CN1906536A - Photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Abstract

A photosensitive resin composition comprising an alkali-soluble unsaturated resin as an organic binder produced by reacting an epoxy compound (a) having two or more epoxy groups in its molecule with an unsaturated group-containing carboxylic acid (b) and further reacting the reaction product with an isocyanate group-containing compound (c). A photosensitive resin composition comprising an alkali-soluble unsaturated resin produced by reacting a phenolic hydroxyl group-containing compound (f) having two or more phenolic hydroxyl groups in its molecule with an unsaturated group-containing epoxy compound (g) and further reacting the reaction product with an isocyanate group-containing compound (c).

Description

Photosensitive polymer combination, color filter and LCD

Technical field

The present invention relates to a kind of photosensitive polymer combination, be used for for example color filter of liquid crystal board such as LCD, this photosensitive polymer combination is suitable for pattern formation, black matrix" (blackmatrix), overlayer (overcoat), rib wall (rib) and sept (spacer).The invention still further relates to color filter and the LCD of using described photosensitive polymer combination.

Background technology

Usually, at the color filter that is used for liquid crystal boards such as LCD for example, use the photosensitive polymer combination (resist) that contains resin, photopolymerization monomer and light trigger to carry out the formation of colour element, black matrix", overlayer, rib wall and sept.Consider from development capability, pattern precision and adhering angle, proposed many compositions that are used for the resist of color filter.For example, for processing time and the raising yield rate that shortens forming process, disclose and used the resin that contains unsaturated group as the technology that is included in the resin in the above-mentioned resin combination (spy opens 2001-174621 communique, No. the 2878486th, special permission and spy and opens flat 10-168033 communique).The described process for preparing resins that contains unsaturated group is as follows: make epoxy resin and the carboxylic acid or its anhydride reaction that contain unsaturated group, make reaction product again with polybasic carboxylic acid or its anhydride reaction.

Many resin combinations also are disclosed in the paint field.For example United States Patent (USP) discloses a kind of composition that uses following resin No. 5109097, and described resin contains the reaction product of following reaction: have the reaction of the compound of side group and bivalent reaction group and compound that per molecule has two isocyanate groups.But, because resist needs processing such as for example development and have accurate machining precision in this processing, and the purpose difference between coating resin composition and the resist, and those skilled in the art can not predict applicability and the effect of resin combination as resist, so this based resin composition can not be used for the resist that color filter is used usually.

But, the above-mentioned conventional resist that is generally used for liquid crystal board is crosslinked by ester bond, described ester bond forms by following structural unit and polybasic carboxylic acid or its anhydride reaction, and described structural unit comprises epoxy resin and the reaction product that contains carboxylic acid or its acid anhydrides of unsaturated group.If ester moiety splits when storing, then resist has different molecular weight because of crosslinked the splitting of ester, and has significantly different resin properties such as for example viscosity and developing rate etc., thereby the resist performance is significantly different.This generally causes trouble in coating process and/or pattern forming process.

The photosensitive polymer combination (for example above-mentioned photosensitive color resin combination) that contains optical polymerism component, light trigger and adhesive resin generally comprises the photoetching process of coating (coating), drying, exposure and developing process.In these processes, resin combination must always satisfy:

Do not produce residue in the part that developing process will be removed, toner is not deposited on the patterned background;

In the part that will remove, has sufficient solubleness; With

Improve for example patterns such as sharpness (pixel) formation property of pattern edge.When use contained the photosensitive color resin combination formation pixel of a large amount of coloured materials, following phenomenon often took place:

In developing process, on the unexposed portion of substrate, produce residue and/or toner is deposited on the patterned background;

Make the blur margin of pixel clear because the solubleness of unexposed portion is bad; With

The light sensitivity deficiency of the pixel that forms at exposed portion has rough surface.

Need have under the situation of light shielding ability in the whole wavelength coverage at light at for example resin black matrix etc., then following point can take place:

Between exposed portion and unexposed portion, be difficult to realize the significant difference of cross-linking density;

Even in exposed portion, there is the difference of cross-linking density in different parts on thickness direction, that is, although fully solidified near the resin of exposed,, do not solidify fully near resin with the exposed opposite surfaces; With

Owing to a large amount of insoluble black colorant materials is arranged, in developer solution so development capability reduces significantly.This can hinder to resin combination and give good photonasty.

Summary of the invention

Therefore, an object of the present invention is to provide a kind of photosensitive polymer combination, described photosensitive polymer combination has good adhesiveness to substrate, even in the situation of the painted material such as for example pigment and/or carbon black etc. that contains high concentration, with do not need for example situation of painted material such as pigment being used for light spacer (photospacer) or rib wall, the light sensitivity of described photosensitive polymer combination and solubleness obtain good equilibrium, and generation has pixel edge and wedge-like portion clearly, have excellent adhesiveness and surface smoothness, prevent that satisfactorily toner is deposited on the patterned background, and have excellent thermotolerance and storage stability.

Another object of the present invention provides a kind of high-quality color filter and high quality lcd of using described photosensitive polymer combination.

Particularly, first aspect, the invention provides a kind of photosensitive polymer combination that contains organic bond, wherein said organic bond contains the alkali solubility unsaturated polyester, described alkali solubility unsaturated polyester be by the epoxy compound that has at least two epoxy radicals in the per molecule (a) and contain unsaturated group carboxylic acid (b) reaction product with have a reaction product of the compound (c) of at least one isocyanate groups.

Second aspect, the invention provides a kind of photosensitive polymer combination that contains organic bond, wherein said organic bond contains the alkali solubility unsaturated polyester, described alkali solubility unsaturated polyester be have the compound that contains phenolic hydroxyl (f) of at least two phenolic hydroxyls in the per molecule and contain unsaturated group epoxy compound (g) reaction product with have a reaction product of the compound (c) of at least one isocyanate groups.

Description of drawings

Fig. 1 is illustrated in the evaluation that light spacer forms the maximum displacement H[max of loading-unloading test] and displacement H[last at last] synoptic diagram.

Embodiment

The photosensitive polymer combination of first aspect is the photosensitive polymer combination that comprises organic bond, and wherein said organic bond contains the alkali solubility unsaturated polyester.Described alkali solubility unsaturated polyester is prepared as follows: make per molecule have the epoxy compound (a) of at least two epoxy radicals and contain carboxylic acid (b) reaction of unsaturated group, make gained reaction product and compound (c) reaction with at least one isocyanate groups.

Epoxy compound (a) can comprise the compound of following general formula (I-a) expression:

Wherein, the X in the general formula (I-a) is represented by following general formula (II):

Wherein, R ¹～R ¹⁶Represent hydrogen atom independently of one another, have the alkyl of 1～12 carbon atom or have or do not have substituent phenyl, wherein, work as R ¹With R ²Be all alkyl and/or R ³With R ⁴When being all alkyl, R ¹With R ²And/or R ³With R ⁴Be combined into ring or be not combined into ring; N represents 0 or 1.

The photosensitive polymer combination of second aspect is the photosensitive polymer combination that contains organic bond, and wherein said organic bond contains the alkali solubility unsaturated polyester.Being prepared as follows of described alkali solubility unsaturated polyester: make per molecule have the compound that contains phenolic hydroxyl (f) of at least two phenolic hydroxyls and contain epoxy compound (g) reaction of unsaturated group, make gained reaction product and compound (c) reaction with at least one isocyanate groups.

The compound (f) that contains phenolic hydroxyl can comprise the compound of following general formula (I-f) expression:

HO-X-OH …(I-f)

Wherein, the X in the general formula (I-f) is represented by following general formula (II):

Wherein, R ¹～R ¹⁶Represent hydrogen atom independently of one another, have the alkyl of 1～12 carbon atom or have or do not have substituent phenyl, wherein, work as R ¹With R ²Be all alkyl and/or R ³With R ⁴When being all alkyl, R ¹With R ²And/or R ³With R ⁴Be combined into ring or be not combined into ring; N represents 0 or 1.

The per molecule of compound (c) can have two or more isocyanate groups.

General formula (I-a) and (I-f) in X can be following general formula (IIA), (IIB) and (IIC) in any:

At general formula (IIA), (IIB) with (IIC), R ¹～R ¹⁶With the definition of n such as the definition in the general formula (II).

General formula (IIA) can be following general formula (IIAa) and (IIAb) in one:

At general formula (IIAa) with (IIAb), R ¹And R ²As the definition in the general formula (II).

The photosensitive polymer combination of first and second aspects can also comprise light trigger.

The photosensitive polymer combination of first and second aspects can also comprise coloured material.

Can use any preparation color filter in the photosensitive polymer combination of the present invention.

Use the parts such as for example color filter, sept and rib wall of any preparation in the photosensitive polymer combination of the present invention can be used for LCD.

Photosensitive polymer combination of the present invention has good adhesion to substrate.Even in the situation of the painted material such as for example pigment and/or carbon black etc. that contains high concentration, or do not need for example situation of painted material such as pigment being used for light spacer or rib wall, the light sensitivity of described photosensitive polymer combination and solubleness also have good equilibrium, and produce and to have the pixel at edge and wedge-like portion clearly, have excellent adhesiveness and surface smoothness, prevent that satisfactorily toner is deposited on the patterned background, have excellent thermotolerance and storage stability.Use described photosensitive polymer combination, high-quality color filter and high-quality LCD can be provided.

Explain the preferred embodiments of the invention in more detail below.

＜alkali solubility unsaturated polyester 〉

For the alkali solubility unsaturated polyester that in photosensitive polymer combination of the present invention, comprises as organic bond, do not limit their preparation method, as long as finally have the similar chemical constitution of being put down in writing in the claims to the application of compound, this is can reach objects and advantages of the present invention owing to such resin.The example of alkali solubility unsaturated polyester comprises following [A-1] and [A-2].

The alkali solubility unsaturated polyester that [A-1] is prepared as follows: make per molecule have the epoxy compound (a) of at least two epoxy radicals and contain carboxylic acid (b) reaction of unsaturated group, make gained reaction product and compound (c) reaction with at least one isocyanate groups.In order to regulate acid value, preferably prepare the alkali solubility unsaturated polyester: make epoxy compound (a) and carboxylic acid (b) reaction that contains unsaturated group with following method, the compound (c) that will have at least one isocyanate groups adds on the hydroxyl of gained reaction product, again to its addition multi-anhydride (d).They can also be prepared as follows: multi-anhydride (d) is added on the addition product of isocyanate compound (c) of epoxy compound (a) and the reaction product of the carboxylic acid (b) that contains unsaturated group, the compound (e) that will contain epoxy radicals again adds on the formed part carboxyl.

The alkali solubility unsaturated polyester that [A-2] is prepared as follows: make per molecule have the compound that contains phenolic hydroxyl (f) and epoxy compound (g) reaction that contains unsaturated group of at least two phenolic hydroxyls, the gained reaction product is reacted with the compound with at least one isocyanate groups (c) again.In order to regulate acid value, preferably prepare the alkali solubility unsaturated polyester: make compound (f) that contains phenolic hydroxyl and epoxy compound (g) reaction that contains unsaturated group with following method, the compound (c) that will have at least one isocyanate groups adds on the hydroxyl of gained reaction product, again to its addition multi-anhydride (d).They can also be prepared as follows: multi-anhydride (d) is added on the addition product of the compound (f) that contains phenolic hydroxyl and the isocyanate compound (c) of the reaction product of the epoxy compound (g) that contains unsaturated group, the compound (e) that will contain epoxy radicals again adds on the part carboxyl that obtains.

Photosensitive polymer combination of the present invention should comprise at least a as organic bond among alkali solubility unsaturated polyester [A-1] and [A-2], two or more alkali solubility unsaturated polyester [A-1], two or more alkali solubility unsaturated polyester [A-2] be can comprise, or at least a alkali solubility unsaturated polyester [A-1] and at least a alkali solubility unsaturated polyester [A-2] comprised.

[per molecule has the epoxy compound (a) of at least two epoxy radicals]

Stop collar oxygen compound (a) particularly not is as long as have at least two epoxy radicals in the per molecule.Its example comprises the epoxy compound of following general formula (I-a) expression:

Wherein, the X in the general formula (I-a) is represented by following general formula (II):

Wherein, R ¹～R ¹⁶Represent hydrogen atom independently of one another, have the alkyl of 1～12 carbon atom or have or do not have substituent phenyl, wherein, work as R ¹With R ²Be all alkyl and/or R ³With R ⁴When being all alkyl, R ¹With R ²And/or R ³With R ⁴Be combined into ring or be not combined into ring; N represents 0 or 1.

