF ₃) ₂-,-Si (CH ₃) ₂-,-CH ₂-,-C (CH ₃) ₂-,-O-, 9,9-fluorenylidenes or singly-bound; L ¹represent the tetravalence carboxylic acid residues containing fluorine atom or the tetravalence carboxylic acid residues not containing fluorine atom; Y ¹represent the dibasic carboxylic acid residue containing fluorine atom or the dibasic carboxylic acid residue not containing fluorine atom; R ¹represent hydrogen atom or methyl; A represents the integer of 1 to 20; L ¹and Y ¹in, at least one contains fluorine atom.

Multibranched polymers (D) is the many sulfhydryl compounds represented by formula (II) and multiple functional radical (methyl) acrylate reactions represented by formula (I) and is formed.

Specifically, multiple functional radical (methyl) acrylate represented by formula (I) is as follows.

In formula (I), R ²represent that hydrogen atom or carbon number are the alkyl of 1 to 4;

R ³represent the residue of n hydroxyl after esterification had in the compound of the hydroxyl of m hydroxyl, wherein m≤n, n represent the integer of 2 to 20,

The compound of above-mentioned hydroxyl is R ⁴(OH) _mor R ⁴(OH) _mthrough the compound of epoxypropane (propyleneoxide), epichlorokydrin (epichlorohydrin), alkyl, alkoxy or hydroxypropyl acrylate (hydroxypropylacrylate) upgrading,

R ⁴(OH) _mfor having the polyvalent alcohol (polyalcohol) that carbon number is 2 to 18, the polyol ethers (polyhydricalcoholethers) formed by above-mentioned polyvalent alcohol, the ester class formed by above-mentioned polyvalent alcohol and acid reaction or silicone (silicone).

The many sulfhydryl compounds represented by formula (II) are as follows.

In formula (II), R ⁵represent singly-bound, carbon number be 1 alkyl or carbon number be the alkyl of the straight or branched of 2 to 22, R ⁵skeleton in the oxygen atom that also can comprise sulphur atom or form in ester group,

P represents the integer of 2 to 6, wherein works as R ⁵when representing singly-bound, p represents 2; Work as R ⁵when representing that carbon number is the alkyl of 1, p represents the integer of 2 to 4; Work as R ⁵when representing that carbon number is the alkyl of the straight or branched of 2 to 22, p represents the integer of 2 to 6.

In one embodiment of this invention, in above-mentioned multibranched polymers (D), the sulfydryl of the many sulfhydryl compounds represented by formula (II) is 1/200 to 1/2 relative to the addition molar ratio of the carbon-to-carbon double bond of multiple functional radical (methyl) acrylate represented by formula (I).

In one embodiment of this invention, above-mentioned multibranched polymers (D), for after the many sulfhydryl compounds represented by formula (II) and multiple functional radical (methyl) acrylate reactions represented by formula (I), remaining (methyl) is acrylate-based, reacts with the sulfhydryl compound with carboxyl represented by formula (III) further and is formed.

In formula (III), R ⁶represent that carbon number is the alkylidene of 1 to 12, q represents the integer of 1 to 3.

In one embodiment of this invention, in above-mentioned multibranched polymers (D), the many sulfhydryl compounds represented by formula (II) and the sulfydryl with the sulfhydryl compound of carboxyl represented by formula (III) are 1/200 to 1/2 relative to the addition molar ratio of the carbon-to-carbon double bond of multiple functional radical (methyl) acrylate represented by formula (I).

In one embodiment of this invention, above-mentioned alkali soluble resin (A-1) is reacted by the first potpourri and obtains, and the first potpourri comprises diol compound (a-1), tetrabasic carboxylic acid or its acid dianhydride (a-2) containing polymerism unsaturated group and dicarboxylic acid or its acid anhydrides (a-3).Tetrabasic carboxylic acid or its acid dianhydride (a-2) comprise tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1), other tetrabasic carboxylic acids except the tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) or its acid dianhydride (a-2-2) or the two combination.Dicarboxylic acid or its acid anhydrides (a-3) comprise dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1), other dicarboxylic anhydrides except the dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) or its dicarboxylic acid compound (a-3-2) or the two combination.It should be noted that in tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3), at least one contains fluorine atom.

In one embodiment of this invention, the tetracarboxylic compound containing fluorine atom that the above-mentioned tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) select free style (2-1) to represent and the group that the tetracarboxylic dianhydride's compound containing fluorine atom represented by formula (2-2) forms.Wherein, the tetracarboxylic compound containing fluorine atom represented by formula (2-1) and as follows containing tetracarboxylic dianhydride's compound of fluorine atom containing fluorine atom represented by formula (2-2).

In formula (2-1) and formula (2-2), L ²one of them in the group selecting free style (L-1) to formula (L-6) to represent.

Formula (L-1) is in formula (L-6), and E independently represents fluorine atom or trifluoromethyl separately, and * represents the position with carbon atom bond.

In one embodiment of this invention, the dicarboxylic acid compound containing fluorine atom that the above-mentioned dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) select free style (3-1) to represent and the group that the dicarboxylic anhydride compound containing fluorine atom represented by formula (3-2) forms.Wherein, the dicarboxylic acid compound containing fluorine atom represented by formula (3-1) and by formula (3-2) represent as follows containing the dicarboxylic anhydride compound of fluorine atom.

In formula (3-1) and formula (3-2), X ¹represent that carbon number is the organic group of the contain fluorine atoms of 1 to 100.

In one embodiment of this invention, the molal quantity of the molal quantity of diol compound (a-1) containing polymerism unsaturated group, the tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) and meet relational expression [(a-2-1)+(a-3-1)]/(a-1)=0.4 ~ 1.6 containing the dicarboxylic acid of fluorine atom or the molal quantity of its acid anhydrides (a-3-1).

In one embodiment of this invention, use amount based on alkali soluble resin (A) is 100 weight portions, the use amount of the first alkali soluble resin (A-1) is 10 weight portion to 100 weight portions, the use amount with the compound (B) of ethene unsaturated group is 15 weight portion to 200 weight portions, the use amount of light initiator (C) is 5 weight portion to 55 weight portions, the use amount of multibranched polymers (D) is 3 weight portion to 35 weight portions, the use amount of solvent (E) is 1000 weight portion to 5000 weight portions, and the use amount of black pigment (F) is 60 weight portion to 600 weight portions.

In one embodiment of this invention, the above-mentioned compound (B) with ethene unsaturated group comprises the compound (B-1) with acidic groups and at least three ethene unsaturated groups.

In one embodiment of this invention, the use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount with the compound (B-1) of acidic groups and at least three ethene unsaturated groups is 15 weight portion to 150 weight portions.

The present invention more provides a kind of manufacture method of colored filter, and it comprises use by above-mentioned black matrix" photosensitive polymer combination to form black matrix".

The present invention separately provides a kind of black matrix", and it is formed by above-mentioned black matrix" photosensitive polymer combination.

The present invention also provides a kind of colored filter, comprises black matrix" described above.

The present invention separately provides a kind of liquid crystal indicator, comprises colored filter described above.

Based on above-mentioned, black matrix" photosensitive polymer combination of the present invention is due to the alkali soluble resin containing the aromatic structure and ad hoc structure with fluorine and multibranched polymers (D), and the adherence of black matrix" and the not good problem of hardness can be improved, and then be applicable to colored filter and liquid crystal indicator.

For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below is described in detail below.

Embodiment

Hereinafter, be represent acrylic acid and/or methacrylic acid with (methyl) acrylic acid, and represent acrylate and/or methacrylate with (methyl) acrylate; Similarly, acryloyl group and/or methacryl is represented with (methyl) acryloyl group.

< black matrix" photosensitive polymer combination >

The invention provides a kind of black matrix" photosensitive polymer combination (following, also referred to as " photosensitive polymer combination "), it comprises alkali soluble resin (A), has the compound (B) of ethene unsaturated group, light initiator (C), multibranched polymers (D), solvent (E) and black pigment (F).In addition, if desired, photosensitive polymer combination also can comprise adjuvant (G).Each composition being used for photosensitive polymer combination of the present invention will be described in detail below.

Alkali soluble resin (A)

Alkali soluble resin (A) comprises the first alkali soluble resin (A-1).In addition, alkali soluble resin (A) optionally comprises the second alkali soluble resin (A-2) and other alkali soluble resins (A-3).

First alkali soluble resin (A-1)

First alkali soluble resin (A-1) is the compound represented by formula (1):

In formula (1), A represents phenylene or has substituent phenylene, wherein substituting group to be carbon number be 1 to 5 alkyl, halogen atom or phenyl; B represents-CO-,-SO ₂-,-C (CF ₃) ₂-,-Si (CH ₃) ₂-,-CH ₂-,-C (CH ₃) ₂-,-O-, 9,9-fluorenylidenes or singly-bound; L ¹represent the tetravalence carboxylic acid residues containing fluorine atom or the tetravalence carboxylic acid residues not containing fluorine atom; Y ¹represent the dibasic carboxylic acid residue containing fluorine atom or the dibasic carboxylic acid residue not containing fluorine atom; R ¹represent hydrogen atom or methyl; M represents the integer of 1 to 20; L ¹and Y ¹in, at least one contains fluorine atom.

It should be noted that L ¹can be the tetravalence carboxylic acid residues containing fluorine atom or the tetravalence carboxylic acid residues not containing fluorine atom, be preferably the tetravalence aromatic group with fluorine, and be more preferred from the phenyl ring with fluorine.

Specifically, alkali soluble resin (A-1) is reacted by the first potpourri and obtains.First potpourri comprises diol compound (a-1), tetrabasic carboxylic acid or its acid dianhydride (a-2) containing polymerism unsaturated group and dicarboxylic acid or its acid anhydrides (a-3).In tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3), at least one need contain fluorine atom.Each composition of first potpourri is below described.

Diol compound (a-1) containing polymerism unsaturated group

Diol compound (a-1) containing polymerism unsaturated group is obtained by the bisphenol compound with two epoxy radicals (a-1-i) and compound (a-1-ii) reaction with at least one carboxylic acid group and at least one ethene unsaturated group.The reactant of the diol compound (a-1) of synthesis containing polymerism unsaturated group also can comprise other compounds.

The bisphenol compound (a-1-i) with two epoxy radicals can, such as under alkali metal hydroxide exists, make bisphenol compound and halogenated epoxy propane carry out de-hydrogen halide and obtain.

The concrete example being used for synthesizing the bisphenols of the bisphenol compound (a-1-i) with two epoxy radicals comprises two (4-hydroxy phenyl) ketone, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ketone, two (4-hydroxyl-3,5-dichlorophenyl) ketone, two (4-hydroxy phenyl) sulfone, two (4-hydroxyl-3,5-3,5-dimethylphenyl) sulfone, two (4-hydroxyl-3,5-dichlorophenyl) sulfone, two (4-hydroxy phenyl) HFC-236fa, two (4-hydroxyl-3,5-3,5-dimethylphenyl) HFC-236fa, two (4-hydroxyl-3,5-dichlorophenyl) HFC-236fa, two (4-hydroxy phenyl) dimethylsilane, two (4-hydroxyl-3,5-3,5-dimethylphenyl) dimethylsilane, two (4-hydroxyl-3,5-dichlorophenyl) dimethylsilane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-3,5-dichlorophenyl) methane, two (4-hydroxyl-3,5-dibromo phenyl) methane, two (4-hydroxy phenyl) propane of 2,2-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2,2-, two (4-hydroxyl-3, the 5-dichlorophenyl) propane of 2,2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-, two (4-hydroxyl-3-chlorphenyl) propane of 2,2-, two (4-hydroxy phenyl) ether, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ether, two (4-hydroxyl-3,5-dichlorophenyl) ether etc., 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-3,5-dimethylphenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-chlorphenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-bromophenyl) fluorenes, 9 of 9-, the combination of two (4-hydroxyl-3-fluorophenyl) fluorenes of 9-, 9,9-two (4-hydroxyl-3,5-3,5-dimethylphenyl) fluorenes or above-claimed cpd.

The concrete example being used for synthesizing the halogenated epoxy propane of the bisphenol compound (a-1-i) with two epoxy radicals comprises the combination of chloro-1, the 2-epoxypropane of 3-, bromo-1, the 2-epoxypropane of 3-or above-claimed cpd.Be 1 equivalent based on the hydroxyl total yield in above-mentioned bisphenol compound, the use amount of above-mentioned halogenated epoxy propane can be 1 equivalent to 20 equivalent, and is preferably 2 equivalent to 10 equivalents.