If the X in the general formula (I-a) partly has too low molecular weight, the resin that obtains will too promptly be dissolved in the alkaline-based developer.Like this, especially in the situation of resin black matrix, developer solution also will soak into exposure position, thereby make the adhesiveness variation.If the X in the general formula (I-a) partly has too high molecular weight, the resin that obtains will be dissolved in the alkaline-based developer too lentamente.Like this, prolong the common variation of production efficiency owing to produce the quiescent interval (tact time).The molecular weight of X part is preferably 200 or greater than 200, more preferably 220 or greater than 220, further preferred 280 or greater than 280, preferred especially 300 or greater than 300, especially preferred 330 or greater than 330, and be preferably 430 or, more preferably 410 or, further preferred 380 or less than 380 less than 410 less than 430.After this, the epoxy compound with molecular weight of 200～430 of general formula (I-a) expression is called " epoxy compound (a-1) ".

In general formula (I-a), R ¹～R ¹⁶Each alkyl of expression can be straight chained alkyl, branched alkyl and naphthenic base.In the situation of straight chained alkyl or branched alkyl, preferably has 1～10 carbon atom.In the situation of naphthenic base, preferably have 5～10 carbon atoms.

By R ¹With R ²Or R ³With R ⁴The example of the ring that forms is naphthenic hydrocarbon ring and the diamantane ring with 5～15 carbon atoms.By R ¹With R ²Or R ³With R ⁴The ring that forms can have the substituting group of arbitrary number at an arbitrary position.Substituent example is the alkyl with 1～5 carbon atom.

X in the general formula (I-a) is preferably by following general formula (IIA), (IIB) with an expression (IIC):

Wherein, general formula (IIA), (IIB) and (IIC) in R ¹～R ¹⁶With the definition in n such as the general formula (II).

General formula (IIA) is preferably by following general formula (IIAa) with an expression (IIAb):

R wherein ¹And R ²As the definition in the general formula (II).

The X object lesson partly that satisfies above-mentioned condition is including, but not limited to descending array structure:

Wherein, R ⁴¹And R ⁴²Expression independently of one another has or does not have substituent alkylidene or has or do not have substituent arlydene; J and k represent 0～10 integer independently of one another.

In above-mentioned structure of giving an example, structure (X-1)～(X-12) and (X-40)～(X-43) be in the general formula (I-a) X by general formula (IIAa) or (IIAb) expression object lesson.In them, preferably have (X-1), (X-2), (X-40) and (X-41) those of structure of expression.

Epoxy compound used in this invention (a) can be the epoxy compound of general formula (I-a) expression, and wherein X has less than 200 or surpasses 480 molecular weight (after this being called " epoxy compound (a-2) ").Epoxy compound (a-2) can be used in combination with epoxy compound (a-1).The object lesson of epoxy compound (a-2) is the compound of general formula (I-a) expression, and wherein X is by following general formula (IID) or (IIE) expression.

At general formula (IID) with (IIE), R ¹And R ²As the definition in the general formula (II); R ¹⁷～R ²⁴Represent hydrogen atom independently of one another or have or do not have substituent alkyl with 1～3 carbon atom.

In epoxy compound (a-2), preferred especially X is the compound by following general formula (IIDa) expression.

In general formula (IIDa), R ¹And R ²As the definition in the general formula (II); R ¹⁷And R ²¹Represent hydrogen atom independently of one another or have or do not have substituent alkyl with 1～3 carbon atom.

In being used in combination of epoxy compound (a-2) and epoxy compound (a-1), generally with 20 weight % of epoxy compound (a-1) or be lower than 20 weight %, preferred 15 weight % or the amount that is lower than 15 weight % are used epoxy compound (a-2).

Epoxy compound by general formula (I-a) expression can for example be prepared by following approach: the compound that uses following general formula (IV) expression, in the presence of for example alkali metal hydroxide such as NaOH or potassium hydroxide, under 20～120 ℃ temperature, reacted 1～10 hour with for example epihalohydrins such as chloropropylene oxide or epibromohydrin.

HO-X-OH (IV)

Definition in X in the general formula (IV) such as the general formula (I-a).

In the reaction of the epoxy compound that preparation general formula (I-a) is represented, can use alkali metal hydroxide with the form of aqueous solution.In this case, epoxy compound can prepare with following process: be added to the aqueous solution of alkali metal hydroxide in the reaction system continuously, under decompression or normal pressure, steam water and epihalohydrins continuously simultaneously, separate distillate again, therefrom remove and anhydrate, epihalohydrins is looped back in the reaction system continuously.

Epoxy compound also can be with the preparation of following process: for example quaternary ammonium salts such as tetramethyl-ammonium chloride, tetramethylammonium bromide or Variquat B 200 are added in the dissolving mixt of the compound of general formula (IV) expression and epihalohydrins as catalyzer, this potpourri reacted 1～5 hour down at 50～150 ℃, generate the halohydrin etherate of the compound of general formula (IV) expression, add solid alkali metal oxyhydroxide or its aqueous solution to it, then under 20～120 ℃ temperature, react 1～10 hour with dehydrohalogenation (closed loop).

Hydroxyl with respect to 1 equivalent in the compound of general formula (IV) expression, amounts of the epihalohydrins that these reactions are used are generally 1 mole or greater than 1 mole, preferred 2 moles or, and be generally 30 moles or less than 30 moles greater than 2 moles, preferred 20 moles or less than 20 moles.Hydroxyl with respect to 1 equivalent in the compound of general formula (IV) expression, the amount of alkali metal hydroxide is generally 0.8 mole or greater than 0.8 mole, preferred 0.9 mole or, and be generally 15 moles or less than 15 moles greater than 0.9 mole, preferred 11 moles or less than 11 moles.

In order successfully to react, can for example alcohols such as methyl alcohol or ethanol and/or for example dimethyl sulfone or dimethyl sulfoxide isopolarity aprotic solvent in the presence of react.If use alcohol, then Chun amount is generally 2 weight % of epihalohydrins or greater than 2 weight %, preferred 4 weight % or greater than 4 weight %, and be generally 20 weight % or less than 20 weight %, preferred 15 weight % or less than 15 weight %.If use polar non-solute, then the amount of polar non-solute is generally 5 weight % of epihalohydrins or greater than 5 weight %, preferred 10 weight % or greater than 10 weight %, and be generally 100 weight % or less than 100 weight %, preferred 90 weight % or less than 90 weight %.

After washing with water or do not wash with water, the reaction product of these epoxidation reactions heats under at 110～250 ℃ and 1.3kPa (10mmHg) or less than the decompression of 1.3kPa, thereby removes other unnecessary components such as epihalohydrins and for example solvent.In order to reduce the water-disintegrable halogen in the epoxy resin, for example also the epoxy resin of above-mentioned preparation can be dissolved in again in toluene or the methyl isobutyl ketone equal solvent; Add for example aqueous solution of alkali metal hydroxide such as NaOH or potassium hydroxide to it, then react to guarantee closed hoop.In this case, with respect to 1 equivalent hydroxyl in the compound of the general formula that uses in the epoxidation (IV) expression, the amount of alkali metal hydroxide is preferably 0.01 mole or greater than 0.01 mole, preferred especially 0.05 mole or greater than 0.05 mole, and be preferably 0.3 mole or, preferred especially 0.2 mole or less than 0.2 mole less than 0.3 mole.Temperature of reaction is 50～120 ℃, and the reaction time was generally 0.5～2 hour.

After reaction was finished, generally with filtering and/or wash with water the salt of removing formation, heating under reduced pressure boiled off for example toluene or methyl isopropyl Ketone equal solvent, thereby generates the epoxy compound of general formula (I-a) expression.

Epoxy compound used in this invention (a) is not defined in the epoxy compound of general formula (I-a) expression especially, its object lesson comprises: bisphenol A type epoxy resin (for example, from Yuka ShellEpoxy Co., " Epicoat 828 " that Ltd. obtains, " Epicoat 1001 ", " Epicoat 1002 " and " Epicoat 1004 "); The epoxy resin of prepared in reaction between the alcoholic hydroxyl of bisphenol A type epoxy resin and the chloropropylene oxide (for example,, having 323 epoxide equivalent and 76 ℃ softening point) from " NER-1302 " that Japanese chemical drug (strain) obtains; Bisphenol F type resin (for example, from Yuka Shell EpoxyCo., " Epicoat 807 ", " EP-4001 ", " EP-4002 ", " EP-4004 " that Ltd. obtains); The epoxy resin of prepared in reaction between the alcoholic hydroxyl of bisphenol f type epoxy resin and the chloropropylene oxide (for example,, having 350 epoxide equivalent and 66 ℃ softening point) from " NER-7406 " that Japanese chemical drug (strain) obtains; Bisphenol-s epoxy resin; The xenyl glycidol ether (for example, from Yuka ShellEpoxy Co., " YX-4000 " that Ltd. obtains); Novolac epoxy resin (for example, " EPPN-201 " that obtains from Japanese chemical drug (strain), from Yuka Shell Epoxy Co., " EP-152 " that Ltd. obtains and " EP-154 ", " DEN-438 " that obtains from Dow Chemical Company); Line style cresol novolak epoxy (for example, " EOCN-102S " that obtains from Japanese chemical drug (strain), " EOCN-1020 " and " EOCN-104S "); Isocyanic acid three-glycidyl ester (for example, from producing " TEPIC " that chemistry (strain) obtains daily); Tris-phenol type epoxy resin (for example, " EPPN-501 " that obtains from Japanese chemical drug (strain), " EPPN-502 " and " EPPN-503 "); Fluorenes epoxy resin (for example, the cardo epoxy resin " ESF-300 " that obtains from Nippon Steel's chemistry (strain)); Alicyclic epoxy resin (from Daicel Chemical Industries, " Celoxide2021P " that Ltd. obtains and " Celoxide EHPE "); Dicyclopentadiene type epoxy resin for preparing with the phenol resin diglycidylization that dicyclopentadiene and phenol reactant are obtained (" XD-1000 " that obtains from Japanese chemical drug society, from Dainippon Ink and Chemical, " EXA-7200 " that Inc. obtains, " NC-3000 " and " NC-7300 " that obtain from Japanese chemical drug society) etc.

Other example of epoxy compound (a) is a copolymerization epoxy resin.Copolymerization epoxy resin comprises the multipolymer by following method preparation: (methyl) glycidyl acrylate, (methyl) acryloyl group methyl cyclohexane olefinic oxide or vinyl cyclohexene oxide (after this being called " first component of copolymerization epoxy resin ") and one or more other compound (after this being called " second component of copolymerization epoxy resin ") that contains simple function ethylenic unsaturated group are reacted.The example of second component is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester, (methyl) acrylic acid, styrene, (methyl) phenoxyethyl acrylate, (methyl) benzyl acrylate, α-Jia Jibenyixi, list (methyl) acrylic acid glyceride and by the compound of following general formula (IA) expression.In this manual, for example, term " (methyl) acrylate " and " (methyl) acryloyl so-and-so " refer to " acrylate or methacrylate " and " acryloyl so-and-so or methacryl so-and-so " respectively." (methyl) acrylic acid " for example mentioned later is meant " acrylic or methacrylic acid ".

Wherein, R ²¹Expression hydrogen or ethyl; R ²²Expression hydrogen or have the alkyl of 1～6 carbon atom; R represents 2～10 integer.

The example of the compound of general formula (IA) has: polyethyleneglycol (methyl) acrylate, for example diethylene glycol list (methyl) acrylate, triethylene glycol list (methyl) acrylate and TEG list (methyl) acrylate; Alkoxy polyglycol (methyl) acrylate, for example methoxyl diethylene glycol list (methyl) acrylate, methoxyl triethylene glycol list (methyl) acrylate and methoxyl TEG list (methyl) acrylate.

Copolymerization epoxy resin preferably has about 1000～200000 molecular weight.The amount of first component is preferably 10 weight % of second component in the copolymerization epoxy resin or greater than 10 weight % in the copolymerization epoxy resin, preferred especially 20 weight % or greater than 20 weight %, and be preferably 70 weight % or less than 70 weight %, preferred especially 50 weight % or less than 50 weight %.

The object lesson of copolymerization epoxy resin obtains " CP-15 ", " CP-30 ", " CP-50 ", " CP-20SA ", " CP-510SA ", " CP-50S ", " CP-50M " and " CP-20MA " from Japanese grease (strain).

In above-mentioned epoxy compound (a), the diglycidyl ether of the bis-phenol of preferred formula (I-a) expression, typically preferred epoxy compound (a-1).

Can be individually or use every kind of epoxy compound (a) in combination.If use in combination, the preferred compositions of epoxy compound is the epoxy compound and the combination with epoxy compound of the epoxy radicals more than three or three with two epoxy radicals.The combination of epoxy compound comprises, for example, product, the Dainippon Ink and Chemical of the compound of general formula (I-a) expression and the commodity " XD-1000 " by name of Japanese chemical drug society system, the commodity of Inc. are called the product of " EXA-7200 " or the combination of tris-phenol type epoxy compound.

[carboxylic acid (b) that contains unsaturated group]

The carboxylic acid (b) that contains unsaturated group comprises the unsaturated carboxylic acid with ethylenic unsaturated double-bond.Its object lesson has: monocarboxylic acid, for example (methyl) acrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid or (methyl) acrylic acid that vinyl benzoic acid and α position are replaced by haloalkyl, alkoxy, halogen, nitro or cyano group; 2-(methyl) acryloxy ethyl succinic acid, 2-(methyl) acryloxy ethyl hexane diacid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy ethyl maleic acid, 2-(methyl) acryloxy propyl group succinic acid, 2-(methyl) acryloxy propyl group hexane diacid, 2-(methyl) acryloxy propyl group tetrahydrophthalic acid, 2-(methyl) acryloxy propyl group phthalic acid, 2-(methyl) acryloxy propyl group maleic acid, 2-(methyl) acryloxy butyl succinic acid, 2-(methyl) acryloxy butyl hexane diacid, 2-(methyl) acryloxy butyl hydrogenation phthalic acid, 2-(methyl) acryloxy butyl phthalic acid and 2-(methyl) acryloxy butyl maleic acid; For example lactones such as 6-caprolactone, beta-propiolactone, gamma-butyrolacton or δ-Wu Neizhi add to the monomer that forms on (methyl) acrylic acid; (methyl) acrylic acid dimer; The compound that three (methyl) acrylic acid pentaerythritol ester and succinic anhydride reaction form; Compound with three (methyl) acrylic acid pentaerythritol ester and phthalic anhydride formation.

In them, preferred especially (methyl) acrylic acid.Can be individually or use in these compounds each in combination.

[epoxy compound (a) and contain reaction between the carboxylic acid (b) of unsaturated group]

Can carry out the epoxy radicals and the reaction that contains the carboxylic acid (b) of unsaturated group of epoxy compound (a) according to known method.For example in organic solvent, in the presence of catalyzer, epoxy compound (a) and the carboxylic acid (b) that contains unsaturated group were reacted under 50～150 ℃ temperature of reaction several hours to tens hours, thereby carboxylic acid can be added in the epoxy compound.The example of catalyzer is a tertiary amines, for example triethylamine and benzyl methyl amine; Quaternary ammonium salt, for example chlorination dodecyl trimethyl ammonium, tetramethyl-ammonium chloride, tetraethyl ammonium chloride(TEAC and benzyltriethylammonium chloride; Pyridine; And triphenylphosphine.

With respect to the potpourri of reactant (epoxy compound (a) and contain the total amount of the carboxylic acid (b) of unsaturated group), the amount of catalyzer is preferably 0.01 weight % or greater than 0.01 weight %, preferred especially 0.3 weight % or greater than 0.3 weight %, and be preferably 10 weight % or less than 10 weight %, preferred especially 5 weight % or less than 5 weight %.In order when reacting, to prevent polymerization, preferably use polymerization inhibitor.The example of polymerization inhibitor is hydroquinone monomethyl ether (methoquinone), quinhydrones, methylnaphthohydroquinone, p methoxy phenol, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol and phenothiazine.Its amount be preferably reactant potpourri 0.01 weight % or greater than 0.01 weight %, preferred especially 0.1 weight % or greater than 0.1 weight %, and be preferably 10 weight % or, preferred especially 5 weight % or less than 5 weight % less than 10 weight %.

The ratio that adds to the carboxylic acid that contains unsaturated group (b) on the epoxy radicals of epoxy compound (a) generally is 90%～100 mole of %.If remaining epoxy radicals is arranged, will influence storage stability unfriendly.Therefore, with respect to 1 equivalent epoxy radicals in the epoxy compound (a), the amount of the carboxylic acid that contains unsaturated group (b) in the reaction generally is preferably 0.8 equivalent or greater than 0.8 equivalent, preferred especially 0.9 equivalent or greater than 0.9 equivalent, and generally be preferably 1.5 equivalents or less than 1.5 equivalents, preferred especially 1.1 equivalents or less than 1.1 equivalents.

[compound (c)] with at least one isocyanate groups

The compound with at least one isocyanate groups (c) that adds to epoxy compound (a) and contain on the hydroxyl of the reaction product between the carboxylic acid (b) of unsaturated group can be any compound that routinizes.Compound (c) can be the isocyanate compound that per molecule has an isocyanate groups, or per molecule has the polyisocyanate compounds of a plurality of isocyanate groups.To have the more resin of high molecular in order producing after crosslinked, preferably to use polyisocyanate compounds.

The example that per molecule has the compound of an isocyanate groups is butane isocyanates, 3-chlorobenzene isocyanates, 4-chlorobenzene isocyanates, cyclohexane isocyanates, benzene isocyanates, the different acryloyl group of 3-(isopropenoyl)-α, α-Er Jiajibianji isocyanates and a toluene diisocyanate.

The example of polyisocyanate compounds is an aromatic diisocyanate, for example to phenylene vulcabond, 2,4-benzal diisocyanate, 2,6-benzal diisocyanate, 4,4 '-methyl diphenylene diisocyanate, naphthalene-1,5-diisocyanate and tolidine diisocyanate; Aliphatic diisocyanate, for example hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate and dimer acid diisocyanate; Alicyclic diisocyanate, isophorone diisocyanate, 4 for example, 4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and ω, ω ' diisocyanate dimethyl cyclohexane; Aliphatic diisocyanate with aromatic rings, for example eylylene diisocyanate and α, α, α ', α '-tetramethyl eylylene diisocyanate; Triisocyanate, lysine ester triisocyanate, 1 for example, 6,11-undecane triisocyanate, 1,8-two isocyanato-s-4-isocyanato-methyloctane, 1,3,6-hexa-methylene triisocyanate, norbornane triisocyanate, three (isocyanato-phenyl) methane and three (isocyanato-phenyl) thiophosphate; With their tripolymer, water addition product and polyvalent alcohol addition product.

In them, two or tripolymer of preferred organic diisocyanate, the most preferably tripolymer of the trimethylolpropane addition product of benzylidene diisocyanate, benzylidene diisocyanate and Trimerization of Isophorone Diisocyanate body.

Can be individually or use every kind of compound (c) in combination with at least one isocyanate groups.

For example prepare the organic diisocyanate tripolymer with the following method: under the catalysis of suitable catalyst for trimerization, the isocyanate groups that makes polyisocyanate is trimerization partly, add catalyst poison and stop trimerization reaction, remove unreacted polyisocyanate with solvent extraction or thin-film distillation, obtain the polyisocyanate that target contains isocyanate groups.The example of catalyst for trimerization is tertiary amine, phosphine, alkoxide, metal oxide and carboxylate.

[addition] with compound (c) of at least one isocyanate groups

Adding to epoxy compound (a) with respect to the carboxylic acid that contains unsaturated group (b) goes up and the hydroxyl of formation, addition number percent with compound (c) of at least one isocyanate groups generally is 10 moles of % or greater than 10 moles of %, preferred 20 moles of % or greater than 20 moles of %, and be generally 95 moles of % or less than 95 moles of %, preferred 90 moles of % or less than 90 moles of %.If addition number percent is low excessively, the performance of the film that resin combination forms reduces.If it is too high, the viscosity that contains the solution of resin increases, and is difficult to handle.

Can be according to known method, the compound (c) that will have at least one isocyanate groups adds on the addition product of epoxy compound (a) and the carboxylic acid (b) that contains unsaturated group.Temperature of reaction is generally 40 ℃ or be higher than 40 ℃, and preferred 50 ℃ or be higher than 50 ℃, and be generally 150 ℃ or be lower than 150 ℃, preferred 100 ℃ or be lower than 100 ℃.Reaction time generally is 1～100 hour, preferably in 24 hours.Temperature of reaction surpasses 130 ℃ will make unsaturated group partially polymerized, cause molecular weight to increase sharply.Reaction is carried out smoothly.

This addition reaction can be carried out in the presence of catalyzer.The example of catalyzer is common polyurethane-reinforcement catalysts, comprising: tin catalyst, for example dibutyl tin laurate, two lauric acid dioctyl tins, two sad dibutyl tin and stannous octoates; Iron catalyst, for example ferric acetyl acetonade and iron chloride; And tertiary amine catalyst, for example triethylamine and triethylenediamine.

[addition of multi-anhydride (d)]

The alkali solubility unsaturated polyester that the present invention relates to is preferably with the preparation of following method: the compound (c) that will have at least one isocyanate groups adds on the hydroxyl of epoxy compound (a) and the reaction product of the carboxylic acid (b) that contains unsaturated group, again to its addition multi-anhydride (d) to regulate acid value.

Conventional multi-anhydride can be used as multi-anhydride (d).Its example is a dicarboxylic anhydride, for example maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl carbic anhydride, chlorendic anhydride and methyl tetrahydrophthalic anhydride; Tetrabasic carboxylic acid dicarboxylic anhydride, for example trihemellitic acid acid anhydride, PMA, benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, biphenyltetracarboxyacid acid dicarboxylic anhydride and biphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride.In them, preferred compositions is used for example dicarboxylic anhydride such as tetrabydrophthalic anhydride or succinic anhydride and for example tetrabasic carboxylic acid dicarboxylic anhydride such as benzophenone tetrabasic carboxylic acid dicarboxylic anhydride or biphenyltetracarboxyacid acid dicarboxylic anhydride.The photosensitive polymer combination that obtains in this situation is produced the film with superperformance.When using the tetrabasic carboxylic acid dicarboxylic anhydride, can add on one of two kinds of anhydride moieties having compound bearing active hydrogen in the molecule, to regulate acid value or to introduce unsaturated group.Have in the compound bearing active hydrogen in these molecules, the compound that uses citric acid, maleic acid, 3-hydroxypivalic acid etc. to have reactive hydrogen and organic acid group is regulated acid value.Use hydroxyethyl (methyl) acrylic acid, hydroxyl butyl (methyl) acrylic acid, 2-methylol methyl acrylate, 2-methylol ethyl acrylate etc. have unsaturated group and compound bearing active hydrogen is introduced unsaturated group.

With respect to add to the hydroxyl that epoxy compound (a) upward forms by the carboxylic acid that contains unsaturated group (b), the addition number percent of multi-anhydride (d) is generally 5 moles of %～90 mole %, preferred 5 moles of %～80 mole %, more preferably 5 moles of %～70 mole %.Too low addition number percent causes inadequate solubleness or to the inadequate adhesiveness of substrate.

According to known method, multi-anhydride (d) can be added to epoxy compound (a) and contain on the addition product of isocyanate compound (c) of reaction product of carboxylic acid (b) of unsaturated group.Temperature of reaction is generally 80 ℃ or be higher than 80 ℃, and preferred 90 ℃ or be higher than 90 ℃, and be generally 130 ℃ or be lower than 130 ℃, preferred 125 ℃ or be lower than 125 ℃.Temperature of reaction surpasses 130 ℃ will cause that unsaturated group is partially polymerized, cause molecular weight to increase sharply.Temperature of reaction is lower than 80 ℃ can not make reaction successfully carry out, and cause remnants that unreacted multi-anhydride (d) is arranged.

[containing the addition of the compound (e) of epoxy radicals]

The alkali solubility unsaturated polyester that the present invention relates to can be prepared as follows: multi-anhydride (d) is added to epoxy compound (a) and contain on the addition product of isocyanate compound (c) of reaction product of carboxylic acid (b) of unsaturated group, the compound (e) that will contain epoxy radicals again is added on the formed part carboxyl.

The example that contains the compound (e) of epoxy radicals is: in order to improving light sensitivity (methyl) glycidyl acrylate, (methyl) acrylic acid-3, and 4-epoxy cyclohexyl or have the glycidyl ether compound of polymerism unsaturated group; And/or in order to improve the glycidyl ether compound that does not have the polymerism unsaturated group of development capability.The former and the latter can be used in combination.The object lesson that does not have the glycidyl ether compound of polymerism unsaturated group is the glycidyl ether compound with phenyl or alkyl, for example " the Denacol EX-111 " that obtains from Nagase Chemtex Corporation, " DenacolEX-121 ", " Denacol EX-141 ", " Denacol EX-145 ", " Denacol EX-146 ", " Denacol EX-171 " and " Denacol EX-192 ".