The concrete example of alkali metal hydroxide comprises the combination of NaOH, potassium hydroxide or above-claimed cpd.Be 1 equivalent based on the hydroxyl total yield in above-mentioned bisphenol compound, the use amount of the alkali metal hydroxide added in above-mentioned de-hydrogen halide can be 0.8 equivalent to 15 equivalent, and is preferably 0.9 equivalent to 11 equivalent.

It should be noted that before carrying out de-hydrogen halide, can add in advance or in course of reaction, add the alkali metal hydroxide such as NaOH, potassium hydroxide.The operating temperature of de-hydrogen halide is 20 DEG C to 120 DEG C, and its running time scope is 1 little of 10 hours.

In one embodiment, the alkali metal hydroxide added in above-mentioned de-hydrogen halide also can use its aqueous solution.In this embodiment, above-mentioned alkali metal hydroxide aqueous solution is added into continuously de-hydrogen halide intrasystem while, can under decompression or normal pressure, continuous still water outlet and halogenated epoxy propane, be separated by this and except anhydrating, halogenated epoxy propane can be back in reactive system continuously simultaneously.

Before above-mentioned de-hydrogen halide carries out, also can add the quarternary ammonium salt of tetramethyl-ammonium chloride, tetramethylammonium bromide, trimethyl benzyl ammonia chloride etc. as catalyzer.Then, at 50 DEG C at 150 DEG C, reaction 1 is little of 5 hours, then adds alkali metal hydroxide or its aqueous solution.Then, at the temperature of 20 DEG C to 120 DEG C, it makes reaction 1 little of 10 hours, to carry out de-hydrogen halide.

In addition, in order to make above-mentioned de-hydrogen halide carry out smoothly, also can add outside the alcohols such as methyl alcohol, ethanol, the polarity solvent etc. that also can add the aprotic such as dimethyl sulfone, dimethyl sulfoxide reacts.When using alcohols, the total amount based on above-mentioned halogenated epoxy propane is 100 % by weight, and the use amount of alcohols can be 2 % by weight to 20 % by weight, and is preferably 4 % by weight to 15 % by weight.In the example of polarity solvent using aprotic, the total amount based on halogenated epoxy propane is 100 % by weight, and the use amount of the polarity solvent of aprotic can be 5 % by weight to 100 % by weight, is preferably 10 % by weight to 90 % by weight.

After completing de-hydrogen halide, optionally carry out washing process.Afterwards, utilize the mode of heating decompression, such as in temperature be 110 DEG C to 250 DEG C and pressure be 1.3kPa (10mmHg) below, the polarity solvent etc. of removing halogenated epoxy propane, alcohols and aprotic.

In order to avoid the epoxy resin formed contains hydrolyzable halogen, solution after de-hydrogen halide can be added benzene, toluene, methyl isobutyl ketone (methylisobutylketone) equal solvent, and add the alkali metal hydroxide aqueous solution such as NaOH, potassium hydroxide, again to carry out de-hydrogen halide.In de-hydrogen halide, be 1 equivalent based on the hydroxyl total yield in above-mentioned bisphenol compound, the use amount of alkali metal hydroxide can be 0.01 mole to 1 mole, is preferably 0.05 mole to 0.9 mole.In addition, the operating temperature range of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, and its running time scope is 0.5 little of 2 hours.

After completing de-hydrogen halide, by filter and the step such as washing removes salt.In addition, can utilize the mode of heating decompression, by benzene, toluene, methyl isobutyl ketone equal solvent is heated up in a steamer removes, then can obtain the bisphenol compound (a-1-i) with two epoxy radicals.

The bisphenol compound (a-1-i) with two epoxy radicals is preferably the bisphenol compound with two epoxy radicals represented by following formula (1-1), or the bisphenol compound with two epoxy radicals represented by following formula (1-2) is the polymkeric substance of monomer polymerization.

In formula (1-1) and formula (1-2), A ¹to A ⁸the respective alkyl or phenyl independently representing hydrogen atom, halogen atom, carbon number 1 to 5.B represents-CO-,-SO ₂-,-C (CF ₃) ₂-,-Si (CH ₃) ₂-,-CH ₂-,-C (CH ₃) ₂-,-O-, 9,9-fluorenylidenes or singly-bound.M1 can represent the integer of 1 to 10, and m1 is more preferred from the integer of expression 1 to 2.

The special good bisphenol compound with two epoxy radicals represented for following formula (1-3) of bisphenol compound of two epoxy radicals that what formula (1-1) represented have.

In formula (1-3), A ¹, A ², A ³, A ⁴, A ⁷and A ⁸the respective alkyl or phenyl independently representing hydrogen atom, halogen atom, carbon number 1 to 5.

The bisphenol compound with two epoxy radicals represented by formula (1-3) is such as the bisphenol fluorene type compound with two epoxy radicals being reacted by bisphenol fluorene type compound (bisphenolfluorene) and halogenated epoxy propane (epihalohydrin) and obtain.

The concrete example of bisphenol fluorene type compound comprises 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-chlorphenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-bromophenyl) fluorenes, 9 of 9-, two (4-hydroxyl-3-fluorophenyl) fluorenes, 9 of 9-, two (the 4-hydroxy 3-methoxybenzene base) fluorenes, 9 of 9-, two (the 4-hydroxyl-3 of 9-, 5-3,5-dimethylphenyl) fluorenes, 9,9-two (4-hydroxyl-3,5-dichlorophenyl) fluorenes, 9, the combination of two (4-hydroxyl-3, the 5-dibromo phenyl) fluorenes of 9-or above-claimed cpd.

The concrete example of halogenated epoxy propane comprises the combination of bromo-1, the 2-epoxypropane (epibromohydrin) of chloro-1, the 2-epoxypropane of 3-(epichlorohydrin), 3-or above-claimed cpd.

The concrete example with the bisphenol fluorene type compound of epoxy radicals comprises the commodity of (1) Nippon Steel chemistry manufacture: such as ESF-300 or its analog; (2) commodity of Osaka gas manufacture: such as PG-100, EG-210 or its analog; Or the commodity that (3) S.M.STechnologyCo. manufactures: such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or its analog.

The compound (a-1-ii) with at least one carboxylic acid group and at least one ethene unsaturated group is selected from least one compound in the group that is made up of following compound: acrylic acid, methacrylic acid, 2-methylacryoyloxyethyl succinic acid, 2-methacryl oxygen-butyl succinic acid, 2-methylacryoyloxyethyl hexane diacid, 2-methacryl oxygen-butyl hexane diacid, 2-methylacryoyloxyethyl hexahydrophthalic acid, 2-methylacryoyloxyethyl maleic acid, 2-methacryloxypropyl maleic acid, 2-methacryl oxygen-butyl maleic acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl hexane diacid, 2-methacryloxypropyl tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryl oxygen-butyl phthalic acid, or 2-methacryl oxygen-butyl hydrogen phthalic acid, the compound being reacted by (methyl) acrylate and the dicarboxylic acid compound of hydroxyl and obtained, wherein dicarboxylic acid compound is including but not limited to hexane diacid, succinic acid, maleic acid, phthalic acid, the half ester compound being reacted by (methyl) acrylate and the compound carboxylic acid anhydride of hydroxyl and obtained, wherein (methyl) acrylate of hydroxyl is including but not limited to 2-hydroxyethylmethacry,ate, 2-HEMA, 2-acrylate, 2-hydroxy propyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol acrylate trimethyl etc.In addition, the concrete example of compound carboxylic acid anhydride described herein can be identical with the dicarboxylic anhydride concrete example in the tetracarboxylic dianhydride's concrete example in other tetrabasic carboxylic acids following or its acid dianhydride (a-2-2) and other dicarboxylic acid following or its acid anhydrides (a-3-2), therefore separately do not repeat.

Tetrabasic carboxylic acid or its acid dianhydride (a-2)

Tetrabasic carboxylic acid or its acid dianhydride (a-2) comprise tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1), other tetrabasic carboxylic acids except described tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) or its acid dianhydride (a-2-2) or the two combination.

The tetracarboxylic compound containing fluorine atom that tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) select free style (2-1) to represent and the group that the tetracarboxylic dianhydride's compound containing fluorine atom represented by formula (2-2) forms.Specifically, the tetracarboxylic compound containing fluorine atom represented by formula (2-1) and by formula (2-2) represent as follows containing tetracarboxylic dianhydride's compound of fluorine atom.

In formula (2-1) and formula (2-2), L ²for having the tetravalence aromatic group of fluorine, and be preferably there is phenyl ring.Specifically, the wherein one in the group selecting free style (L-1) to formula (L-6) to represent is preferably.

In detail, the concrete example of the tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) comprises 4,4'-hexafluoroisopropyli,ene two phthalic acid, 1,4-difluoro Pyromellitic Acid (1,4-difluoropyromelliticacid), the mono-fluorine Pyromellitic Acid of 1-, 1, the aromatic tetracarboxylic acid that 4-bis-(trifluoromethyl) Pyromellitic Acid etc. are fluorine-containing, or the dianhydride compound of above-mentioned tetrabasic carboxylic acid, or the combination of above-claimed cpd.

The concrete example of the tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) also comprises 3, 3'-hexafluoroisopropyli,ene two phthalic acid (3, 3'-(hexafluoroisopropylidene) diphthalicacid), 5, 5'-[2, 2, the fluoro-1-of 2-tri-[3-(trifluoromethyl) phenyl] ethylidene] two phthalic acids, 5, 5'-[2, 2, 3, 3, the fluoro-1-of 3-five (trifluoromethyl) propylidene] two phthalic acids, 5, 5'-oxygen base two [4, 6, the fluoro-Pyromellitic Acid of 7-tri-] (5, 5'-oxybis [4, 6, 7-trifluoro-pyromelliticacid], 3, two (trifluoromethyl) Pyromellitic Acid of 6-, 4-(trifluoromethyl) Pyromellitic Acid, 1, 4-two (3, 4-dicarboxylic acid trifluoromethoxy phenoxy base) the fluorine-containing tetrabasic carboxylic acid such as phenyl tetrafluoride, or the dianhydride compound of above-mentioned tetrabasic carboxylic acid, or the combination of above-claimed cpd.

Other tetrabasic carboxylic acids or its acid dianhydride (a-2-2) comprise Saturated straight-chain paraffin tetrabasic carboxylic acid, ester ring type tetrabasic carboxylic acid, aromatic tetracarboxylic acid, or the dianhydride compound of above-mentioned tetrabasic carboxylic acid, or its combination.

The concrete example of Saturated straight-chain paraffin tetrabasic carboxylic acid comprises BTCA, pentane tetrabasic carboxylic acid, hexane tetrabasic carboxylic acid, or the combination of above-claimed cpd.Saturated straight-chain paraffin tetrabasic carboxylic acid also can have substituting group.

The concrete example of ester ring type tetrabasic carboxylic acid comprises cyclo-butane tetrabasic carboxylic acid, cyclopentane tetrabasic carboxylic acid, thiacyclohexane tetrabasic carboxylic acid, norbornane tetrabasic carboxylic acid, or the combination of above-claimed cpd.Ester ring type tetrabasic carboxylic acid also can have substituting group.

The concrete example of aromatic tetracarboxylic acid comprises Pyromellitic Acid, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid, Biphenyl Ether tetrabasic carboxylic acid, diphenyl sulfone tetrabasic carboxylic acid, 1,2,3,6-tetrahydrophthalic acid, or the combination of above-claimed cpd.Aromatic tetracarboxylic acid also can have substituting group.

Dicarboxylic acid or its acid anhydrides (a-3)

Dicarboxylic acid or its acid anhydrides (a-3) comprise dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1), other dicarboxylic acid except described dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) or its acid anhydrides (a-3-2) or the two combination.

The dicarboxylic acid compound containing fluorine atom that dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) select free style (3-1) to represent and the group that the dicarboxylic anhydride compound containing fluorine atom represented by formula (3-2) forms.Specifically, the dicarboxylic acid compound containing fluorine atom represented by formula (3-1) and by formula (3-2) represent as follows containing the dicarboxylic anhydride compound of fluorine atom.

The concrete example of the dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) comprises 3-fluorine phthalic acid, 4-fluorine phthalic acid, ptfe phthalate, 3,6-difluoro phthalic acid, tetrafluoro succinic acid, or the anhydride compound of above-mentioned dicarboxylic acid, or the combination of above-claimed cpd.

The concrete example of other dicarboxylic acid or its acid anhydrides (a-3-2) comprises Saturated straight-chain paraffin dicarboxylic acid, saturated cyclic hydrocarbon dicarboxylic acid, unsaturated dicarboxylic, or the acid anhydrides of above-mentioned dicarboxylic acid compound, or the combination of above-claimed cpd.

The concrete example of Saturated straight-chain paraffin dicarboxylic acid comprises succinic acid, acetyl-malic acid, hexane diacid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartrate, ketoglutaric acid, heptandioic acid, decanedioic acid, suberic acid, diethylene glycol acid, or the combination of above-claimed cpd.Alkyl in Saturated straight-chain paraffin dicarboxylic acid also can be substituted.

The concrete example of saturated cyclic hydrocarbon dicarboxylic acid comprises hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, six hydrogen trimellitic acids, or the combination of above-claimed cpd.Saturated cyclic hydrocarbon dicarboxylic acid also can be the ester ring type dicarboxylic acid that stable hydrocarbon is substituted.

The concrete example of unsaturated dicarboxylic comprises maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylene tetrahydrophthalic acid (methylendo-methylenetetrahydrophthalicacid), chlorine mattress acid (chlorendicacid), trimellitic acid, or the combination of above-claimed cpd.

The concrete example of other dicarboxylic acid or its acid anhydrides (a-3-2) comprises trimethoxysilylpropyl succinic anhydride, tri-ethoxy silylpropyl succinic anhydride, methyl dimethoxysilane base propyl succinimide acid anhydrides, methyldiethoxysilane base propyl succinimide acid anhydrides, trimethoxy silane Ji Dingji succinic anhydride, triethoxysilicane alkyl butyl succinic anhydride, methyldiethoxysilane Ji Dingji succinic anhydride, to (trimethoxy silane base) phenylsuccinic acid acid anhydride, to (triethoxysilicane alkyl) phenylsuccinic acid acid anhydride, to (methyl dimethoxysilane base) phenylsuccinic acid acid anhydride, to (methyldiethoxysilane base) phenylsuccinic acid acid anhydride, between (trimethoxy silane base) phenylsuccinic acid acid anhydride, between (triethoxysilicane alkyl) phenylsuccinic acid acid anhydride, between the dicarboxylic anhydride such as (methyldiethoxysilane base) phenylsuccinic acid acid anhydride, or the dicarboxylic acid compound of above-mentioned dicarboxylic anhydride, or the combination of above-claimed cpd.

Dicarboxylic acid compound is preferably the combination of succinic acid, itaconic acid, tetrahydrophthalic acid, six hydrogen trimellitic acids, phthalic acid, trimellitic acid or above-claimed cpd, is more preferred from the combination of succinic acid, itaconic acid, tetrahydrophthalic acid or above-claimed cpd.

Dicarboxylic anhydride is preferably the combination of succinic anhydride, itaconic anhydride, tetrabydrophthalic anhydride, six hydrogen trimellitic anhydrides, phthalic anhydride, trimellitic anhydride or above-claimed cpd.

There is no particular restriction for the synthetic method of alkali soluble resin (A-1), as long as the diol compound (a-1) containing polymerism unsaturated group, tetracarboxylic dianhydride or its tetrabasic carboxylic acid (a-2) and dicarboxylic anhydride or its dicarboxylic acid (a-3) reaction can be obtained.

When preparing above-mentioned alkali soluble resin (A-1), being accelerated reaction, usually can adding alkali compounds as catalysts in reaction solution.The concrete example of above-mentioned catalysts comprises the combination of triphenylphosphine (triphenylphosphine), antimony triphenyl (triphenylstibine), triethylamine, triethanolamine, tetramethyl ammonium chloride, benzyltriethylammonium chloride or above-mentioned catalysts.Above-mentioned catalysts can multiplely alone or in combination use.

In addition, in order to control the degree of polymerization, usually also polymerization inhibitor can be added in reaction solution.The concrete example of above-mentioned polymerization inhibitor comprises methoxyl phenol, methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), 2,6-BHT (2,6-di-tert-butyl-p-cresol), phenothiazine (phenothiazine) or its analog.Above-mentioned polymerization inhibitor can multiplely alone or in combination use.

When preparing above-mentioned alkali soluble resin (A-1), polymerization solvent can be used if desired.The concrete example of above-mentioned polymerization solvent comprises: the alcohol compound of ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, 2-butanols, hexanol, ethylene glycol or its analog; The ketone compounds of MEK, cyclohexanone or its analog; The aromatic hydrocarbon compounds of toluene, dimethylbenzene or its analog; Match Luo element (cellosolve) compounds of match Luo element, butyl match Luo element (butylcellosolve) or its analog; Card must appropriate, butyl card must the card of appropriate or its analog must appropriate compounds; The propylene glycol alkyl ether compound of propylene glycol monomethyl ether or its analog; Many propylene glycol alkyls ether compound of dipropylene glycol monomethyl ether or its analog; The acetic ester compounds of ethyl acetate, butyl acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate or its analog; The lactic acid alkane ester type compound of ethyl lactate, butyl lactate or its analog; Or dialkyl group glycol ethers; Or other ester classes such as 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate (EEP), ethoxy ethyl acetate.Above-mentioned polymerization solvent can be used alone or combines multiple use.In addition, the acid value of above-mentioned alkali soluble resin (A-1) is 50mgKOH/g to 200mgKOH/g, is preferably 60mgKOH/g to 180mgKOH/g.

In addition, synthetic method such as can adopt as described in Japanese Patent Laid-Open 9-325494 publication, at temperature of reaction is 90 DEG C to 140 DEG C, make the known method that diol compound and tetracarboxylic dianhydride react.In addition, at temperature of reaction is 90 DEG C to 130 DEG C, the first potpourri dissolved equably and make it react, then carrying out reacting and maturation (aging) at temperature of reaction is 40 DEG C to 80 DEG C.

Reacted by the first potpourri and the alkali soluble resin (A-1) of acquisition is a kind of alkali soluble resin containing fluorine atom, and be preferably the alkali soluble resin containing the aromatic structure with fluorine.

On the other hand, in each composition of the first potpourri forming alkali soluble resin (A-1), in tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3), at least one contains fluorine atom, and is preferably tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3) all containing fluorine atom.When tetrabasic carboxylic acid or its acid dianhydride (a-2) or dicarboxylic acid or its acid anhydrides (a-3) are neither containing fluorine atom, resolution and the resistance to developability of photosensitive polymer combination are not good.In detail, when tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3) are all containing fluorine atom, tetrabasic carboxylic acid or its acid dianhydride (a-2) comprise tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1), and dicarboxylic acid or its acid anhydrides (a-3) comprise dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1).

Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount of the first alkali soluble resin (A-1) can be 10 weight portion to 100 weight portions, be preferably 12 weight portion to 100 weight portions, and be more preferred from 15 weight portion to 100 weight portions.

It should be noted that the adherence of photosensitive polymer combination is not good when alkali soluble resin (A) is not containing the first alkali soluble resin (A-1).Furthermore, when photosensitive polymer combination comprises the first alkali soluble resin (A-1), because fluorine atom effectively can improve the water-repellancy (waterrepellency) of alkali soluble resin, therefore when follow-up development step, part through exposure lateral erosion (lateraletching) is less likely to occur and comes off, and can solve the problem that the adherence of photosensitive polymer combination is not good by this.

In addition, the molal quantity of the molal quantity of diol compound (a-1) containing polymerism unsaturated group, the tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) and be preferably containing the dicarboxylic acid of fluorine atom or the molal quantity of its acid anhydrides (a-3-1) relational expression [(a-2-1)+(a-3-1)]/(a-1)=0.4 ~ 1.6 can be met.When [(a-2-1)+(a-3-1)]/(a-1)=0.4 ~ 1.6, can further improve the adherence of photosensitive polymer combination.

Second alkali soluble resin (A-2)

Second alkali soluble resin (A-2) comprises the derived units with the structure represented by formula (4).

In formula (4), R ²and R ³respective be independently hydrogen atom, carbon number be 1 to 5 straight or branched alkyl, phenyl or halogen atom.

Second alkali soluble resin (A-2) is reacted by the compound of the compound and other copolymerizable reactions with the structure represented by formula (4) and obtains.The compound with the structure represented by formula (4) can be the following bisphenol fluorene type compound containing two epoxy radicals represented by formula (5) or the bisphenol fluorene type compound containing two hydroxyls represented by formula (6).

In formula (5), R ⁴with the R of formula (4) ²identical; R ⁵with the R of formula (4) ³identical, do not repeat separately at this.

In formula (6), R ⁶with the R of formula (4) ²identical; R ⁷with the R of formula (4) ³identical, do not repeat separately at this; R ⁸and R ⁹the alkylidene of respective independent expression carbon number 1 to 20 or sub-alicyclic group; P and q independently represents the integer of 1 to 4 separately.

The concrete example of the compound of other copolymerizable reactions comprises the unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid; Dicarboxylic acids class and the acid anhydrides thereof such as maleic acid, itaconic acid, succinic acid, phthalic acid, four hydrogen phthalates, hexahydrobenzene dioctyl phthalate, methyl four hydrogen phthalate, methyl hexahydrobenzene dioctyl phthalate, methylendomethylene tetrahydrophthalic acid, the acid of chlorine mattress, glutaric acid; Tricarboxylic acid class and the acid anhydrides thereof such as trimellitic acid; And the combination of the quaternary carboxylic acids such as Pyromellitic Acid, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid, Biphenyl Ether tetrabasic carboxylic acid and acid anhydrides or above-claimed cpd.

Second alkali soluble resin (A-2) is preferably Nippon Steel's chemistry system, and product are called the products such as V259ME, V301ME.

Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of the second alkali soluble resin (A-2) can be 0 weight portion to 90 weight portion, is preferably 0 weight portion to 88 weight portion, and is more preferred from 0 weight portion to 85 weight portion.

Other alkali soluble resins (A-3)

Alkali soluble resin (A) also alternative comprises other alkali soluble resins (A-3).Other alkali soluble resins (A-3) be the first alkali soluble resin (A-1) with the second alkali soluble resin (A-2) beyond resin.Other alkali soluble resins (A-3) such as having the resin of carboxylic acid group or hydroxyl, but are not limited to the resin with carboxylic acid group or hydroxyl.The concrete example of other alkali soluble resins (A-3) comprises acrylic resin, amido formate (urethane) is the resin such as resin, novolaks (novolac) resin.

Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of other alkali soluble resins (A-3) is 0 weight portion to 30 weight portion, is preferably 0 weight portion to 20 weight portion, and is more preferred from 0 weight portion to 10 weight portion.

There is the compound (B) of ethene unsaturated group

The compound (B) with ethene unsaturated group can comprise the compound (B-1) with acidic groups and at least three ethene unsaturated groups.In addition, the compound (B) with ethene unsaturated group still can comprise other compounds with ethene unsaturated group (B-2).

There is the compound (B-1) of acidic groups and at least three ethene unsaturated groups

Have acidic groups in the compound (B-1) of acidic groups and at least three ethene unsaturated groups can with alkaline developer generation effect.The concrete example of acidic groups comprises carboxyl, sulfonic group or phosphate etc., and wherein, acidic groups is preferably and can produces the carboxyl of good action with alkaline developer.

The compound (B-1) with acidic groups and at least three ethene unsaturated groups comprises (1) and carries out upgrading reaction, to synthesize carboxylic multifunctional (methyl) acrylate by having multifunctional (methyl) acrylate of hydroxyl and dicarboxylic acid anhydride or dibasic acid; And multifunctional for aromatic series (methyl) acrylate and the concentrated sulphuric acid or oleum are carried out upgrading reaction, to synthesize containing sulfonic multifunctional (methyl) acrylate by (2).

There is acidic groups and be preferably with the compound (B-1) of at least three ethene unsaturated groups the structure having and represented by formula (IV) or (V).

In formula (IV), B ¹expression-CH ₂-,-OCH ₂-,-OCH ₂cH ₂-,-OCH ₂cH ₂cH ₂-or-OCH ₂cH ₂cH ₂cH ₂-; B ²represent the structure represented by formula (IV-1) or formula (IV-2); B ³represent the structure represented by formula (IV-3), formula (IV-4) or formula (IV-5), the phenyl ring in the structure that its Chinese style (IV-5) represents also can through tetrahydro or hexahydro, and c represents the integer of 1 to 8; B represents the integer of 0 to 14.Work as B ¹and B ²when existing multiple, B ¹and B ²can be identical or different separately.