[compound that contains phenolic hydroxyl (f) that has at least two phenolic hydroxyls in the per molecule]

Do not limit the compound (f) that contains phenolic hydroxyl particularly, as long as have at least two phenolic hydroxyls in the per molecule, its example is the compound that contains phenolic hydroxyl of following general formula (I-f) expression:

HO-X-OH …(I-f)

Wherein, the X in the general formula (I-f) is represented by following general formula (II):

Wherein, R ¹～R ¹⁶Represent hydrogen atom independently of one another, have the alkyl of 1～12 carbon atom or have or do not have substituent phenyl, wherein, work as R ¹With R ²Be all alkyl and/or R ³With R ⁴When being all alkyl, R ¹With R ²And/or R ³With R ⁴Be combined into ring or be not combined into ring; N represents 0 or 1.

The definition of X in X in the general formula (I-f) and the general formula (I-a) is identical, and that describes in its preferred structure and other condition and the general formula (I-a) is identical.

[epoxy compound (g) that contains unsaturated group]

Qualification contains the epoxy compound (g) of unsaturated group especially, has at least one epoxy radicals in ethylenic unsaturated double-bond and the molecule as long as have.Its preferred example is the acrylate that contains epoxy radicals, for example (methyl) glycidyl acrylate and (methyl) acrylic acid 3,4-epoxy cyclohexyl.

[contain the compound (f) of phenolic hydroxyl and contain the reaction of the epoxy compound (g) of unsaturated group]

Can contain the compound (f) of phenolic hydroxyl and contain the reaction of the epoxy compound (g) of unsaturated group according to known method.For example, in organic solvent, in the presence of catalyzer, under 50～150 ℃ temperature of reaction, make the compound (f) and epoxy compound (g) reaction that contains unsaturated group several hours to tens hours that contain phenolic hydroxyl, the epoxy compound (g) that will contain unsaturated group adds on the compound (f) that contains phenolic hydroxyl.The object lesson of catalyzer is a tertiary amines, for example triethylamine and benzyl methyl amine; Quaternary ammonium salt, for example chlorination dodecyl trimethyl ammonium, tetramethyl-ammonium chloride, tetraethyl ammonium chloride(TEAC and benzyltriethylammonium chloride; Pyridine; And triphenylphosphine.

Potpourri (compound (f) and the total amount that contains the epoxy compound (g) of unsaturated group that contain phenolic hydroxyl) with respect to reactant, the amount of catalyzer is preferably 0.01 weight % or greater than 0.01 weight %, preferred especially 0.3 weight % or greater than 0.3 weight %, and be preferably 10 weight % or less than 10 weight %, preferred especially 5 weight % or less than 5 weight %.In order when reacting, to prevent polymerization, preferably use polymerization inhibitor.The example of polymerization inhibitor is hydroquinone monomethyl ether (methoquinone), quinhydrones, methylnaphthohydroquinone, p methoxy phenol, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol and phenothiazine.Its amount be preferably reactant potpourri 0.01 weight % or greater than 0.01 weight %, preferred especially 0.1 weight % or greater than 0.1 weight %, and be preferably 10 weight % or, preferred especially 5 weight % or less than 5 weight % less than 10 weight %.

The ratio that contains the epoxy compound (g) of unsaturated group generally is 90 moles of %～120 mole % of the compound (f) that contains phenolic hydroxyl.Remaining epoxy radicals will influence storage stability unfriendly.Therefore, with respect to 1 equivalent epoxy radicals in the epoxy compound that contains unsaturated group (g), preferably with general 0.8 equivalent or greater than 0.8 equivalent, preferred especially 0.9 equivalent or greater than 0.9 equivalent, and generally be preferably 1.5 equivalents or less than 1.5 equivalents, preferred especially 1.2 equivalents or use the compound (f) that contains phenolic hydroxyl less than the amount of 1.2 equivalents.

[have the compound (c) of at least one isocyanate groups addition, polybasic acid anhydride (d) addition and contain the addition of the compound (e) of epoxy radicals]

According to add on epoxy compound (a) and the reaction product of carboxylic acid (b) that contains unsaturated group with the compound that will have at least one isocyanate groups (c), the addition of multi-anhydride (d) and contain the same procedure of addition of the compound (e) of epoxy radicals, the compound (c) that carries out respectively having at least one isocyanate groups adds to the compound (f) that contains phenolic hydroxyl and contains the addition of addition on the reaction product of epoxy compound (g) of unsaturated group, multi-anhydride (d) and contain the addition of the compound (e) of epoxy radicals.

[physical property of alkali solubility unsaturated polyester]

Measure with GPC (gel permeation chromatography), the alkali solubility unsaturated polyester that the present invention relates to for above-mentioned preparation, be generally 700 or with the weight-average molecular weight (Mw) of polystyrene conversion greater than 700, preferred 1000 or greater than 1000, and be generally 50000 or less than 50000, preferred 30000 or less than 30000.The too low weight-average molecular weight of alkali solubility unsaturated polyester causes the thermal stability and the film strength of difference.On the contrary, too high weight-average molecular weight will make the solubleness in developer solution insufficient.

The acid value (mg-KOH/g) of the alkali solubility unsaturated polyester that the present invention relates to is generally 10 or greater than 10, preferred 30 or greater than 30, and is generally 200 or less than 200, preferred 150 or less than 150.The too low acid value of alkali solubility unsaturated polyester causes inadequate solubleness.On the contrary, too high acid value causes that curable is insufficient, thereby causes that surface property reduces.

＜light trigger 〉

Photosensitive polymer combination of the present invention can also comprise light trigger.

There is no particular limitation to light trigger used in this invention, as long as it is to make ethylenic unsaturated group polymeric compounds with active ray.When photosensitive polymer combination of the present invention comprises ethylenic compound when having the compound of polymerizable group, light trigger is preferably the light trigger with following ability, this light trigger causes decomposition reaction or dehydrogenation reaction by direct absorbing light or by photoactivate, thereby forms the polymerization activity free radical.

The object lesson of light trigger used in this invention is: the pyrrolotriazine derivatives of halomethylation, 2-(4-methoxyphenyl)-4 for example, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxy naphthyl)-4, two (trichloromethyl)-s-triazine of 6-and 2-(4-ethoxy carbonyl naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-; Halomethylation De oxadiazole derivant, 2-trichloromethyl-5-(2 '-benzofuranyl)-1 for example, 3,4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-benzofuranyl) vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-(6 "-benzofuranyl) vinyl)]-1; 3; 4-oxadiazole and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; Imdazole derivatives, 2-(2 '-chlorphenyl)-4 for example, 5-diphenyl-imidazole dimer, 2-(2 '-chlorphenyl)-4, two (3 '-methoxyphenyl) imidazoles dimers of 5-, 2-(2 '-fluorophenyl)-4,5-diphenyl-imidazole dimer, 2-(2 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer and (4 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer; Benzoin alkylether, for example benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; Anthraquinone derivative, for example 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone and 1-chloroanthraquinone; Benzophenone derivates, for example benzophenone, Michler's keton (Michler ' sketone), 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone and 2-carboxyl benzophenone; Acetophenone derivative, for example 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-(4 '-(methyl mercapto) phenyl)-2-morpholinyl-1-acetone and 1,1,1-trichloromethyl-(to butyl phenyl) ketone; Thioxanthone derivates, for example thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone and 2,4-diisopropyl thioxanthones; Benzoate derivatives, for example (dimethylamino)-ethyl benzoate, to the lignocaine ethyl benzoate; Acridine derivatives, for example 9-phenylacridine and 9-(p-methoxyphenyl) acridine; The azophenlyene derivant, for example 9,10-dimethylbiphenyl azophenlyene; Anthracyclinone derivatives, for example benzanthrone; With luxuriant titanium derivative, for example cyclopentadienyl titanium dichloride, hexichol two luxuriant titaniums, two (2,3,4,5,6-phenyl-pentafluoride-1-yl) two luxuriant titaniums, two (2,3,5,6-phenyl tetrafluoride-1-yl) two luxuriant titaniums, two (2,4,6-trifluoro-benzene-1-yl) two luxuriant titaniums, 2,6-two fluorobenzene-1-base two luxuriant titaniums, 2,4-two fluorobenzene-1-base two luxuriant titaniums, two (2,3,4,5,6-phenyl-pentafluoride-1-yl) dimethyl cyclopentadienyltitanium, two (2,6-two fluorobenzene-1-yl) dimethyl cyclopentadienyltitanium and 2,6-two fluoro-3-(pyrroles-1-yl)-benzene-1-base dimethyl cyclopentadienyltitanium.In addition, particularly advantageously use the special oxime initiating agent of describing in the 2000-80068 communique of opening.

Other light trigger used in this invention can find in following document: FineChemical, Vol.20, No.4,16-26 page or leaf (on March 1st, 1991), spy open clear 59-152396 communique and the clear 61-151197 communique of Te Kai, special public clear 45-37377 communique, spy open clear 58-40302 communique and the flat 10-39503 communique of Te Kai.

＜coloured material 〉

Photosensitive polymer combination of the present invention can be the photosensitive color resin combination that also comprises coloured material.

Dyestuff and pigment can be used as coloured material, from the angle of thermal stability and light stability, preferred pigments.This class pigment comprises versicolor pigment, for example blueness, green, redness, yellow, purple, orange, brown and black pigment.About their structure, can use for example organic pigment and various inorganic pigments such as azo, phthalocyanine, quinoline a word used for translation ketone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene pigment.Those pigment of the useful following pigment numbering of the object lesson of pigment used herein expression.Term " C.I. " in " C.I. paratonere 2 " is meant pigment index (C.I.).

The example of red pigment is a C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275 and 276.In them, preferred C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242 and 254, more preferably the C.I. paratonere 177,209,224 and 254.

The example of blue pigment is C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78 and 79.In them, preferred C.I. pigment blue 15,15:1,15:2,15:3,15:4 and 15:6, more preferably C.I. pigment blue 15: 6.

The example of viridine green is a C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54 and 55.In them, preferred C.I. pigment Green 7 and 36.

The example of yellow uitramarine is a C.I. pigment yellow 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207 and 208.In them, preferred C.I. pigment yellow 83,117,129,138,139,150,155,180 and 185, more preferably C.I. pigment yellow 83,138,139,150 and 180.

The example of orange pigment is a C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78 and 79.In them, preferred C.I. pigment orange 38 and 71.

The example of violet pigment is C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49 and 50.In them, preferred C.I. pigment violet 19 and 23, more preferably C.I. pigment Violet 23.

When photosensitive color resin combination that photosensitive polymer combination of the present invention is used as the resin black matrix of color filter, can use the black colorant material as coloured material.The black colorant material can be single black colorant material, or painted mixtures of material such as redness, green and blueness.These coloured materials can be selected from inorganic suitably or organic pigment and dyestuff in.In the situation of inorganic or organic pigment, preferably disperse having 1 μ m or less than 1 μ m, and preferred 0.5 μ m or less than the mean grain size of 0.5 μ m.

Example as the coloured material for preparing the black colorant mixtures of material is Victoria's ethereal blue (Victoria Pure Blue) (42595), auramine O (Auramine O) (41000), Catilon lucidin (Catilon Brilliant Flavin) (alkalescence 13), rhodamine (Rhodamine) 6GCP (45160), rhodamine B (45170), safranine (Safranine) OK 70:100 (50240), small-mouthed jar red (Erioglaucine) X (42080), NO.120/LionolYellow (21090), LionolYellow GRO (21090), Symuler Fast Yellow 8GF (21105), benzidine yellow 4J-564D (21095), Symuler Fast Red 4015 (12355), Lionol Red 7B4401 (15850), Fastgen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (pigment blue 15: 6), Lionogen Red GD (paratonere 168) and Lionol Green 2YS (pigment green 36).Numeral pigment index (C.I.) in the above-mentioned bracket.

Be used as the example of other pigment of potpourri, when representing, be C.I. pigment yellow 20,24,86,93,109,110,117,125,137,138,147,148,153,154 and 166 with the C.I. numbering; C.I. pigment orange 36,43,51,55,59 and 61; C.I. Pigment Red 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228 and 240; C.I. pigment violet 19,23,29,30,37,40 and 50; C.I. pigment blue 15,15:1,15:4,22,60 and 64; C.I. pigment Green 7; With C.I. bistre 23,25 and 26.

Separately the black colorant examples of material of using is carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine, cyanines are black and titanium dioxide black (titanium is black).