In formula (V), B ¹, B ², B ³and the B in b and formula (IV) ¹, B ², B ³and b synonym, do not repeat separately at this; B ⁴the structure representing-O-or represented by formula (V-1).Work as B ¹and B ²when existing multiple, B ¹and B ²can be identical or different separately.

In formula (V-1), d represents the integer of 1 to 8.

Such as there is the compound of acidic groups and three ethene unsaturated groups or there is the compound of acidic groups and five ethene unsaturated groups in the above-mentioned compound (B-1) with acidic groups and at least three ethene unsaturated groups represented by formula (IV) or formula (V).

The monoester compound containing carboxyl that two acids of monohydroxy oligomerization acrylate or monohydroxy oligomerization methacrylate and malonic acid, succinic acid, glutaric acid, m-phthalic acid, terephthalic acid (TPA), phthalic acid etc. that the concrete example with the compound of acidic groups and three ethene unsaturated groups comprises pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, Dipentaerythritol Pentaacrylate or dipentaerythritol pentamethacrylates etc. are formed.The concrete example with the commercial goods of the compound of acidic groups and three ethene unsaturated groups comprises TO-756 (Toagosei Co., Ltd's system), PE3A-MS, PE3A-MP (Kyoeisha Chemical Co., Ltd.'s system), or the combination of above-mentioned commercial goods.

The concrete example with the commercial goods of the compound of acidic groups and five ethene unsaturated groups comprises TO-1382, TO-1385 (Toagosei Co., Ltd's system), DPE6A-MS, DPE6A-MP (Kyoeisha Chemical Co., Ltd.'s system), or the combination of above-mentioned commercial goods.

The concrete example with the compound (B-1) of acidic groups and at least three ethene unsaturated groups is preferably the monoester compound containing carboxyl that pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, Dipentaerythritol Pentaacrylate or dipentaerythritol pentamethacrylates and succinic acid or phthalic acid are formed.

The above-mentioned compound (B-1) with acidic groups and at least three ethene unsaturated groups can be used alone or combine multiple use.

Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount with the compound (B-1) of acidic groups and at least three ethene unsaturated groups can be 15 weight portion to 150 weight portions, be preferably 20 weight portion to 140 weight portions, be more preferred from 25 weight portion to 130 weight portions.

It should be noted that, because the acidic groups of the compound (B-1) with acidic groups and at least three ethene unsaturated groups can increase the Van der Waals force (VanderWaalsforce) between black matrix" and substrate (such as glass) that photosensitive polymer combination formed, and at least three ethene unsaturated groups can participate in photochemical reaction and increase the cross-linking density of hardening thing (black matrix"), can promote adherence and the hardness of the black matrix" manufactured by photosensitive polymer combination by this.

Other have the compound (B-2) of ethene unsaturated group

Other compounds (B-2) with ethene unsaturated group comprise the compound with an ethene unsaturated group, the compound with more than two ethene unsaturated groups, or the two combination.

The concrete example with the compound of an ethene unsaturated group includes but not limited to (methyl) acrylamide ((meth) acrylamide), (methyl) acryloyl morpholine ((meth) acrylmorpholine), (methyl) acrylic acid-7-amido-3,7-dimethyl monooctyl ester, isobutoxymethyl (methyl) acrylamide, (methyl) isobomyl acrylate base 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite, ethyl diethylene glycol (methyl) acrylate, tertiary octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) DMAM, (methyl) dodecylacrylate, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid-2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate (tetrahydrofurfuryl (meth) acrylate), (methyl) tetrabromophenyl acrylate, (methyl) acrylic acid-2-tetrabromo phenoxy ethyl, (methyl) acrylic acid-2-Trichlorophenoxy ethyl ester, (methyl) tribromophenyl acrylate, (methyl) acrylic acid-2-tribromophenoxy ethyl ester, 2-hydroxyl-(methyl) ethyl acrylate, 2-hydroxyl-(methyl) propyl acrylate, caprolactam, NVP, (methyl) acrylate, (methyl) Pentachlorophenyl Acrylate, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid second diester, poly-single (methyl) acrylic acid propylene diester, (methyl) acrylic acid norbornene ester, or its combination.The compound with an ethene unsaturated group can be used alone or combine multiple use.

The concrete example with the compound of more than two ethene unsaturated groups includes but not limited to ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid dicyclopentenyl ester, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid two (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid three (methyl) acrylate, through three (2-hydroxyethyl) isocyanic acid three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of ethane via epoxyethane (being called for short EO) upgrading, through three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane upgrading (being called for short PO), tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, polyester two (methyl) acrylate, polyglycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol four (methyl) acrylate, through dipentaerythritol six (methyl) acrylate of caprolactone upgrading, through dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid two trihydroxy methyl propyl ester (di (trimethylolpropane) tetra (meth) acrylate), bisphenol-A two (methyl) acrylate of ethane via epoxyethane upgrading, through bisphenol-A two (methyl) acrylate of epoxypropane upgrading, hydrogenated bisphenol A two (methyl) acrylate of ethane via epoxyethane upgrading, through hydrogenated bisphenol A two (methyl) acrylate of epoxypropane upgrading, Bisphenol F two (methyl) acrylate of ethane via epoxyethane upgrading, novolaks polyglycidyl ether (methyl) acrylate, or its combination.The compound with more than two ethene unsaturated groups can be used alone or combine multiple use.

Other concrete examples with the compound (B-2) of ethene unsaturated group are preferably and comprise three acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of ethane via epoxyethane upgrading, through three acrylic acid trihydroxy methyl propyl ester of epoxypropane upgrading, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol tetraacrylate, through the dipentaerythritol acrylate of caprolactone upgrading, tetrapropylene acid two trihydroxy methyl propyl ester, through the glycerol tri-acrylate of epoxypropane upgrading, or its combination.

Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount with the compound (B) of ethene unsaturated group can be 15 weight portion to 200 weight portions, be preferably 20 weight portion to 190 weight portions, be more preferred from 25 weight portion to 180 weight portions.

Light initiator (C)

Light initiator (C) is such as the combination of acetophenone based compound (acetophenone), diimidazole based compound (biimidazole), acyl oxime compound (acyloxime) or above-claimed cpd.

The concrete example of acetophenone based compound comprises dimethylamine acetophenone, α, α '-dimethoxy azoxy acetophenone, 2,2 '-dimethyl-2-phenyl acetophenone, acetanisole, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone, 2-benzyl-2-nitrogen, the combination of nitrogen-dimethylamine-1-(4-morphlinophenyl)-1-butanone or above-claimed cpd.

The concrete example of diimidazole based compound comprises 2, 2 '-bis-(o-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(ortho-fluorophenyl base)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-aminomethyl phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-ethylphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(p-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2, 2 ', 4, 4 '-tetramethoxy phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, the combination of 5 '-tetraphenyl diimidazole or above-claimed cpd.

The concrete example of acyl oxime compound comprises ethane ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9 hydrogen-carbazole-3-substituting group]-1-(oxygen-acetyl oxime) [Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime), as the OXE-02 that Ciba company limited (CibaSpecialtyChemicals) manufactures, its structure is by formula (7) Suo Shi], 1-(4-(phenyl) phenyl)-octane-1, 2-diketone-2-oxime-oxygen-benzoic ether [1-(4-phenyl-thio-phenyl)-octane-1, 2-dion-2-oxime-O-benzoate, as the OXE-01 that Ciba company limited manufactures, its structure is by formula (8) Suo Shi], ethane ketone, 1-[9-ethyl-6-(the chloro-4-benzyl-sulfo--benzoyl of 2-)-9 hydrogen-carbazole-3-substituting group]-, 1-(oxygen-acetyl oxime) [Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime), by rising sun electrification, company manufactures, its structure is by formula (9) Suo Shi] or the combination of above-claimed cpd.

Light initiator (C) is preferably 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone, 2-benzyl-2-nitrogen; nitrogen-dimethylamine-1-(4-morphlinophenyl)-1-butanone, 2; 2 '-bis-(o-chlorphenyl)-4; 4 '; 5; 5 '-tetraphenyl diimidazole, ethane ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9 hydrogen-carbazole-3-substituting group]-, the combination of 1-(oxygen-acetyl oxime) or above-claimed cpd.

Light initiator (C) optionally can add following compound further: thioxanthones (thioxanthone), 2,4-diethyl thioxanthone, thioxanthones-4-sulfone, benzophenone, 4, benzophenone (benzophenone) based compounds such as 4 '-bis-(dimethylamine) benzophenone, 4,4 '-bis-(diethylamine) benzophenone; α-diketone (α-diketone) classes such as benzil (benzil), acetyl group (acetyl); Keto-alcohol (acyloin) class of diphenylhydroxyethanone (benzoin) etc.; The keto-alcohol ethers such as diphenylhydroxyethanone methyl ether (benzoinmethylether), diphenylhydroxyethanone ether (benzoinethylether), diphenylhydroxyethanone isopropyl ether (benzoinisopropylether); 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide), two-(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide] etc. acyl phosphine oxide class; The quinones such as anthraquinone (anthraquinone), 1,4-naphthoquinone (Isosorbide-5-Nitrae-naphthoquinone); The halogenide such as chloroacetophenone (phenacylchloride), trisbromomethyl benzene sulfone (tribromomethyl-phenylsulfone), three (trichloromethyl)-s-triazine [tris (trichloromethyl)-s-triazine]; The superoxide such as two-tert-butyl peroxide (di-tertbutylperoxide); Or the combination of above-claimed cpd.The compound making an addition to light initiator (C) is preferably benzophenone based compound, and is more preferred from 4,4 '-bis-(diethylamine) benzophenone.

Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of light initiator (C) can be 5 weight portion to 55 weight portions, is preferably 7 weight portion to 50 weight portions, and is more preferred from 10 weight portion to 45 weight portions.

Multibranched polymers (D)

Multibranched polymers (D) can be the polymkeric substance that the many sulfhydryl compounds represented by formula (II) are formed through reversal of the Michael addition (MichaelAdditionReaction) with multiple functional radical (methyl) acrylate represented by formula (I).

In formula (I), R ²represent that hydrogen atom or carbon number are the alkyl of 1 to 4; R ³represent the residue of n hydroxyl after esterification had in the compound of the hydroxyl of m hydroxyl, wherein m≤n, n represent the integer of 2 to 20.

The compound of above-mentioned hydroxyl is R ⁴(OH) _mor R ⁴(OH) _mthrough the compound of epoxypropane, epichlorokydrin, alkyl, alkoxy or hydroxypropyl acrylate upgrading.

R ⁴(OH) _mfor having the polyvalent alcohol that carbon number is 2 to 18, the polyol ethers formed by above-mentioned polyvalent alcohol, the ester class formed by above-mentioned polyvalent alcohol and acid reaction or silicone.

In addition, the many sulfhydryl compounds represented by formula (II) are as follows.

In formula (II), R ⁵represent singly-bound, carbon number be 1 alkyl or carbon number be the alkyl of the straight or branched of 2 to 22, R ⁵skeleton in more can comprise sulphur atom or form oxygen atom in ester group (also namely R5 is singly-bound, carbon number is the alkyl of 1, the alkyl of the carbon number of sulfur atom-containing or oxygen atom to be the alkyl of the straight or branched of 2 to 22 or the carbon number of non-sulfur atom-containing or oxygen atom the be straight or branched of 2 to 22); P represents the integer of 2 to 6, wherein works as R ⁵when representing singly-bound, p represents 2; Work as R ⁵when representing that carbon number is the alkyl of 1, p represents the integer of 2 to 4; Work as R ⁵when representing that carbon number is the alkyl of the straight or branched of 2 to 22, p represents the integer of 2 to 6.

Again, (methyl) that multibranched polymers of the present invention (D) is remaining after being preferably the many sulfhydryl compounds represented by formula (II) and multiple functional radical (methyl) acrylate reactions represented by formula (I) is acrylate-based, reacts further and the polymkeric substance formed with the sulfhydryl compound with carboxyl represented by formula (III).

The sulfhydryl compound with carboxyl represented by formula (III) is as follows.

In detail, the many sulfhydryl compounds represented by formula (II) are be added to via light reaction on the carbon-to-carbon double bond of multiple functional radical (methyl) acrylate represented by formula (I) with the sulfydryl contained by the sulfhydryl compound with carboxyl represented by formula (III).Generally speaking, in the carbon-to-carbon double bond of multiple functional radical (methyl) acrylate represented by formula (I), the carbon-to-carbon double bond carrying out light reaction is preferably 0.1% to 50% relative to all carbon-to-carbon double bonds.

Furthermore, the sulfydryl of the many sulfhydryl compounds represented by formula (II), or the many sulfhydryl compounds to be represented by formula (II) and the sulfydryl with the sulfhydryl compound of carboxyl represented by formula (III), 1/200 to 1/2 is can be relative to the addition molar ratio of the carbon-to-carbon double bond of multiple functional radical (methyl) acrylate represented by formula (I), be preferably 1/100 to 1/3, be more preferred from 1/50 to 1/5, then be more preferred from 1/20 to 1/8.

Multibranched polymers (D) is preferably has sufficient photopolymerization functional group, such as carbon-to-carbon double bond.Specifically, the molecular weight of the multibranched polymers (D) corresponding to carbon-to-carbon double bond of every 1 mole is preferably 100 to 100,000.The molecular weight of multibranched polymers (D) is preferably 1,000 to 50,000, is more preferred from 1,500 to 40,000, and special good is 2,000 to 30,000.

In addition, for manufacturing the photosensitive polymer combination of alkali-developable, multibranched polymers (D) is preferably has sufficient carboxyl.Specifically, the molecular weight of the multibranched polymers (D) corresponding to the carboxyl of every 1 mole is preferably 200 to 20,000, is more preferred from 250 to 6,000.

The acrylate-based number (n) contained by multiple functional radical (methyl) acrylate represented by formula (I) is preferably 2 to 20, is more preferred from 2 to 10, then is more preferred from 2 to 6.R in formula (I) ²when representing that carbon number is the alkyl of 1 to 4, R ²can be methyl, ethyl, propyl group or butyl, be preferably methyl.Again, R ⁴(OH) _mthe carbon number had is preferably 2 to 18, is more preferred from 2 to 14, and good is especially 4 to 12.

The concrete example of multiple functional radical (methyl) acrylate represented by formula (I) comprises ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tetramethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris (methyl) acrylate of ethane via epoxyethane upgrading, through trimethylolpropane tris (methyl) acrylate of epoxypropane upgrading, trimethylolethane trimethacrylate (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, through pentaerythrite three (methyl) acrylate of caprolactone upgrading, through pentaerythrite four (methyl) acrylate of caprolactone upgrading, through dipentaerythritol six (methyl) acrylate of caprolactone upgrading, through hexahydro-phthalic acid two (methyl) acrylate of epichlorokydrin upgrading, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate (hydroxypivalicacidneopentylglycoldi (meth) acrylate), neopentyl glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate of ethane via epoxyethane upgrading, through neopentyl glycol two (methyl) acrylate of epoxypropane upgrading, through 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate of caprolactone upgrading, through pentaerythrite two (methyl) acrylate of stearic acid upgrading, through phthalic acid two (methyl) acrylate of epichlorokydrin upgrading, poly-(ethylene glycol tetramethylene glycol) two (methyl) acrylate, poly-(propylene glycol tetramethylene glycol) two (methyl) acrylate, polyester (methyl) acrylate, polyglycol two (methyl) acrylate, polyglycol polypropylene glycol polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, through propylene glycol two (methyl) acrylate of epichlorokydrin upgrading, through bisphenol A diglycidyl ether two (methyl) acrylate of epoxypropane upgrading, silicone two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, through trimethylolpropane two (methyl) acrylate of neopentyl glycol upgrading, tripropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate of ethane via epoxyethane upgrading, triglycerin two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, through glycerine three (methyl) acrylate of epichlorokydrin upgrading, glycerine three (methyl) acrylate of ethane via epoxyethane upgrading, through glycerine three (methyl) acrylate of epoxypropane upgrading, tricresyl phosphate (methyl) acrylate of ethane via epoxyethane upgrading, through trimethylolpropane tris (methyl) acrylate of caprolactone upgrading, through trimethylolpropane tris (methyl) acrylate of hydroxypropyl acrylate (hydroxypropylacrylate is called for short HPA) upgrading, trimethylolpropane tris (methyl) acrylate of ethane via epoxyethane upgrading, through trimethylolpropane tris (methyl) acrylate of epoxypropane upgrading, trimethylolpropane benzoic ether (methyl) acrylate, three ((methyl) acryloyl ethyl) chlorinated isocyanurates, through trimethylolpropane tris (methyl) acrylate of alkoxy upgrading, dipentaerythritol gathers (methyl) acrylate, through dipentaerythritol three (methyl) acrylate of alkyl upgrading, (methyl) acrylate of two trimethylolpropane four (methyl) acrylate etc., or the combination of above-claimed cpd.

R in the many sulfhydryl compounds represented by formula (II) ⁵the carbon number had be preferably 0 to 22 (when carbon number is 0, R ⁴for singly-bound, and formula (II) represents HS-CH ₂-CH ₂-SH), be more preferred from 1 to 16, good is especially 2 to 12.The concrete example of the many sulfhydryl compounds represented by formula (II) comprises 1,2-dimercaptoethane, 1,3-dimercaptopropane, Isosorbide-5-Nitrae-dimercapto butane, two dimercaptoethane mercaptan (HS-CH ₂cH ₂-S-CH ₂cH ₂-SH), dimercapto triethylene glycol, trimethylolpropane tris (thioglycollate), trimethylolpropane tris (mercaptopropionic acid ester), pentaerythrite four (thioglycollate), pentaerythrite three (thioglycollate), pentaerythrite four (mercaptopropionic acid ester), dipentaerythritol six (thioglycollate), dipentaerythritol six (mercaptopropionic acid ester), or the combination of above-claimed cpd.

The R had in the sulfhydryl compound of carboxyl represented by formula (III) ⁶the carbon number had be 1 to 12 alkylidene can be the alkylidene of straight or branched.Specifically, this alkylidene is such as the bases such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, Ya Xinji, sub-nonyl, sub-decyl, sub-undecyl or sub-dodecyl.The sulfhydryl compound with carboxyl represented by formula (III) can be enumerated as mercaptoacetic acid (thioglycolicacid).

In the present invention, multiple functional radical (methyl) acrylate (monomer) represented by formula (I) can first mix with the many sulfhydryl compounds represented by formula (II) by above-mentioned addition reaction, at room temperature to 100 DEG C, and add base catalyst to carry out.Reaction time is generally 30 minutes to about 6 hours.So, multibranched polymers can be obtained.

Then, also can add the sulfhydryl compound with carboxyl represented by formula (III) in this multibranched polymers, then carry out an addition reaction.So, the multibranched polymers with carboxyl can be obtained.

In addition, the general analysis instrument of liquid chromatography (liquidchromatography), gel-filtration chromatography (gelfiltrationchromatography) etc. can be utilized to confirm the end of synthesis of multibranched polymers (D).

Again, when synthesizing multibranched polymers (D), as required, polymerization inhibitor can be added if desired.Polymerization inhibitor can use benzenediol (hydroquinone) compounds, the phenol compound that are generally used for suppressing the polymerization of (methyl) acrylate compounds, or its combination.The concrete example of polymerization inhibitor includes but not limited to p-dihydroxy-benzene, methoxyl p-dihydroxy-benzene, catechol, p-tert-butyl catechol, cresols, dibutyl hydroxy toluene, 2,4,6-tri--tert-butyl phenols (BHT), or the combination of above-claimed cpd.

Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of multibranched polymers (D) can be 3 weight portion to 35 weight portions, is preferably 4 weight portion to 30 weight portions, and is more preferred from 5 weight portion to 25 weight portions.

It should be noted that the adherence of photosensitive polymer combination and hardness are not good when photosensitive polymer combination is not containing multibranched polymers (D).Specifically, when photosensitive polymer combination comprises multibranched polymers (D), the sulfydryl of multibranched polymers (D) can increase the affinity between black matrix" and substrate (such as glass) that photosensitive polymer combination formed, and can solve the problem that the adherence of the black matrix" manufactured by photosensitive polymer combination is not good by this.In addition, multibranched polymers also has ethene unsaturated group, can increase the cross-linking density of hardening thing, can solve the problem that the hardness of black matrix" is not good by this.

Again, when multibranched polymers (D) has carboxyl, the Van der Waals force between black matrix" and substrate (such as glass) that photosensitive polymer combination formed can be increased, and this carboxyl can participate in photochemical reaction and increase the cross-linking density of hardening thing (black matrix"), can promote adherence and the hardness of the black matrix" manufactured by photosensitive polymer combination by this further.

Solvent (E)

Solvent (E) refers to and alkali soluble resin (A), the compound (B) with ethene unsaturated group, light initiator (C), multibranched polymers (D) and black pigment (F) can be dissolved, but the organic solvent do not reacted with mentioned component, and be preferably there is suitable evaporative.

Solvent (E) is such as the combination of (gathering) alkylene glycol mono alkane ethers, (gathering) alkylene glycol mono alkane ether acetic acid ester class, other ethers, ketone, lactic acid alkane ester class, other ester classes, aromatic hydrocarbons class, carboxylic acyloxy amine or above-mentioned solvent.

The concrete example of (gathering) alkylene glycol mono alkane ethers comprises ethylene glycol monomethyl ether, ethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol positive propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, tri ethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol positive propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, the combination of tripropylene glycol ether or above-mentioned solvent.

The concrete example of (gathering) alkylene glycol mono alkane ether acetic acid ester class comprises the combination of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or above-mentioned solvent.

The concrete example of other ethers comprises the combination of diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, tetrahydrofuran or above-mentioned solvent.

The concrete example of ketone comprises the combination of the first and second alkane ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone or above-mentioned solvent.

The concrete example of lactic acid alkane ester class comprises the combination of 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester or above-mentioned solvent.

The concrete example of other ester classes comprises 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate (Ethyl3-ethoxypropionate, be called for short EEP), ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, the combination of 2-oxygen base ethyl butyrate or above-mentioned solvent.

The concrete example of aromatic hydrocarbons class comprises the combination of toluene, dimethylbenzene or above-mentioned solvent.

The concrete example of carboxylic acyloxy amine comprises the combination of 1-METHYLPYRROLIDONE, DMF, DMA or above-mentioned solvent.

Solvent (E) is preferably the combination of propylene glycol monomethyl ether acetate, 3-ethoxyl ethyl propionate or above-mentioned solvent.Above-mentioned solvent (E) can be used alone or combines multiple use.

Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount of solvent (E) can be 1000 weight portion to 5000 weight portions, be preferably 1200 weight portion to 4500 weight portions, and be more preferred from 1400 weight portion to 4000 weight portions.

Black pigment (F)

Black pigment (F) is preferably the black pigment with thermotolerance, photostability and solvent resistance.

The concrete example of black pigment (F) comprising: the black organic pigment of perylene black (peryleneblack), cyanine black (cyanineblack) or nigrosine (anilineblack) etc.; In pigment by red, blue, green, purple, yellow, cyanine (cyanine) or fuchsin (magenta) etc., select two or more pigment to mix, make it be formed close to blackened colour mixture organic pigment; The lightproof material of carbon black (carbonblack), chromium oxide, iron oxide, titanium black (titaniumblack) or graphite etc., wherein the concrete example of above-mentioned carbon black comprises C.I. pigment black 1,7 (C.I.pigmentblack1,7), commercially available product (trade name MA100, MA230, MA8, #970, #1000, #2350 or #2650) manufactured by Mitsubishi Chemical.Above-mentioned black pigment (F) can be used alone or combines multiple use.

Black pigment (F) is preferably carbon black or C.I. pigment black 7, and carbon black is such as commercially available product MA100 manufactured by Mitsubishi Chemical or MA230.

Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of black pigment (F) can be 60 weight portion to 600 weight portions, is preferably 80 weight portion to 500 weight portions, and is more preferred from 100 weight portion to 400 weight portions.

Adjuvant (G)

Under the prerequisite not affecting effect of the present invention, photosensitive polymer combination of the present invention also alternative adds adjuvant (G) further.The concrete example of adjuvant (G) comprises surfactant, filling agent, polymkeric substance (referring to the polymkeric substance beyond above-mentioned alkali soluble resin (A)), adherence promoter, antioxidant, ultraviolet light absorber or anti-agglutinant.