In them, from the angle of light shielding ability and pattern performance, preferred carbon black and titanium are black.The example of carbon black is as follows:

The product of Mitsubishi Chemical society: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL 7B, OIL 9B, OIL 11B, OIL 30B and OIL 31B;

The product of Degussa (Degussa): Printex 3, Printex 3 OP, Printex 30, Printex30 OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160 and Color BlackS170;

The product of Cabot (Cabot Corporation): Monarch 120, Monarch 280, Monarch460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARL S480, PEARL S130, VULCAN XC72R and ELFTEX-8;

The product of Colombia carbon black company (Colombian Carbon Company): RAVEN11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN22, RAVEN 30, RAVEN35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750 and RAVEN 7000.

The example for preparing the black method of titanium is including, but not limited to following method: the potpourri by heating titania and Titanium in reducing atmosphere reduces the method (spy opens clear 49-5432 communique) of titania; Hydrolysis titanium tetrachloride at high temperature, the method (spy opens clear 57-205322 communique) of the superfine titanic oxide that reduction obtains in containing the reducing atmosphere of hydrogen; The method of high temperature reduction titania or titanium hydroxide in the presence of ammonia (spy opens clear 60-65069 and 61-201610 communique); High temperature reduction has the method (spy opens clear 61-201610 communique) of the titania or the titanium hydroxide of vfanadium compound in the presence of ammonia.

The example of the black product of commercially available titanium is to deceive 10S, 12S, 13R, 13M and 13M-C from the titanium that Mitsubishi Materials Corporation obtains.

The example of other black pigment is that titanium is black, nigrosine, iron oxides black pigment and as the black pigment of the potpourri of red, green and blue organic pigment.

In addition, pigment also comprises for example barium sulphate, lead sulfate, titanium dioxide, chrome yellow, iron oxide red and chromium oxide.

Can use these different pigment in combination.In order to regulate colourity, can be used in combination viridine green and yellow uitramarine, maybe can be used in combination blue pigment and violet pigment.

The mean grain size of these pigment is generally 1 μ m or less than 1 μ m, preferred 0.5 μ m or less than 0.5 μ m, more preferably 0.25 μ m or less than 0.25 μ m.The example that is used as the dyestuff of coloured material is azo dyes, anthraquinone dye, phthalocyanine dye, quinoneimine dye, quinoline dye, nitro dye, carbonyl dyestuff and methine dyes.

The example of azo dyes is the C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. direct yellow 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. mordant rouge 7, C.I. mordant yellow 5 and C.I. mordant dyeing black 7.

The example of anthraquinone dye is C.I. vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56 and C.I. disperse blue 60.

Phthalocyanine dye comprises that for example the C.I. vat blue 5.Quinoneimine dye comprises, for example C.I. alkali blue 3 and C.I. alkali blue 9.Quinoline dye comprises, for example C.I. solvent yellow 33, C.I. quinoline yellow and C.I. dispersion yellow 64.Nitro dye comprises, for example C.I. Indian yellow 1, C.I. acid orange 3 and C.I. Disperse Yellow 42.

＜spreading agent 〉

When photosensitive polymer combination of the present invention is that this photosensitive color resin combination can also comprise spreading agent when containing the photosensitive color resin combination of coloured material.

Spreading agent used in this invention is preferably the spreading agent of nitrogen atom.General use surfactant and macromolecule dispersing agent are as the spreading agent of nitrogen atom, preferably macromolecule dispersing agent.Every kind of macromolecule dispersing agent preferably contains at least a following material:

[1] polyurethane dispersant;

[2] nitrogenous graft copolymer; With

[3] A-B segmented copolymer and/or B-A-B segmented copolymer, every kind of multipolymer is included in block A that has quaternary ammonium salt group in the side chain and the B block that does not have quaternary ammonium salt group.

Can be individually or use in these spreading agents each in combination.

According to the present invention, by spreading agent that uses nitrogen atom in combination and the aforementioned specific alkali solubility unsaturated polyester that the present invention relates to, the coated film that forms by described photosensitive color resin combination when developing and substrate have high adhesiveness, and remaining undissolved material minimizing, can keep satisfied dispersion stabilization simultaneously.

Nitrogen-atoms in the nitrogenous spreading agent is preferably the form of amino or quaternary ammonium salt.These functional groups generally have alkalescence, easily and the acidic-group coordination of pigment and pigment derivative etc., thereby cause stable dispersion.The amine value of spreading agent is generally 2mg-KOH/g or greater than 2mg-KOH/g, preferred 3mg-KOH/g or greater than 3mg-KOH/g, and be generally 100mg-KOH/g or less than 100mg-KOH/g, preferred 80mg-KOH/g or less than 80mg-KOH/g.Nitrogenous spreading agent with too low amine value has inadequate alkalescence, can not produce stable dispersion fully.When amine value is too high, be used at the composition that obtains under the situation of LCD, can reduce the voltage confining force of liquid crystal and cause display defect.

At length explain preferred dispersing agent below.

[1] polyurethane dispersant

Polyurethane dispersant is preferably the dispersion resin that is prepared as follows: the compound (3) that has reactive hydrogen and tertiary amine groups in the compound (2) that has one or two hydroxyl in polyisocyanate compounds (1) and the molecule and the molecule is reacted.

(1) polyisocyanate compounds

The example of polyisocyanate compounds has: aromatic diisocyanate, for example to phenylene vulcabond, 2,4-benzal diisocyanate, 2,6-benzal diisocyanate, 4,4 '-methyl diphenylene diisocyanate, naphthalene-1,5-diisocyanate and tolidine diisocyanate; Aliphatic diisocyanate, for example hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate and dimer acid diisocyanate; Alicyclic diisocyanate, isophorone diisocyanate, 4 for example, 4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and ω, ω '-two isocyanato-dimethyl cyclohexane; Aliphatic diisocyanate with aromatic rings, for example eylylene diisocyanate and α, α, α ', α '-tetramethyl eylylene diisocyanate; Triisocyanate, lysine ester triisocyanate, 1 for example, 6,11-undecane triisocyanate, 1,8-two isocyanato-s-4-isocyanato-methyloctane, 1,3,6-hexa-methylene triisocyanate, bicycloheptane triisocyanate, three (isocyanato-phenylmethane) and three (isocyanato-phenyl) thiophosphate; Their tripolymer, water addition product and polyvalent alcohol addition product.The tripolymer of organic diisocyanate is preferably as polyisocyanate, most preferably benzal diisocyanate trimer and isophorone diisocyanate trimer.Can be individually or use in them each in combination.

For example prepare described organic diisocyanate tripolymer with the following method: under the catalysis of suitable catalyst for trimerization, the isocyanate groups that makes polyisocyanate is trimerization partly, adding catalyst poison stops trimerization reaction, remove unreacted polyisocyanate with solvent extraction or membrane filtration, obtain the polyisocyanate that contains isocyanate groups of target.The example of catalyst for trimerization is tertiary amine, phosphine, alkoxide, metal oxide and carboxylate.

(2) molecules have the compound of one or two hydroxyl

The example that molecule has the compound of one or two hydroxyl is PTMEG, polyester-diol, PCDL and polyolefin diols, and the alkyl of a terminal hydroxyl of these compounds with 1～25 carbon atom carries out the material of alkoxide.Can be individually or use in these materials each in combination.

Described PTMEG comprises two or more the potpourri in PTMEG, polyether ester two pure and mild these compounds.The example of described PTMEG is the product of the homopolymerization or the copolymerization of alkylene oxide, for example the potpourri of two or more in polyglycol, polypropylene glycol, tygon-propylene glycol, polyoxygenated tetramethylene glycol, polyoxygenated hexamethylene glycol, polyoxygenated eight methylene glycols and these compounds.The example of polyether ester glycol has, the reaction product between the potpourri of the glycol of ether-containing group or itself and another kind of dibasic alcohol and reaction product, polyester-diol and the alkylene oxide of dicarboxylic acids or its acid anhydrides, for example poly-(polyoxygenated tetramethylene) adipate.Most preferred PTMEG is polyglycol, polypropylene glycol, polyoxygenated tetramethylene glycol, and the alkyl of a terminal hydroxyl of these compounds with 1～25 carbon atom carries out the compound of alkoxide.

Described polyester-diol comprises the polycondensation product between dicarboxylic acids or its acid anhydrides and the dibasic alcohol.The example of dicarboxylic acids is succinic acid, glutaric acid, hexane diacid, decanedioic acid, fumaric acid, maleic acid and phthalic acid.The example of dibasic alcohol is aliphatics two dibasic alcohol, for example ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, the 2-butylene glycol, 1, the 3-butylene glycol, 1, the 4-butylene glycol, 2, the 3-butylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, the 2-methyl isophthalic acid, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, the 5-pentanediol, 1, the 6-hexanediol, 2-methyl-2, the 4-pentanediol, 2,2,4-trimethyl-1, the 3-pentanediol, 2-ethyl-1, the 3-hexanediol, 2,5-dimethyl-2, the 5-hexanediol, 1, the 8-ethohexadiol, the 2-methyl isophthalic acid, 8-ethohexadiol and 1,9-nonanediol; Alicyclic dibasic alcohol, for example two methylol cyclohexanes; Aromatic diol, for example two pure and mild pairs of hydroxy ethoxy benzene of xylylene; With N-alkyl two alkanolamines, for example N methyldiethanol amine.The example of polycondensation product is polyethylene adipate, poly-hexane diacid butylidene ester, poly-hexane diacid hexa-methylene ester and poly-hexane diacid ethylidene/propylidene ester; Make polylactone glycol or the polylactone list alcohol that initiating agent forms, for example polycaprolactone glycol and poly-methylpent lactone by aforementioned dibasic alcohol or monohydroxy alcohol with 1～25 carbon atom; With two or more the potpourri in these compounds.Most preferred polyester-diol is the polycaprolactone that alcohol that polycaprolactone dibasic alcohol or use have 1～25 carbon atom is done the initiating agent preparation, for example makes monohydroxy alcohol and 6-caprolactone carry out the prepared compound of ring opening polyaddition.

The example of PCDL is poly-(1, the 6-hexylidene) carbonic ester and poly-(3-methyl isophthalic acid, 5-pentylidene) carbonic ester.The example of polyolefin dibasic alcohol is polybutylene dibasic alcohol, hydrogenated polybutene dibasic alcohol and hydrogenated polyisoprene dibasic alcohol.In a molecule, have in the compound of 1 or 2 hydroxyl preferred, polyethers two pure and mild polyester-diols.

The number-average molecular weight that has the compound of 1 or 2 hydroxyl in molecule is generally 300 or greater than 300, preferred 500 or greater than 500, more preferably 1000 or greater than 1000, and be generally 10000 or less than 10000, preferred 6000 or less than 6000, more preferably 4000 or less than 4000.

The compound that has reactive hydrogen and tertiary amine groups in (3) molecules

Reactive hydrogen is the hydrogen atom of Direct Bonding on oxygen atom, nitrogen-atoms or sulphur atom, comprises the hydrogen atom in the functional groups such as hydroxyl, amino and mercapto for example.In them, the hydrogen atom in the preferred amino, the hydrogen atom of preferred especially primary amino radical.

Tertiary amine groups including, but not limited to: have the dialkyl amido that for example methyl, ethyl, isopropyl or normal-butyl etc. have the alkyl of 1～4 carbon atom; Be connected to form the group of heterocycle structure, for example imidazole ring or triazole ring etc. by this dialkyl amido.

The example that has the compound of reactive hydrogen and tertiary amine groups in this molecule is N, N-dimethyl-1,3-propane diamine, N, N-diethyl-1,3-propane diamine, N, N-dipropyl-1,3-propane diamine, N, N-dibutyl-1,3-propane diamine, N, N-dimethyl-ethylenediamine, N, N-diethyl ethylenediamine, N, N-dipropyl ethylenediamine, N, N-dibutyl ethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine and N, N-dibutyl-1, the 4-butanediamine.

Example as nitrogenous heterocyclic tertiary amine groups is: nitrogenous five-ring heterocycles, for example pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring and diazosulfide ring; With nitrogenous hexa-member heterocycle, for example pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring.In these nitrogen heterocyclic rings, preferred imidazole ring or triazole ring.

Object lesson with compound of imidazole ring and primary amino radical is 1-(3-aminopropyl) imidazoles, histidine, 2-aminooimidazole and 1-(2-amino-ethyl) imidazoles.Object lesson with compound of triazole ring and primary amino radical is a 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorphenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-glycol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole.In them, preferred N, N-dimethyl-1,3-propane diamine, N, N-diethyl-1,3-propane diamine, 1-(3-aminopropyl) imidazoles and 3-amino-1,2,4-triazole.