Surfactant contributes to the coating improving photosensitive polymer combination.The concrete example of surfactant comprises the combination of kation system surfactant, negative ion system surfactant, nonionic system surfactant, amphoteric surfactant, polysiloxane series surfactant, fluorine prime system surfactant or above-mentioned surfactant.

Specifically, surface active agents polyethoxy lauryl ether, polyethoxy stearoyl ether, polyethoxy alkyl ether (polyoxyethylenealkylethers) such as polyethoxy oil ether etc. in this way; The polyethoxy alkyl benzene ethers such as polyethoxy octyl group phenylate, polyethoxy nonyl phenylate; The polyethylene glycol di such as polyethylene glycol dilaurate, polyglycol distearate class; Sorbitan fatty acid ester class; The polyesters of fatty acid upgrading; Or the polyurethane class of tertiary amine upgrading.Above-mentioned surfactant can be used alone or combines multiple use.

The concrete example of surfactant comprises the KP product manufactured by SHIN-ETSU HANTOTAI's chemical industry, by Daokangning Toray Co., Ltd (DowCorningTorayCo., Ltd.) the SF-8427 product manufactured, Puli's furlong (Polyflow) product manufactured by common prosperity society oil chemical industry, (TochemProductsCo. is manufactured by get Ke Mu incorporated company, Ltd.) Ai Fuduopu (F-Top) product, Mei Kafuke (Megafac) product manufactured by large Japanese ink chemical industry, Fu Luoduo (Fluorade) product manufactured by Sumitomo 3M, A Sakaduo (AsahiGuard) product manufactured by Asahi Glass or Sa Fulong (Surflon) product manufactured by Asahi Glass company.

The concrete example of filling agent comprises glass, aluminium etc.

The concrete example of polymkeric substance comprises the combination of polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether, poly-perfluoroalkyl acrylate alkane ester or above-mentioned polymkeric substance.

The concrete example of adherence promoter comprises vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, N-(2-amido ethyl)-3-aminocarbonyl propyl trimethoxy silane, 3-aminocarbonyl propyl triethoxysilane, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol hydroxypropyl methyl diethoxy silane, 3-epoxy prapanol hydroxypropyl methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methylpropionyloxy propyl trimethoxy silicane, 3-mercaptopropyl trimethoxysilane, the combination of 3-glycidoxypropyltrime,hoxysilane or above-claimed cpd.

The concrete example of antioxidant comprises the combination of 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-bis--tert-butyl phenols or above-claimed cpd.

The concrete example of ultraviolet light absorber comprises 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl and to change the combination of nitrogen, alkoxy benzophenone (alkoxyphenone) or above-claimed cpd.

The concrete example of anti-agglutinant comprises sodium polyacrylate (sodiumpolyacrylate) etc.

Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of adjuvant (G) is 0.1 weight portion to 10 weight portion, is preferably 0.5 weight portion to 8 weight portion, and is more preferred from 1 weight portion to 6 weight portion.

The preparation method > of < photosensitive polymer combination

Can be used to prepare the method for photosensitive polymer combination such as: alkali soluble resin (A), the compound (B) with ethene unsaturated group, light initiator (C), multibranched polymers (D), solvent (E) and black pigment (F) are positioned in stirrer and stir, it is made to be uniformly mixed into solution state, also adjuvant (G) can be added if desired, after giving Homogeneous phase mixing, just can obtain the photosensitive polymer combination of solution state.

Again, the preparation method of photosensitive polymer combination has no particular limits.The alkali soluble resin (A) of a part, the compound (B) with ethene unsaturated group are first scattered in the solvent (E) of a part, to form dispersion soln by the preparation method of photosensitive polymer combination; And then mix remaining alkali soluble resin (A), there is the compound (B) of ethene unsaturated group, light initiator (C), multibranched polymers (D), solvent (E) and black pigment (F) prepare.

Or photosensitive polymer combination also can by first the black pigment (F) of a part being scattered in the potpourri that is made up of the solvent (E) of part alkali soluble resin (A) and a part to after forming black pigment dispersion liquid; And add alkali soluble resin (A), there is the compound (B) of ethene unsaturated group, light initiator (C), multibranched polymers (D), solvent (E) and black pigment (F) prepare.Again, the dispersion steps of above-mentioned black pigment (F) is undertaken by the such as mixer such as ball mill (beadsmill) or roller mill (rollmill) mixing.

The manufacture method > of < black matrix"

The manufacture method of black matrix" comprises sequentially to be bestowed pre-baked, exposure, development and rear roasting process and obtains on substrate by Photosensitve resin composition.Black matrix" is in order to isolate each picture element layer.Again, when the thickness of black matrix" is 1 μm, optical density (OD) scope can be more than 3.0, is preferably 3.2 to 5.5, and is more preferred from 3.5 to 5.5.The manufacture method of black matrix" is below described in detail in detail.

First, by coating methods such as rotary coating (spincoating) or cast coat (castcoating), the photosensitive polymer combination of coating solution state equably on substrate, to form film.The concrete example of above-mentioned base material comprises: for alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass and the person that adheres to nesa coating on this glass of liquid crystal indicator etc.; Or for the photo-electric conversion device substrate (as: silicon substrate) etc. of solid-state image sensor etc.

After forming film, remove most of solvent with drying under reduced pressure, then the solvent of remnants is removed completely, to form pre-baked film in pre-baked (pre-bake) mode.It should be noted that drying under reduced pressure and pre-baked condition, according to the kind of each composition, ratio and changing.Generally speaking, drying under reduced pressure is under the pressure being less than 200mmHg, carry out 1 second to 20 seconds, and pre-baked be the heating at 70 DEG C to 110 DEG C temperature, film carried out 1 minute to 15 minutes.

Then, with the light shield with specific pattern, above-mentioned pre-baked film is exposed.The light used in exposure process is such as g line, the ultraviolet of h line or i line etc. is good, and ultraviolet lamp can be (surpassing) high-pressure mercury-vapor lamp or metal halid lamp.

Then, at the temperature of 23 ± 2 DEG C, the above-mentioned pre-baked film through exposure be impregnated in developer solution (developingsolution), to remove the pre-baked film of the above-mentioned part without exposure, specific pattern can be formed on substrate by this.

Developer solution is such as the alkali compounds etc. of NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylphosphonihydroxide hydroxide amine, tetraethylamine hydroxide, choline, pyrroles, piperidines or 1,8-diazabicyclo [5.4.0]-7-hendecene etc.The concentration of developer solution is generally 0.001 % by weight to 10 % by weight, is preferably 0.005 % by weight to 5 % by weight, and is more preferred from 0.01 % by weight to 1 % by weight.

At pre-baked film after development, the substrate with specific pattern is cleaned with water, then with pressurized air or compressed nitrogen by air-dry for above-mentioned specific pattern.Then, rear roasting process is carried out with the heating arrangement such as hot plate or baking oven.Rear roasting temperature is generally 150 to 250 DEG C, wherein uses the heat time of hot plate to be 5 minutes to 60 minutes, and uses the heat time of baking oven to be 15 minutes to 150 minutes.After above-mentioned treatment step, black matrix" can be formed on substrate.

The manufacture method > of < picture element layer and colored filter

The manufacture method of picture element layer and the manufacture method of black matrix" similar.Specifically, formed on the substrate of black matrix" above colored filter photosensitive composite is coated on, then sequentially bestowed pre-baked, exposure, development and rear roasting process and obtaining.Only, in the condition of drying under reduced pressure, drying under reduced pressure is under the pressure of 0mmHg to 200mmHg, carry out 1 second to 60 seconds.After above-mentioned treatment step, can specific pattern be fixed, form picture element layer by this.Further, repeat above-mentioned steps, sequentially on substrate, form the picture element layers such as red, green, blue, above can obtaining, define the substrate (namely there is the colored filter of picture element layer) of black matrix" and picture element layer.

The manufacture method > of < liquid crystal indicator

First, the colored filter manufacture method by above-mentioned colored filter formed and be provided with thin film transistor (TFT) (thinfilmtransistor; Be called for short TFT) substrate do subtend configuration, and gap (structure cell interval, cellgap) is set between these.Then, with sticker laminating colored filter and aforesaid substrate peripheral part and leave filling orifice.Then, in the gap that substrate surface and sticker are separated out, inject liquid crystal by filling orifice, finally seal filling orifice to form liquid crystal layer.Subsequently, Polarizer is provided to make liquid crystal indicator by the opposite side of Fluid Contacting crystal layer in the opposite side of Fluid Contacting crystal layer in colored filter and substrate.Above-mentioned used liquid crystal, also i.e. liquid-crystal compounds or liquid-crystal composition, herein and be not particularly limited.Only, any one liquid-crystal compounds and liquid-crystal composition can be used.

In addition, in making in colored filter the liquid crystal orienting film used and be used to limit the orientation of liquid crystal molecule, and have no particular limits, such as inorganics or organism any one, and the present invention is not limited to this.

The preparation example of the diol compound (a-1) containing polymerism unsaturated group

Preparation example 1 to the preparation example 6 of the diol compound (a-1) containing polymerism unsaturated group is below described:

Preparation example 1

First, by fluorenes epoxy compound (model ESF-300, Nippon Steel's chemistry manufacture of 100 weight portions; Epoxide equivalent 231), the propylene glycol monomethyl ether acetate of the acrylic acid of 30 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 130 weight portions is added in the four neck flasks of 500 milliliters with continous way addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C to 110 DEG C, reacts after 15 hours, can obtain the pale yellow transparent mixed liquor that solid constituent concentration is 50 % by weight.Then, make above-mentioned pale yellow transparent mixed liquor stand to extract, filter and the step of heating, drying, solid component content is the diol compound (a-1-1) containing polymerism unsaturated group of the preparation example 1 of 99.9 % by weight.

Preparation example 2

First, by fluorenes epoxy compound (model PG-100, the manufacture of Osaka gas of 100 weight portions; Epoxide equivalent 259), the propylene glycol monomethyl ether acetate of the methacrylic acid of 35 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 135 weight portions is added in the four neck flasks of 500 milliliters with continuous addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C at 110 DEG C, reacts after 15 hours, can obtain the pale yellow transparent mixed liquor that solid component content is 50 % by weight.Make above-mentioned pale yellow transparent mixed liquor stand to extract, filter and the step of heating, drying, solid component content is the diol compound (a-1-2) containing polymerism unsaturated group of the preparation example 2 of 99.9 % by weight.

Preparation example 3

By fluorenes epoxy compound (model ESF-300, Nippon Steel's chemistry manufacture of 100 weight portions; Epoxide equivalent 231), the propylene glycol monomethyl ether acetate of the 2-methacryloyloxyethyl succinate of 100 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 200 weight portions is added in the four neck flasks of 500 milliliters with continuous addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C at 110 DEG C, reacts after 15 hours, can obtain the pale yellow transparent mixed liquor that solid component content is 50 % by weight.Make above-mentioned pale yellow transparent mixed liquor stand to extract, filter and the step of heating, drying, the diol compound (a-1-3) containing polymerism unsaturated group that solid component content is the preparation example 3 of 99.9 % by weight can be obtained.

Preparation example 4

First, there is mechanical raking at device, in 1000 milliliters of there-necked flasks that temperature takes into account reflux condensing tube, add two (4-hydroxy phenyl) sulfone, chloro-1, the 2-epoxypropane of 3-of 9 moles and the tetramethyl-ammonium chlorides of 0.003 mole of 0.3 mole.Then, stir and be heated to 105 DEG C, and react 9 hours at 105 DEG C.Then, decompression distillation goes out chloro-1, the 2-epoxypropane of unreacted 3-.Afterwards, reactive system is down to room temperature, and adds 9 moles of benzene and 0.5 molar sodium hydroxide (30 % by weight aqueous solution of formation soluble in water) when stirring.Then, be warming up to 60 DEG C and maintain 3 hours.Then, repeatedly with water washing reaction solution, till without chlorion (checking with silver nitrate).With decompression distillation removing solvent benzol, then at 75 DEG C dry 24 hours, to obtain the epoxy compound of two (4-hydroxy phenyl) sulfone.

The propylene glycol monomethyl ether acetate of the acrylic acid of the epoxy compound (epoxide equivalent 181) of two (4-hydroxy phenyl) sulfones of 100 weight portions, 30 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 130 weight portions is added in the four neck flasks of 500 milliliters with continuous addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C to 110 DEG C, reacts after 15 hours, can obtain the pale yellow transparent mixed liquor that solid component content is 50 % by weight.Make above-mentioned pale yellow transparent mixed liquor stand to extract, filter and the step of heating, drying, solid component content is the diol compound (a-1-4) containing polymerism unsaturated group of the preparation example 4 of 99.9 % by weight.

Preparation example 5

Two (4-hydroxy phenyl) HFC-236fa, chloro-1, the 2-epoxypropane of 3-of 9 moles and the tetramethyl-ammonium chlorides of 0.003 mole that add 0.3 mole are had in 1000 of mechanical raking, thermometer and reflux condensing tube milliliters of there-necked flasks at device.Then, stir and be heated to 105 DEG C, and react 9 hours at 105 DEG C.Then, decompression distillation goes out chloro-1, the 2-epoxypropane of unreacted 3-.Afterwards, reactive system is down to room temperature, and adds 9 moles of benzene and 0.5 molar sodium hydroxide (30 % by weight aqueous solution of formation soluble in water) when stirring.Then, be warming up to 60 DEG C and maintain 3 hours.Then, repeatedly with water washing reaction solution, till without chlorion (checking with silver nitrate).With decompression distillation removing solvent benzol, then at 75 DEG C dry 24 hours, to obtain the epoxy compound of two (4-hydroxy phenyl) HFC-236fa.

The propylene glycol monomethyl ether acetate of the methacrylic acid of the epoxy compound (epoxide equivalent 224) of two (4-hydroxy phenyl) HFC-236fa of 100 weight portions, 35 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 135 weight portions is added in the four neck flasks of 500 milliliters with continuous addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C to 110 DEG C, reacts after 15 hours, can obtain the pale yellow transparent mixed liquor that solid component content is 50 % by weight.Make above-mentioned pale yellow transparent mixed liquor stand to extract, filter and the step of heating, drying, solid component content is the diol compound (a-1-5) containing polymerism unsaturated group of the preparation example 5 of 99.9 % by weight.

Preparation example 6

Two (4-hydroxy phenyl) dimethylsilane, chloro-1, the 2-epoxypropane of 3-of 9 moles and the tetramethyl-ammonium chlorides of 0.003 mole that add 0.3 mole are had in 1000 of mechanical raking, thermometer and reflux condensing tube milliliters of there-necked flasks at device.Then, stir and be heated to 105 DEG C, and react 9 hours at 105 DEG C.Then, decompression distillation goes out chloro-1, the 2-epoxypropane of unreacted 3-.Afterwards, reactive system is down to room temperature, and adds 9 moles of benzene and 0.5 molar sodium hydroxide (30 % by weight aqueous solution of formation soluble in water) when stirring.Then, be warming up to 60 DEG C and maintain 3 hours.Then, repeatedly with water washing reaction solution, till without chlorion (checking with silver nitrate).With decompression distillation removing solvent benzol, then at 75 DEG C dry 24 hours, to obtain the epoxy compound of two (4-hydroxy phenyl) dimethylsilane.

The propylene glycol monomethyl ether acetate of the 2-methacryloyloxyethyl succinate of the epoxy compound (epoxide equivalent 278) of two (4-hydroxy phenyl) dimethylsilane of 100 weight portions, 100 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 200 weight portions is added in the four neck flasks of 500 milliliters with continuous addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C at 110 DEG C, reacts 15 hours, can obtain the pale yellow transparent mixed liquor that solid component content is 50 % by weight.Make above-mentioned pale yellow transparent mixed liquor stand to extract, filter and the step of heating, drying, solid component content is the diol compound (a-1-6) containing polymerism unsaturated group of the preparation example 6 of 99.9 % by weight.

The synthesis example of the first alkali soluble resin (A-1)

Below illustrate that the synthesis example A-1-1 of the first alkali soluble resin (A-1) is to synthesis example A-1-10:

Synthesis example A-1-1

First, by the diol compound (a-1-1) containing polymerism unsaturated group of 1.0 moles, 0.1 mole 4, 4'-hexafluoroisopropyli,ene two O-phthalic acid dianhydride (a-2-1-a), the pyromellitic acid anhydride (a-2-2-c) of 0.2 mole, the maleic acid (a-3-2-a) of 0.4 mole, the tetrabydrophthalic anhydride (a-3-2-b) of 1.0 moles, the benzyltriethylammonium chloride of 1.9 grams, 0.6 gram 2, the propylene glycol monomethyl ether acetate of 6-BHT and 750 grams with while addition manner be added in the four neck flasks of 500 milliliters, with forming reactions solution.At this, " add " is referred in the same reaction time and adds tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3) simultaneously.Then, above-mentioned reaction solution is heated to 110 DEG C, and reacts 2 hours, acid value be 129 milligrams KOH/ gram and number average molecular weight be 2368 the first alkali soluble resin A-1-1.

Synthesis example A-1-2

By the diol compound (a-1-2) containing polymerism unsaturated group of 1.0 moles, the benzyltriethylammonium chloride of 2.0 grams, 0.7 gram 2, the 1-Methoxy-2-propyl acetate of 6-BHT and 700 grams is added in the four neck flasks of 500 milliliters, with forming reactions solution.Then, add the Isosorbide-5-Nitrae-difluoro pyromellitic acid anhydride (a-2-1-b) of 0.2 mole, the benzophenone tetracarboxylic dianhydride (a-2-2-b) of 0.2 mole, and react 2 hours at 90 DEG C.Then, add the tetrabydrophthalic anhydride (a-3-2-b) of 1.2 moles, and react 4 hours at 90 DEG C.At this, " segmentation interpolation " is referred in the different reaction time and adds tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3) respectively, that is first add tetrabasic carboxylic acid or its acid dianhydride (a-2), add dicarboxylic acid or its acid anhydrides (a-3) afterwards again.Through above-mentioned synthesis step, can obtain acid value be 125 milligrams KOH/ gram and number average molecular weight be 3388 the first alkali soluble resin A-1-2.

Synthesis example A-1-3, synthesis example A-1-5, synthesis example A-1-7 and synthesis example A-1-9

First alkali soluble resin of synthesis example A-1-3, synthesis example A-1-5, synthesis example A-1-7 and synthesis example A-1-9 prepares with the step identical with synthesis example A-1-1, and its difference be in: change the composition kind of the first alkali soluble resin and use amount, reaction time, temperature of reaction and reactant add the time (as shown in table 1).

Synthesis example A-1-4, synthesis example A-1-6, synthesis example A-1-8 and synthesis example A-1-10

First alkali soluble resin of synthesis example A-1-4, synthesis example A-1-6, synthesis example A-1-8 and synthesis example A-1-10 prepares with the step identical with synthesis example A-1-2, and its difference be in: change the composition kind of the first alkali soluble resin and use amount, reaction time, temperature of reaction and reactant add the time (as shown in table 1).

The compound corresponding to abbreviation in table 1 and table 2 is as follows.

Table 1

Table 1 (Continued)

The synthesis example of the second alkali soluble resin (A-2)

Below illustrate that the synthesis example A-2-1 of the second alkali soluble resin (A-2) is to synthesis example A-2-3:

Synthesis example A-2-1

By the diol compound (a-1-1) containing polymerism unsaturated group of 1.0 moles, the benzyltriethylammonium chloride of 1.9 grams and 0.6 gram 2,6-BHT is dissolved in the 1-Methoxy-2-propyl acetate of 700 grams, and adds the biphenyltetracarboxyacid acid (a-2-2-a) of 0.3 mole and the maleic acid (a-3-2-a) of 1.4 moles simultaneously.Then, be heated to 110 DEG C and react 2 hours, acid value be 125 milligrams KOH/ gram and number average molecular weight be 2455 the second alkali soluble resin A-2-1.

Synthesis example A-2-2

Second alkali soluble resin of synthesis example A-2-2 prepares with the step identical with synthesis example A-2-1, and its difference be in: change the composition kind of the second alkali soluble resin and use amount, reaction time, temperature of reaction and reactant add the time (as shown in table 2).It should be noted that, at this, " add " is referred in the same reaction time and adds tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3) simultaneously, and " segmentation interpolation " is referred in the different reaction time and adds tetrabasic carboxylic acid or its acid dianhydride (a-2) and dicarboxylic acid or its acid anhydrides (a-3) respectively, also namely first add tetrabasic carboxylic acid or its acid dianhydride (a-2), add dicarboxylic acid or its acid anhydrides (a-3) afterwards again.

Table 2

The synthesis example of other alkali soluble resin (A-3)

Below illustrate that the synthesis example A-3-1 of other alkali soluble resin (A-3) is to synthesis example A-3-3:

Synthesis example A-3-1

Be that the four neck flasks of 1000 milliliters arrange nitrogen inlet, stirrer, well heater, condenser pipe and thermometer at volume, after importing nitrogen, add the diethylene glycol dimethyl ether (Diglyme) of the 2-hydroxyethyl methacrylate (HEMA) of 30 weight portions, the benzyl methacrylate (BzMA) of 10 weight portions, the CF9BuMA of 60 weight portions, 2,2'-azos two (2-methylbutyronitrile) (AMBN) of 3 weight portions and 300 weight portions.Then, slowly stir said mixture and make solution warms to 80 DEG C.Then, polycondensation 6 hours at 80 DEG C.Then, after solvent devolatilization (evaporate), other alkali soluble resins A-3-1 can be obtained.

Synthesis example A-3-2 is to synthesis example A-3-3

Other alkali soluble resins of synthesis example A-3-2 to synthesis example A-3-3 prepare with the step identical with synthesis example synthesis example A-3-1, and its difference be in: change the composition kind of other alkali soluble resins and use amount, reaction time, temperature of reaction and reactant add the time (as shown in table 3), be wherein called for short corresponding compound in table 3 as follows.

Table 3

The synthesis example of multibranched polymers (D)

Below illustrate that the synthesis example D-1 of multibranched polymers (D) is to synthesis example D-3:

Synthesis example D-1

Be in the four neck flasks of 1L at capacity, add the trimethylolpropane tris (thioglycollate) (sulfydryl 0.28 mole) of 25 grams, the tetramethylol methane tetraacrylate (carbon-to-carbon double bond 2.01 moles) of 177 grams, the p-dihydroxy-benzene of 0.1 gram and 0.01 gram benzyl dimethyl amine (as light initiator, benzyldimethylamine), react 12 hours and at 60 DEG C.To each resultant of reaction, confirm that sulfydryl disappears by iodimetry, multibranched polymers D-1 can be obtained.Multibranched polymers D-1 is 4,400 through the molecular weight measured by gel-filtration chromatography.

Synthesis example D-2

Be in the four neck flasks of 1L at capacity, add the pentaerythrite four (thioglycollate) (sulfydryl 0.19 mole) of 20 grams, the dipentaerythritol acrylate of 212 grams and the potpourri (carbon-to-carbon double bond 2.12 moles) of Dipentaerythritol Pentaacrylate, the p-dihydroxy-benzene of 0.1 gram and the benzyl dimethyl amine of 0.01 gram, and react 12 hours at 60 DEG C.To each resultant of reaction, confirm that sulfydryl disappears by iodimetry, multibranched polymers D-2 can be obtained.Multibranched polymers D-2 is 11,000 through the molecular weight measured by gel-filtration chromatography.

Synthesis example D-3

Be in the four neck flasks of 1L at capacity, add pentaerythrite four (thioglycollate) 20 grams (sulfydryl 0.19 mole), the dipentaerythritol acrylate of 212 grams and the potpourri (carbon-to-carbon double bond 2.12 moles) of Dipentaerythritol Pentaacrylate, the propylene glycol monomethyl ether acetate (as solvent) of 58 grams, the p-dihydroxy-benzene of 0.1 gram and the benzyl dimethyl amine of 0.01 gram, and react 12 hours at 60 DEG C.To each resultant of reaction, confirm that sulfydryl disappears by iodimetry, can intermediate product be obtained.Be 11,000 by this intermediate product through the molecular weight measured by gel-filtration chromatography.

Then, in four neck flasks, add 20 grams of (0.22 mole) mercaptoacetic acid, and react 12 hours at 60 DEG C.To each resultant of reaction, confirm that sulfydryl disappears by iodimetry, multibranched polymers D-3 can be obtained.Multibranched polymers D-3 is 12,000 through the molecular weight measured by gel-filtration chromatography.