The preferred amounts of polyurethanes dispersion resin raw material is as follows.With respect to 100 weight portion polyisocyanate compounds, the amount that has the compound of 1 or 2 hydroxyl in molecule is generally 10 weight portions or greater than 10 weight portions, preferred 20 weight portions or greater than 20 weight portions, more preferably 30 amount amount parts or greater than 30 weight portions, and be generally 200 weight portions or less than 200 weight portions, preferred 190 weight portions or less than 190 weight portions, more preferably 180 weight portions or less than 180 weight portions; The amount that has the compound of reactive hydrogen and tertiary amine groups in molecule is generally 0.2 weight portion or greater than 0.2 weight portion, preferred 0.3 weight portion or greater than 0.3 weight portion, and be generally 25 weight portions or less than 25 weight portions, preferred 24 weight portions or less than 24 weight portions.

Measure with GPC,, be generally 1,000 or greater than 1 with the weight-average molecular weight of polystyrene conversion for the polyurethanes dispersion resin that the present invention relates to, 000, preferred 2,000 or greater than 2,000, more preferably 3,000 or greater than 3,000, and be generally 200,000 or less than 200,000, preferred 100,000 or less than 100,000, more preferably 50,000 or less than 50,000.If the resin that molecular weight less than 1,000, obtains has poor dispersiveness and dispersion stabilization.If surpass 200,000, resin has poor solubleness and dispersiveness, is difficult to the control reaction.

Known method according to the preparation urethane resin prepares the polyurethanes dispersion resin that the present invention relates to.Generally by using solvent to be prepared.The example of solvent is a ketone, for example acetone, MEK, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone; Ester, for example ethyl acetate, butyl acetate and cellosolve acetate; Hydrocarbon, for example benzene,toluene,xylene and hexane; Some alcohols, for example diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and the tert-butyl alcohol; Chloride, for example methylene chloride and chloroform; Ether, for example tetrahydrofuran and diethyl ether; And polar non-solute, for example dimethyl formamide, N-Methyl pyrrolidone and dimethyl sulfoxide.

The conventional catalyst that adopts the polyurethane-reinforcement reaction is as the catalyzer in this preparation.The example of described catalyzer is a tin catalyst, for example dibutyl tin laurate, two lauric acid dioctyl tins, two sad dibutyl tin and stannous octoates; Iron catalyst, for example ferric acetyl acetonade and iron chloride; And tertiary amine catalyst, for example triethylamine and triethylenediamine.

The amount that has the compound of reactive hydrogen and tertiary amine groups in molecule of preferred control, make that the amine value of reacted dispersion resin is 1mg-KOH/g or greater than 1mg-KOH/g, preferred especially 5mg-KOH/g or greater than 5mg-KOH/g, and be 100mg-KOH/g or less than 100mg-KOH/g, preferred especially 95mg-KOH/g or less than 95mg-KOH/g.The amine value that is lower than above-mentioned scope usually reduces dispersiveness.The amine value that surpasses this scope usually causes that development capability reduces.If dispersion resin contains remaining isocyanate groups after reaction, isocyanate groups preferably with alcohol or ammoniate be used for transform, thereby increase dispersion resin stability in time.

[2] nitrogenous graft copolymer

As nitrogenous graft copolymer, have those graft copolymers of the repetitive of nitrogen atom in the preferred main chain, preferably have the repetitive of following general formula (i) expression and/or those graft copolymers of the repetitive that following general formula is (ii) represented.

At general formula (i) with (ii), R ³¹Expression has the straight or branched alkylidene of 1～5 carbon atom, and for example methylene, ethylidene or propylidene preferably have the alkylidene of 2 or 3 carbon atoms, more preferably ethylidene; A represents that hydrogen atom or following general formula are (iii), (iv) and (any v), preferred following general formula (iii).

General formula (iii) in, W ¹Expression has the straight or branched alkylidene of 2～10 carbon atoms, preferably has the alkylidene of 4～7 carbon atoms, for example butylidene, pentylidene or hexylidene; P represents 1～20 integer, is preferably 5～10 integer.

General formula (iv) in, G ¹The expression divalent linker, preference such as ethylidene or propylidene etc. have the alkylidene of 1～4 carbon atom, or for example inferior ethoxyl or inferior propoxyl group etc. have the alkylene oxide group of 1～4 carbon atom; W ²Expression has the straight or branched alkylidene of 2～10 carbon atoms, and for example ethylidene, propylidene or butylidene preferably have the alkylidene of 2 or 3 carbon atoms, for example ethylidene or propylidene; G ²The expression hydrogen atom or-CO-R ³², R wherein ³²Expression has the alkyl of 1～10 carbon atom, and for example ethyl, propyl group, butyl, amyl group or hexyl preferably have the alkyl of 2～5 carbon atoms, for example ethyl, propyl group, butyl or amyl group; Q represents 1～20 integer, is preferably 5～10 integer.

General formula (v), W ³Alkyl or expression that expression has 1～50 carbon atom have 1～5 hydroxyl and have the hydroxyalkyl of 1～50 carbon atom, preference such as stearyl etc. have the alkyl of 10～20 carbon atoms, or for example monohydroxy stearyl etc. has the hydroxyalkyl of 1 or 2 hydroxyl and 10～20 carbon atoms.

In the graft copolymer that the present invention relates to, preferably by general formula (i) or (ii) the total content of repetitive of expression is higher, be generally 50 moles of % or, preferred 70 moles of % or greater than 70 moles of % greater than 50 moles of %.Graft copolymer can contain the repetitive of general formula (i) expression and the repetitive that general formula is (ii) represented simultaneously.There is no particular limitation to the ratio of these repetitives, but the repetitive of the general formula (i) that preferred described graft copolymer contains expression is more.In graft copolymer, the repetitive of general formula (i) or (ii) expression add up to 1 or greater than 1, preferred 10 or, more preferably 20 or, and be generally 100 or less than 100, preferred 70 or, more preferably 50 or less than 50 less than 70 greater than 20 greater than 10.Except the repetitive of general formula (i) and (ii) expression, graft copolymer can also comprise any other repetitive.The example of other repetitive is alkylidene and alkylene oxide group.The graft copolymer that the present invention relates to is preferably has end-NH ₂With-R ³¹-NH ₂Those graft copolymers, R wherein ³¹Identical with general formula (i) with the definition (ii).

The main chain of above-mentioned graft copolymer can be a straight chain shape or a chain.

Measure with GPC, the weight-average molecular weight of graft copolymer is preferably 3,000 or greater than 3,000, preferred especially 5,000 or greater than 5,000, and is preferably 100,000 or less than 100,000, is preferably 50,000 or less than 50,000 especially.If weight-average molecular weight less than 3,000, can not prevent the coloured material aggegation, the resin that obtains became and glued or gelation.If surpass 100,000, graft copolymer itself becomes full-bodied, and the solubleness in organic solvent is not high.

Can be according to the synthetic method of known method as the preparation spreading agent, the method for describing in for example special public clear 63-30057 communique.

[3] A-B segmented copolymer and/or B-A-B segmented copolymer wherein comprise block A that has quaternary ammonium salt group in the side chain and the B block that does not have quaternary ammonium salt group.

The block A that constitutes the segmented copolymer of spreading agent should have quaternary ammonium salt group, preferably has-N ⁺R ^1aR ^2aR ^3aY ^-The quaternary ammonium salt group of expression, wherein, R ^1a, R ^2aAnd R ^3aRepresent hydrogen atom independently of one another or have or do not have substituent ring-type or chain alkyl, perhaps R ^1a, R ^2aAnd R ^3aIn two or more formation ring texturees that mutually combine; Y ^-The expression balance anion.Quaternary ammonium salt group can directly or by divalent linker be attached on the main chain.

-N ⁺R ^1aR ^2aR ^3aY ^-In, R ^1a, R ^2aAnd R ^3aIn the example of two or more ring texturees of forming of mutually combining are 5～7 member heterocyclic ring containing nitrogen monocycles, or condense the condensed ring that forms by two in these rings.Nitrogen heterocyclic ring does not preferably have aromaticity, more preferably saturated rings.Its object lesson is as follows:

Wherein R represents R ^1a～R ^3aIn any.

These ring texturees can also have substituting group.

-N ⁺R ^1aR ^2aR ^3aY ^-In, R ^1aTo R ^3aIn each more preferably have or do not have substituent alkyl with 1～3 carbon atom, or for having or not having substituent phenyl.

Block A is preferably the block of the part-structure that contains following general formula (1) expression:

In general formula (1), R ^1a, R ^2aAnd R ^3aRepresent hydrogen atom independently of one another or have or do not have substituent ring-type or chain alkyl, perhaps R ^1a, R ^2aAnd R ^3aIn two or more formation ring texturees that mutually combine; R ^4aExpression hydrogen atom or methyl; Q represents divalent linker; Y ^-The expression balance anion.

In general formula (1), divalent linker Q for the alkylidene that for example has 1～10 carbon atom, arlydene ,-CONH-R ^5a-or-COO-R ^6a-, R wherein ^5aAnd R ^6aThe expression Direct Bonding, has the alkylidene of 1～10 carbon atom or by-R ^7a-O-R ^8aThe ether group with 1～10 carbon atom of-expression, wherein R ^7aAnd R ^8aRepresent alkylidene independently of one another.Q is preferably-COO-R ^6a-.

Balance anion Y ^-Example be Cl ^-, Br ^-, I ^-, ClO ₄ ^-, BF ₄ ^-, CH ₃COO ^-And PF ₆ ^-

Block A can have two or more the part-structure with above-mentioned specific quaternary ammonium salt group in a block.In this case, can comprise the described part-structure that contains quaternary ammonium salt group in the mode of random copolymerization or block copolymerization with two or more.Block A can also comprise one or more the part-structure that does not contain quaternary ammonium salt group, and the example of such part-structure is the part-structure of mentioning later of being derived by (methyl) acrylic ester monomer.This part-structure content in block A that does not contain quaternary ammonium salt group is preferably 0～50 weight %, more preferably 0～20 weight %.But most preferably block A does not comprise this part-structure that does not contain quaternary ammonium salt group.

Formation is the polymer architecture that is formed by the comonomer copolymerization as the B block of the segmented copolymer of spreading agent.The example of comonomer is a styrene monomer, for example styrene and α-Jia Jibenyixi; (methyl) acrylate monomer, for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) glycidyl acrylate, (methyl) benzyl acrylate, (methyl) hydroxy-ethyl acrylate, ethyl propylene acid glycidyl ester and (methyl) acrylic acid N, the N-dimethylamino ethyl ester; (methyl) acrylate monomers, for example (methyl) acryloyl chloride; (methyl) acrylamide monomer, for example (methyl) acrylamide, N hydroxymethyl acrylamide, N,N-DMAA and N, N-dimethylaminoethyl acrylamide; Vinyl acetate; Vinyl cyanide; Allyl glycidyl ether, crotonic acid glycidyl ether; With N-methacryl morpholine.

B block is preferably the part-structure of being derived by (methyl) acrylate monomer by following general formula (2) expression especially.

In general formula (2), R ^9aExpression hydrogen atom or methyl; R ^10aExpression has or does not have substituent ring-type or chain-like alkyl, has or do not have substituent aryl or has or do not have substituent aralkyl.

B block can have two or more the part-structure of being derived by (methyl) acrylate monomer in a block.Certainly, B block also can comprise other parts structure arbitrarily.When the part-structure of being derived by two or more different monomers is included in the B block that does not contain quaternary ammonium salt group, can comprise every kind of part-structure in the mode of random copolymerization or block copolymerization.If comprise the part-structure the part-structure of deriving except that (methyl) acrylate monomer in the B block, then its content in B block is preferably 0～50 weight %, more preferably 0～20 weight %.Most preferably B block does not contain the part-structure the part-structure of deriving except that (methyl) acrylate monomer.

Spreading agent used in this invention is to contain the A-B block of block A and B block or the macromolecular compound of B-A-B segmented copolymer form.For example, prepare this segmented copolymer with following living polymerisation process.

Described living polymerisation process comprises living anion polymerization method, cation activity polymerization and radical living polymerization method.The living anion polymerization method uses negative ion to make the polymerization activity kind, for example represents with following synoptic diagram.

The living anion polymerization method

When adopting following monomer (1) and (2):

Monomer (1):

Monomer (2):

The radical living polymerization method uses free radical to make the polymerization activity kind, for example represents with following synoptic diagram.

Radical living polymerization method: nitroxyl method

When adopting following monomer (1) and (2):

Monomer (1): Monomer (2):

Radical living polymerization method: ATRP method

When adopting following monomer (1) and (2):

Monomer (1):

Monomer (2):

Can synthesize this class spreading agent according to known method, these methods can find from following document: for example, the spy opens flat 9-62002 communique; P.Lutz, P.Masson etc., Polym.Bull.12,79 (1984); B.C.Anderson, G.D.Andrews etc., Macromolecules, 14,1601 (1981); K.Hatada, K.Ute etc., Polym.J.17,977 (1985), 18,1037 (1986); Koichi Migite, Koichi Hatada, Kobunshikako (Japanese), 36,366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Papers of Polymers, 46,189 (1989); M.Kuroki, T.Aida, J.Am.Chem.Sci, 109,4737 (1987); TakuzoAida, Shohei Inoue, Yuikigoseikagaku (Japanese), 43,300 (1985); And D.Y.Sogoh, W.R.Hertler etc., Macromolecules, 20,1473 (1987).

The block A that constitutes the spreading agent that the present invention uses and B block preferably be generally 1/99 or greater than 1/99 than (weight ratio), more preferably 5/95 or greater than 5/95, and be generally 80/20 or less than 80/20, more preferably 60/40 or less than 60/40, in as the A-B segmented copolymer of spreading agent and B-A-B segmented copolymer, all be like this.If this ratio outside above-mentioned scope, can not obtain satisfied thermal stability and dispersiveness simultaneously.

In the A-B segmented copolymer and B-A-B segmented copolymer that the present invention of every 1g uses, the amount of quaternary ammonium salt group generally is preferably 0.1～10 mM.If should measure outside above-mentioned scope, can not obtain satisfied thermal stability and dispersiveness simultaneously.These segmented copolymers can contain the amino that forms usually in their preparation process, its amine value is about 1～100mg-KOH/g.Alkalescence is amino carries out acid-base titration with acid, shows amine value with milligram numerical table of the KOH of corresponding acid value, determines amine value with this.

Although the acid value of segmented copolymer changed with the having or not with kind of acidic-group of performance acid value, segmented copolymer is general preferably to have 10mg-KOH/g or less than the low acid value of 10mg-KOH/g.Its with the weight-average molecular weight of polystyrene conversion preferably general 1,000 or greater than 1,000 and 100,000 or less than 100,000 scope in.The segmented copolymer that has less than 1,000 molecular weight shows low dispersion stabilization.Have those segmented copolymers that surpass 100,000 molecular weight and show low development capability and sharpness.

In the present invention, except the block copolymerization beyond the region of objective existence, preferably also contain phosphate dispersant.This improves the dissolubility when developing.

Phosphate can be any in one-level, secondary and the three grades of esters, but from the angle of dispersiveness, is preferably the one-level ester.In the locational example of structure with the phosphate bonding is the structure with terminal hydroxyl, typically is for example polyester construction such as polycaprolactone or for example polyether structure such as polyglycol.These also can be the multipolymers of polyester and polyethers.In addition, also can for example have two keys such as (methyl) acrylate, thereby form multipolymer with other free-radical polymerised compounds at an end of polyester chain and/or polyether chain.

Particularly, phosphate preferably has the part of following structural (3) expression.

For example prepare these phosphates according to the method for describing in public clear 50-22536 communique of spy and the clear 58-128393 communique of Te Kai.

The scope of the molecular weight Mw of described phosphate dispersant is generally 200 or greater than 200 and be generally 5,000 or less than 5,000, preferred 1,000 or less than 1,000.The purpose that adds phosphate dispersant is the solubleness of giving in the development, so not preferred too high molecular weight.

＜photopolymerization monomer 〉

For good light sensitivity, except light trigger, photosensitive polymer combination of the present invention preferably also comprises one or more photopolymerization monomer (optical polymerism compound).Photopolymerization monomer used in this invention comprises the compound with at least one ethylenic unsaturated group.The object lesson that each molecule has the compound of at least one ethylenic unsaturated group is (methyl) acrylic acid, (methyl) acrylic acid Arrcostab, vinyl cyanide, styrene and has the carboxylic acid of an ethylenic unsaturated link and the monoesters of polynary or monohydroxy alcohol.

In photopolymerization monomer, preferably use per molecule to have the multi-functional ethylenic monomer of two or more ethylenic unsaturated groups.The example of multi-functional ethylenic monomer is: the ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid; The ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid; Ester by the preparation of the esterification of for example polyol such as aliphatic polyhydroxy compound or aromatic polyhydroxy compounds and unsaturated carboxylic acid and polybasic carboxylic acid.

The example of the ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid is: the acrylate of aliphatic polyhydroxy compound, for example glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane trimethacrylate acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate and acrylic acid glyceride; The methacrylate of these compound correspondences, different is to replace acrylate with methacrylate; The itaconate of these compound correspondences, different is to replace acrylate with itaconate; The crotonates of these compound correspondences, different is to replace acrylate with crotonates; The maleate of these compound correspondences, different is to replace acrylate with maleate.

The example of the ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid is the acrylate and the methacrylate of aromatic polyhydroxy compounds, for example quinhydrones diacrylate, quinhydrones dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate and 1,2,3,-thrihydroxy-benzene triacrylate.

The always not single material of ester of the esterification preparation of polyol and unsaturated carboxylic acid and polybasic carboxylic acid, its representational example is the condensation product between acrylic acid, phthalic acid and the ethylene glycol; Condensation product between acrylic acid, maleic acid and the diethylene glycol; Condensation product between methacrylic acid, terephthalic acid (TPA) and the pentaerythrite; Condensation product between acrylic acid, hexane diacid, butylene glycol and the glycerine.

The useful example of multi-functional ethylenic monomer used in this invention is: polyurethane (methyl) acrylate, for example reaction product of (methyl) acrylate of (methyl) acrylate of polyisocyanate compounds and hydroxyl or polyisocyanate compounds and polyvalent alcohol and hydroxyl; Epoxy acrylate, for example multivalence epoxy compound and hydroxyl (methyl) acrylate or (methyl) acrylic acid addition product; Acrylamide, for example ethene bisacrylamide; Allyl ester, for example diallyl phthalate; The compound that contains vinyl, for example phthalic acid divinyl ester.

Other component of＜photosensitive polymer combination 〉

Except said components, if suitable, photosensitive polymer combination of the present invention can also comprise for example organic solvent, adhesion promoter, coating improver, development improver, ultraviolet light absorber, antioxidant and/or silane coupling agent.

(1) organic solvent

Representative examples of organic is including, but not limited to Di Iso Propyl Ether, Mineral spirits, normal heptane, amyl ether, ethyl caprilate, normal hexane, diethyl ether, isoprene, the ethyl isobutyl ether, butyl stearate, normal octane, Varsol #2, Apco #18 solvent, diisobutylene, pentyl acetate, butyl butyrate, Apco thinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal Sovent No.1 and No.2, amyl formate, two hexyl ethers, diisopropyl ketone, Solvesso#150, acetate (just, secondary, uncle) butyl ester, hexene, Shell TS28 solvent, chlorobutane, ethyl pentyl group ketone, ethyl benzoate, chloropentane, ethylene glycol diethyl ether, ethyl orthoformate, the methoxy pentanone, methyl butyl ketone, methohexitone, methyl isobutyrate, benzonitrile, ethyl propionate, methylcellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, pentyl acetate, amyl formate, the connection cyclohexane, the diethylene glycol monoethyl ether acetate, cinene, the methoxy amylalcohol, methyl amylketone, methyl isopropyl Ketone, propyl propionate, the glycol tertiary butyl ether, MEK, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, the propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid esters, propylene glycol monoethyl ether, ethoxy propyl acetate, dipropylene glycol one ether, the dipropylene glycol monomethyl ether, ethoxy propyl acetate, dipropylene glycol monomethyl ether acetic acid esters, the 3-methoxypropionic acid, the 3-ethoxy-propionic acid, the 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, the dipropylene glycol monomethyl ether, the acetate glycol ester, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether (EGMBE), the glycol tertiary butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether and acetate 3-methyl-3-methoxyl butyl ester.

Preferential selection can be with have 100～250 ℃ of single components dissolved or dispersion, more preferably the solvent of the boiling point in 120～170 ℃ of scopes.Can be individually or use in these each in combination.

(2) silane coupling agent

Can add silane coupling agent to improve adhesiveness to substrate.Can use plurality of silane coupling agents, for example epoxies, methacrylic and amino one type of silane coupling agent, wherein preferred epoxies silane coupling agent.

The preparation method of＜photosensitive polymer combination 〉

Prepare photosensitive polymer combination of the present invention according to known method.

The photosensitive color resin combination that for example contains coloured material with the following manner preparation.At first, weigh up a certain amount of coloured material, solvent and spreading agent, the dispersion staining material forms liquid coloured composition (printing ink sample liquid) in the dispersion treatment process.In the dispersion treatment process, can use coating preparer, sand mill, bowl mill, roll kneader, stonebreaker, jet mill and/or homogenizer.Generate fine grain coloured material by dispersion treatment, thereby improve the coating of photosensitive color resin combination and the transmittance of improvement product filter substrate.

In the dispersion of coloured material, can use aforementioned bases dissolubility unsaturated polyester in combination.In the situation of disperseing with sand mill, the preferred use has beaded glass or the zirconium oxide bead of 0.1mm to several mm dias.The temperature that generally makes dispersion treatment in 0～100 ℃ scope, preferred room temperature to 80 ℃.Because suitable jitter time generally changes with the composition (coloured material, solvent and spreading agent) and the size of sand mill of printing ink sample liquid, so must set jitter time suitably.

The printing ink sample liquid of dispersion process preparation is mixed with solvent, alkali solubility unsaturated polyester, light trigger and other component that needs, form equal phase dispersant liquid.Since disperse and mixed process in thin contamination by dust is arranged, so the photosensitive color resin combination that obtains preferably uses filtrator etc. to filter.

The photosensitive polymer combination that does not contain coloured material can be with the preparation method's of above-mentioned photosensitive color resin combination program preparation, and different is mixes each component and the dispersion treatment of not carrying out coloured material.

The amount of component in the＜photosensitive polymer combination 〉

Total solids content with respect to photosensitive polymer combination of the present invention, the amount of alkali solubility unsaturated polyester is generally 10 weight % or greater than 10 weight %, preferred 20 weight % or greater than 20 weight %, and be generally 80 weight % or less than 80 weight %, preferred 70 weight % or less than 70 weight %.When photosensitive polymer combination of the present invention is when containing the photosensitive color resin combination of coloured material, the ratio of alkali solubility unsaturated polyester and coloured material is at general 5 weight % or greater than 5 weight %, preferred 10 weight % or greater than 10 weight %, and general 500 weight % or less than 500 weight %, in preferred 200 weight % or the scope less than 200 weight %.The too low content of alkali solubility unsaturated polyester will make the solubleness of unexposed portion in developer solution reduce, and cause poor visualization.On the contrary, too high content is difficult to obtain the pixel of ideal thickness.

Term among the present invention " total solids content " is meant and desolventizes all outer other components.The total solids content of photosensitive polymer combination of the present invention is generally 10 weight % or greater than 10 weight % to 90 weight % or less than 90 weight %.

If adding light trigger, then with respect to the total solids content of photosensitive polymer combination of the present invention, the content of light trigger is generally 0.1 weight % or greater than 0.1 weight %, preferred 0.5 weight % or greater than 0.5 weight %, more preferably 0.7 weight % or greater than 0.7 weight %, and be generally 30 weight % or less than 30 weight %, preferred 20 weight % or less than 20 weight %.The too low content of light trigger will make light sensitivity reduce.On the contrary, too high content will make the solubleness of unexposed portion in developer solution reduce, and usually cause poor visualization.

If the adding coloured material, then with respect to the total solids content of photosensitive polymer combination of the present invention, the content of coloured material is selected from the scope of 1 weight %～70 weight % usually.In this scope, this content is 10 weight %～70 weight % more preferably, wherein preferred especially 20 weight % or greater than 20 weight % to 60 weight % or less than 60 weight %.The too low content of coloured material will cause the too big layer thickness with respect to colour saturation, and this will be unfavorable for for example clearance control when making liquid crystal cell.On the contrary, too high content can not provide sufficient pattern formation property.

If with polyurethane dispersant [1] as the spreading agent that is selected from the spreading agent of nitrogen atom, then with respect to the coloured material component in the photosensitive color resin combination, the content of polyurethane dispersant [1] is generally 10 weight % or greater than 10 weight %, preferred 20 weight % or greater than 20 weight %, preferred especially 30 weight % or greater than 30 weight %, and be generally 300 weight % or less than 300 weight %, preferred 100 weight % or less than 100 weight %, preferred especially 80 weight % or less than 80 weight %.If the content of the spreading agent of nitrogen atom is too low, then the adsorption coloring agent is to prevent gathering fully for spreading agent, and the composition that obtains is crossed sticking or gelation.On the contrary, if this too high levels, then layer thickness is excessive, when this will and make liquid crystal cell after said composition forms color filter, causes the control of cel-gap bad.