The embodiment of photoresist

Embodiment 1 to embodiment 10 and comparative example 1 to the comparative example 6 of photoresist are below described:

Embodiment 1

A. photosensitive polymer combination

By the first alkali soluble resin A-1-1 of 100 weight portions, the pentaerythritol triacrylate of 15 weight portions and the carboxylate (referred to as B-1-1) of phthalic acid, 1-[9-ethyl-6-(2-methyl benzoyl)-9 hydrogen-carbazole-3-substituting group]-1-(oxygen-acetyl oxime) (referred to as C-1) of 5 weight portions, the multibranched polymers D-1 (referred to as D-1) of 5 weight portions and the C.I.PigmentBK7 (referred to as F-1) of 60 weight portions adds in the propylene glycol monomethyl ether acetate (referred to as E-1) of 1000 weight portions, and after stirring with swing-out stirrer (shakingtypestirrer), the photosensitive polymer combination of embodiment 1 can be obtained.

B. film forming

The photosensitive polymer combination of embodiment 1 is coated on plain glass substrate (being of a size of 100mm × 100mm × 0.7mm) in rotary coating mode, to form the film that thickness is about 6 μm.Then, by film at 90 DEG C pre-baked 2 to 3 minutes.Then, light shield is inserted between exposure machine and film, and with the ultraviolet of 100mJ/cm2, patterned exposure (exposure machine model, for AG500-4N, is manufactured by M & R nanosecond science and technology (M & RNanotechnology)) is carried out to pre-baked film.Film through exposure be impregnated in the potassium hydroxide aqueous solution 45 to 90 seconds of 0.05%, to remove the unwanted part of the above-mentioned film through exposure.Then, plain glass baseplate is cleaned with water.Finally, bake 30 minutes after film is carried out with baking oven at 235 DEG C, above can obtaining, form the glass substrate of the film of embodiment 1.Evaluated with aftermentioned each evaluation method by the film of embodiment 1, its result is as shown in table 4.

Embodiment 2 to embodiment 10

The photosensitive polymer combination of embodiment 2 to embodiment 10 and film prepare with the step identical with embodiment 1, and its difference be in: change the composition kind of photosensitive polymer combination and use amount (as shown in table 4) thereof, be wherein called for short corresponding compound in table 4 as follows.Evaluated with following each evaluation method by obtained film, its result is as shown in table 4.

Compound in table 4 and table 5 corresponding to label is as follows.

Comparative example 1 to comparative example 6

The photosensitive polymer combination of comparative example 1 to comparative example 6 and film prepare with the step identical with embodiment 1, and its difference be in: change the composition kind of photosensitive polymer combination and use amount (as shown in table 5) thereof.Evaluated with following each evaluation method by obtained film, its result is as shown in table 5.

< evaluation method >

A. adherence

Adherence measures according to the netted lattice (cross-hatched) of the 8.5.2 in the 8.5 adherence test method(s)s of JISK-5400-1990 to evaluate.Film above-described embodiment and comparative example obtained is slit into 100 netted lattice with pocket knife.Then, tear after sticking with adhesive tape, observe the situation that netted lattice are residual.The netted lattice quantity come off is fewer, represents that the adherence between film and substrate is better.According under show that assessment level evaluates adherence.

◎: 0%≤netted lattice Shuo Liang≤3% that comes off

Netted lattice Shuo Liang≤5% that zero: 3% < comes off

Netted lattice Shuo Liang≤35% that △: 5% < comes off

Netted lattice Shuo Liang≤100% that ╳: 35% < comes off

B. hardness

By the film that above-described embodiment and comparative example obtain, according to the 8.4.1 pencil test (pencilscratchtest) of JISK-5400-1990, evaluate its pencil hardness.According under show that assessment level carrys out the hardness of evaluated for film.

◎: 3H≤pencil hardness

Zero: 1H≤pencil hardness < 3H

△: HB≤pencil hardness < 1H

╳: pencil hardness < HB

Table 4

Table 5

< evaluation result >

Learnt by table 4 and table 5, compared with the film (embodiment 1 to embodiment 10) formed with the photosensitive polymer combination containing the first alkali soluble resin (A-1) (alkali soluble resin of aromatic structure containing having fluorine), the adherence of the film (comparative example 3 and comparative example 4) that the film (comparative example 1, comparative example 2 and comparative example 6) that the photosensitive polymer combination only containing the second alkali soluble resin (A-2) is formed, photosensitive polymer combination only containing other alkali soluble resins (A-3) are formed is not good.

In addition, compared with the film (embodiment 1 to embodiment 10) formed with the photosensitive polymer combination containing multibranched polymers (D), the hardness of the film (comparative example 5 and comparative example 6) that the photosensitive polymer combination not containing multibranched polymers (D) is formed is not good.

Again, when in multibranched polymers (D) containing carboxyl time (embodiment 6 and embodiment 8), the adherence of the film that photosensitive polymer combination is formed and hardness better.

In addition, when the molal quantity containing the molal quantity of diol compound (a-1) of polymerism unsaturated group, the tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) in the first alkali soluble resin (A-1) and when meeting relational expression [(a-2-1)+(a-3-1)]/(a-1)=0.4 ~ 1.6 containing the dicarboxylic acid of fluorine atom or the molal quantity of its acid anhydrides (a-3-1) (also embodiment 4, embodiment 5, embodiment 6, embodiment 9 and embodiment 10), the adherence of the film that photosensitive polymer combination is formed is better.

Again, when the compound (B) with ethene unsaturated group is containing when having compound (B-1) of acidic groups and at least three ethene unsaturated groups (embodiment 1, embodiment 2, embodiment 6 and embodiment 9), the adherence of the film that photosensitive polymer combination is formed and hardness better.

In sum, photosensitive polymer combination of the present invention is due to the alkali soluble resin containing the aromatic structure and ad hoc structure with fluorine and multibranched polymers (D), effectively can improve lateral erosion problem, increase affinity between black matrix" and substrate and the cross-linking density simultaneously increased in black matrix", therefore have the feature that adherence is good and hardness is good concurrently, be thus applicable to the black matrix" making colored filter.

Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims

1. a black matrix" photosensitive polymer combination, is characterized in that, comprising:

Alkali soluble resin (A);

There is the compound (B) of ethene unsaturated group;

Light initiator (C);

Multibranched polymers (D);

Solvent (E); And

Black pigment (F),

Wherein said alkali soluble resin (A) comprises the first alkali soluble resin (A-1) represented by formula (1),

In formula (1), A represents phenylene or has substituent phenylene, wherein said substituting group to be carbon number be 1 to 5 alkyl, halogen atom or phenyl; B represents-CO-,-SO ₂-,-C (CF ₃) ₂-,-Si (CH ₃) ₂-,-CH ₂-,-C (CH ₃) ₂-,-O-, 9,9-fluorenylidenes or singly-bound; L ¹represent the tetravalence carboxylic acid residues containing fluorine atom or the tetravalence carboxylic acid residues not containing fluorine atom; Y ¹represent the dibasic carboxylic acid residue containing fluorine atom or the dibasic carboxylic acid residue not containing fluorine atom; R ¹represent hydrogen atom or methyl; A represents the integer of 1 to 20; L ¹and Y ¹in, at least one contains fluorine atom;

Described multibranched polymers (D) is the many sulfhydryl compounds represented by formula (II) and multiple functional radical (methyl) acrylate reactions represented by formula (I) and is formed,

The compound of described hydroxyl is R ⁴(OH) _mor described R ⁴(OH) _mthrough the compound of epoxypropane, epichlorokydrin, alkyl, alkoxy or hydroxypropyl acrylate upgrading,

R ⁴(OH) _mfor having the polyvalent alcohol that carbon number is 2 to 18, the polyol ethers formed by described polyvalent alcohol, the ester class formed by described polyvalent alcohol and acid reaction or silicone,

2. black matrix" photosensitive polymer combination according to claim 1, wherein, in described multibranched polymers (D), the sulfydryl of the described many sulfhydryl compounds represented by formula (II) is 1/200 to 1/2 relative to the addition molar ratio of the carbon-to-carbon double bond of described multiple functional radical (methyl) acrylate represented by formula (I).

3. black matrix" photosensitive polymer combination according to claim 1, wherein said multibranched polymers (D) is for by after described many sulfhydryl compounds of being represented by formula (II) and described multiple functional radical (methyl) acrylate reactions represented by formula (I) and remaining (methyl) is acrylate-based, react with the sulfhydryl compound with carboxyl represented by formula (III) further and formed

4. black matrix" photosensitive polymer combination according to claim 3, wherein, in described multibranched polymers (D), described many sulfhydryl compounds of being represented by formula (II) and the described sulfydryl with the sulfhydryl compound of carboxyl represented by formula (III) are 1/200 to 1/2 relative to the addition molar ratio of the carbon-to-carbon double bond of described multiple functional radical (methyl) acrylate represented by formula (I).

5. black matrix" photosensitive polymer combination according to claim 1, wherein said the first alkali soluble resin (A-1) represented by formula (1) is reacted by the first potpourri and obtains, and described first potpourri comprises:

Diol compound (a-1) containing polymerism unsaturated group;

Tetrabasic carboxylic acid or its acid dianhydride (a-2); And

Dicarboxylic acid or its acid anhydrides (a-3),

Described tetrabasic carboxylic acid or its acid dianhydride (a-2) comprise tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1), other tetrabasic carboxylic acids except described tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) or its acid dianhydride (a-2-2) or the two combination;

Described dicarboxylic acid or its acid anhydrides (a-3) comprise dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1), other dicarboxylic acid except described dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) or its acid anhydrides (a-3-2) or the two combination;

In described tetrabasic carboxylic acid or its acid dianhydride (a-2) and described dicarboxylic acid or acid anhydrides (a-3), at least one contains fluorine atom.

6. black matrix" photosensitive polymer combination according to claim 5, the tetracarboxylic compound containing fluorine atom that wherein said tetrabasic carboxylic acid containing fluorine atom or its acid dianhydride (a-2-1) select free style (2-1) to represent and the group that the tetracarboxylic dianhydride's compound containing fluorine atom represented by formula (2-2) forms

In formula (2-1) and formula (2-2), L ²one of them in the group selecting free style (L-1) to formula (L-6) to represent;

7. black matrix" photosensitive polymer combination according to claim 5, the dicarboxylic acid compound containing fluorine atom that wherein said dicarboxylic acid containing fluorine atom or its acid anhydrides (a-3-1) select free style (3-1) to represent and the group that the dicarboxylic anhydride compound containing fluorine atom represented by formula (3-2) forms

8. black matrix" photosensitive polymer combination according to claim 5, the molal quantity of the wherein said diol compound (a-1) containing polymerism unsaturated group, described containing the tetrabasic carboxylic acid of fluorine atom or the molal quantity of its acid dianhydride (a-2-1) and describedly meet relational expression [(a-2-1)+(a-3-1)]/(a-1)=0.4 ~ 1.6 containing the dicarboxylic acid of fluorine atom or the molal quantity of its acid anhydrides (a-3-1).

9. black matrix" photosensitive polymer combination according to claim 1, use amount wherein based on described alkali soluble resin (A) is 100 weight portions, the use amount of described first alkali soluble resin (A-1) is 10 weight portion to 100 weight portions, the described use amount with the compound (B) of ethene unsaturated group is 15 weight portion to 200 weight portions, the use amount of described smooth initiator (C) is 5 weight portion to 55 weight portions, the use amount of described multibranched polymers (D) is 3 weight portion to 35 weight portions, the use amount of described solvent (E) is 1000 weight portion to 5000 weight portions, and the use amount of described black pigment (F) is 60 weight portion to 600 weight portions.

10. black matrix" photosensitive polymer combination according to claim 1, the wherein said compound (B) with ethene unsaturated group comprises the compound (B-1) with acidic groups and at least three ethene unsaturated groups.

11. black matrix" photosensitive polymer combinations according to claim 10, use amount wherein based on described alkali soluble resin (A) is 100 weight portions, described in there is the compound (B-1) of acidic groups and at least three ethene unsaturated groups use amount be 15 weight portion to 150 weight portions.

The manufacture method of 12. 1 kinds of colored filters, is characterized in that, comprises and using by the black matrix" photosensitive polymer combination such as according to any one of claim 1 to 11 to form black matrix".

13. 1 kinds of black matrix"s, is characterized in that, are to be formed by the black matrix" photosensitive polymer combination as described in any one of claim 1 to 11.

14. 1 kinds of colored filters, is characterized in that, comprise black matrix" as claimed in claim 13.

15. 1 kinds of liquid crystal indicators, is characterized in that, comprise colored filter as claimed in claim 14.