If graft copolymer [2] is as spreading agent, then with respect to the coloured material component in the photosensitive color resin combination, the content of graft copolymer [2] is generally 10 weight % or greater than 10 weight %, preferred 20 weight % or greater than 20 weight %, preferred especially 30 weight % or greater than 30 weight %, and be generally 300 weight % or less than 300 weight %, preferred 100 weight % or less than 100 weight %, preferred especially 80 weight % or less than 80 weight %.If the spreading agent components contents is low excessively, then spreading agent fully the adsorption coloring agent assemble preventing, and the composition that obtains is crossed sticking or gelation.On the contrary, if this too high levels, then layer thickness is excessive, after composition forms color filter and when making liquid crystal cell, causes the control of cel-gap bad.

If segmented copolymer [3] is as spreading agent, then with respect to the coloured material component in the photosensitive color resin combination, the content of segmented copolymer [3] is generally 10 weight % or greater than 10 weight %, preferred 20 weight % or greater than 20 weight %, preferred especially 30 weight % or greater than 30 weight %, and be generally 300 weight % or less than 300 weight %, preferred 100 weight % or less than 100 weight %, preferred especially 80 weight % or less than 80 weight %.If the spreading agent components contents is low excessively, then spreading agent fully the adsorption coloring agent assemble preventing, and the composition that obtains is crossed sticking or gelation.On the contrary, if this too high levels, then layer thickness is excessive, after composition forms color filter and when making liquid crystal cell, causes the control of cel-gap bad.

With respect to 100 parts of block copolymer [3], the usage ratio of aforementioned phosphate dispersant is preferably general 5 weight portions or greater than 5 weight portions, preferred 10 weight portions or greater than 10 weight portions, and general 100 weight portions or less than 100 weight portions, preferred 80 weight portions or less than 80 weight portions.If the ratio of phosphate dispersant is low excessively, then in development, can not show sufficient solubleness.On the contrary, if this ratio is too high, then the effect of phosphate dispersant becomes saturated, and dispersiveness reduces on the contrary.

If the use photopolymerization monomer, then with respect to the total solids content of photosensitive polymer combination of the present invention, the content of photopolymerization monomer is generally 90 weight % or less than 90 weight %, preferred 80 weight % or less than 80 weight %.If the too high levels of photopolymerization monomer, then developer solution soaks into exposed portion excessively, thereby good pattern can not be provided.The lower limit of the content of photopolymerization monomer is generally 0 weight % or greater than 0 weight %, preferred 5 weight % or greater than 5 weight %.

The purposes of＜photosensitive polymer combination 〉

Photosensitive polymer combination of the present invention can be used the photosensitive polymer combination of pattern formation, black matrix", overlayer, rib wall and sept in the color filter with the liquid crystal board that acts on LCD.Except being used in the color filter, they also can install with encapsulant and photo-curable bonding agent with middle layer insulating medium, photonasty optical waveguide, photo-curable liquid crystal sealing material, photo-curable electroluminescence (EL) with anti-solder flux, resist plating, multilayer board as flexible printed circuit board.

[color filter]

Can be by on optical transparent substrate, forming black matrix", and form the image of general redness, green and blue pixel, thus prepare color filter of the present invention.Use contains the photosensitive color resin combination of the present invention of coloured material as forming at least a coating composition in black, redness, green, the blue resist.Form the pattern of pixels of every kind of color by each processing of coating, heat drying, pattern exposure, development and heat curing.With black resist-coating uncoated on glass to the optical transparent substrate.On red, the green or blue resist-coating resin black matrix to the optical transparent substrate, or be applied on the metal black matrix" that shading metal materials such as using chromium compound forms.Use and do not contain the photosensitive color resin combination of the present invention of coloured material as overlayer, rib wall and sept photosensitive polymer combination.

Aspect material, there is no particular limitation with optical transparent substrate to color filter, as long as it is optically transparent and has suitable intensity.Described examples of material is the sheet material of thermoplastic resin, comprises for example polyolefin resin, polycarbonate, polymethylmethacrylate and polysulfones such as vibrin, for example polypropylene and tygon such as polyethylene terephthalate; The sheet material of thermoset resin, for example epoxy resin, unsaturated polyester resin and poly-(methyl) acryl resin; With various glass.In them, from the angle of thermal stability, preferred glass and heat stable resin.

In order for example to improve Surface Physical performance such as adhesiveness, optical transparent substrate and the substrate with black matrix" can carry out Corona discharge Treatment, ozone treatment, with the processing of silane coupling agent and/or form the processing of resin films such as urethane resin for example.

The thickness of optical transparent substrate is generally at 0.05～10mm, in the scope of preferred 0.1～7mm.If the formation resin film, then the thickness of resin film is generally at 0.01～10 μ m, in the scope of preferred 0.05～5 μ m.

[1] black matrix"

Use shading metallic film or resin black matrix photosensitive color resin combination, on optical transparent substrate, form black matrix".The shading metal material comprises the alloy of chromium compound such as crome metal, for example chromium oxide and chromic nitrate for example and nickel and tungsten.Black matrix" can have and comprises sandwich construction multiple in these.

Generally form the shading metal film, use positive photoresist on this film, to form the film of required pattern with sputtering method.Use the etchant etching photoresist, peel off remaining positive photoresist with special remover, thereby obtain black matrix".In the situation of chromium, etchant used herein is ammonium ceric nitrate and the potpourri of crossing chloric acid and/or nitric acid, and in the situation of other material, the etchant of use is the etchant of selecting according to these materials.

In this case, can form black matrix" in the following manner.At first, on optical transparent substrate, form the film of metal or metal-metallic oxide with vapour deposition process or sputtering method etc.Then the film with the photosensitive color resin combination is applied on this film, uses the photomask with repeat patterns such as bar shaped, mosaic or triangles to make this film exposure, develops then, thereby forms the resist pattern.This film of etching then, thus black matrix" formed.

In the situation of resin black matrix, use the photosensitive color resin combination of the present invention that contains the black colorant material to form black matrix" with the photosensitive color resin combination.For example, use and contain the photosensitive color resin combination of black colorant material, thereby can form black matrix" with the formation redness of mentioning later, green and blue pixel method of patterning.The black colorant material can be one or more in the black colorant material, and for example carbon black, graphite, iron oxide black, nigrosine, cyanines are deceived and titanium is black; And the potpourri that is selected from the colorants such as redness, green and blueness of inorganic or organic pigment or dyestuff.

[2] pixel

Can form color filter pattern in the following manner.The film that will contain the photosensitive color resin combination of one of redness, green and blue-colored material is applied on the optical transparent substrate that is furnished with black matrix".After the drying, photomask is covered on this film, this film carries out pattern exposure, development by photomask, carries out heat curing or photocuring as required again, thereby forms the dyed layer of pattern of pixels.Each of promptly red, the green and blue photosensitive color resin combination of three kinds of colors is repeated this program, thereby form color filter pattern.

(2-1) coating process

Be coated with coating photosensitive color resin composition for color such as method (die coating), rolling method or spraying process with spin-coating method, the excellent rubbing method that winds the line, showering (flow coating), mould.In them, in general,, to avoid the influence of hazing that takes place in the spin coating, thereby reduce production of foreign matters in order to reduce the amount of coating composition significantly, preferred mould is coated with method.

The undue senior general of the thickness of coated film makes the clearance control difficulty in pattern development and the liquid crystal cell preparation.Too little thickness can not increase pigment concentration and prepare the color that needs.The thickness of dried coated film preferably in the scope of general 0.2～20 μ m, more preferably 0.5～10 μ m, further preferred 0.8～5 μ m.

(2-2) drying means

Preferably use the coated film of the photosensitive color resin combination on the method dry substrate that uses electric hot plate, infrared ray (IR) baking oven or convection oven.Can select drying condition suitably according to performance of the exsiccator of the kind of solvent composition and use etc.Can select drying time suitably according to performance of the exsiccator of the kind of solvent composition and use etc.Preferred dry 15 second～5 minute under 40～200 ℃ temperature, dry 30 second～3 minute under preferred 50～130 ℃ temperature.

Along with the raising of baking temperature, coated film increases the adhesiveness of optical transparent substrate.But baking temperature is too high, will cause that binder resin decomposes and thermal polymerization, causes poor visualization.The dry run of coated film drying under reduced pressure with can not raising temperature in vacuum chamber.

(2-3) exposure method

The negativity mask pattern is overlayed on the coated film of photosensitive color resin combination, apply for example light of light source such as ultraviolet ray and visible light by mask pattern, thereby carry out the exposure of pattern.If desired, expose after for example on the optical polymerism coated film, forming oxygen separation layer such as polyvinyl alcohol layer, to prevent the photonasty of optical polymerism layer being reduced because of the effect of oxygen.Being used in light source in the pattern exposure comprises but is not defined in especially: lamp source, for example xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc lamp and fluorescent light; LASER Light Source, for example Argon ion laser, YAG (yttrium aluminum garnet) laser instrument, excimer laser, nitrogen laser, helium cadmium laser and semiconductor laser.For the irradiation of the light of using specific wavelength, can use optical filter.

(2-4) developing method

Use above-mentioned light source that the coated film of photosensitive color resin combination is carried out pattern exposure, with an organic solvent or the aqueous solution that contains surfactant and alkali compounds the film of exposure is developed, thereby on substrate, form pattern, can make color filter of the present invention thus.Described aqueous solution can also comprise organic solvent, buffering agent, complexing agent, dyestuff and/or pigment.

The example of alkali compounds (alkali cpd) is: inorganic alkaline compound, for example NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide; Organic basic compound, for example monoethanolamine, diethanolamine or triethanolamine, monomethyl amine, dimethylamine or trimethylamine, monoethyl amine, diethylamine or triethylamine, Mono Isopropylamine or diisopropylamine, n-butylamine, an isopropanolamine, diisopropanolamine or triisopropanolamine, ethylene imine (ethyleneimine), ethylenediamine (ethylenediimine), tetramethyl ammonium hydroxide (TMAH) and choline.Can be used as potpourri and use these alkali compounds in combination.

The example of surfactant is: non-ionic surfactant, for example polyethylene oxide alkyl ethers, polyoxyethylene alkyl aryl ether, polyoxyethylene Arrcostab, alkyl sorbitol dehydration ester and monoglyceride Arrcostab; Anionic surfactant, for example alkyl benzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate and sulfosuccinate ester salt; And amphoteric surfactant, for example alkyl betaine and amino acid.

Representative examples of organic is isopropyl alcohol, benzylalcohol, ethyl Cellosolve, butyl Cellosolve, phenyl Cellosolve, propylene glycol and diacetone alcohol.Can use described organic solvent individually or as potpourri with aqueous solution.

There is no particular limitation to development conditions.Development temperature in general 10～50 ℃ scope, preferred 15～45 ℃, preferred especially 20～40 ℃.For example can adopt any means such as immersion development, spray development, brushing development or ultrasound wave development to develop.

(2-5) thermal curing methods

Filter substrate after the development carries out heat curing.Select the heat curing condition to make temperature, and in preferred 150～250 ℃ scope, be 5～60 minutes set time at 100～280 ℃.Prepare monochromatic pattern by this a series of step.Repeat these steps successively, form black, redness, green and blue pattern, thereby form color filter.The order that forms the pattern of four kinds of colors is not limited to said sequence.

(2-6) method of formation transparency electrode

Form on pattern after the ITO transparency electrodes such as (tin indium oxides), color filter can be as the part of the parts in color monitor and the LCD.When needing, before forming transparency electrode, the top coat that forms polyamide or polyimide on pattern is to improve surface smoothness and/or permanance.Do not form transparency electrode in some purposes for example waiting in plane orthotype drive system (in the face switch (IPS) pattern).

[3] sept

When photosensitive polymer combination of the present invention is used photosensitive polymer combination as sept, generally form sept in the following manner.Specifically, the photosensitive polymer combination that will dissolve or be dispersed in the solvent with methods such as coatings is applied on the substrate of arrangement interval thing with the form of film or pattern, then dry solvent.When with the form coating composition of film, if desired, make film form pattern with the photoetching process that comprises exposure and develop etc.If desired, then carry out heat curing, thereby on this substrate, form sept.

(3-1) be applied to the method for substrate

Photosensitive polymer combination of the present invention generally is applied on the substrate with solution in solvent or dispersion liquid.Can be coated with known method coating compositions such as method, rolling method or spraying process according to for example spin-coating method, the excellent rubbing method that winds the line, curtain coating, mould.Alternatively, said composition can be coated with into pattern by ink-jet method or print process etc.In them, in general,, to avoid the influence of hazing that takes place in the spin coating, thereby reduce production of foreign matters in order to reduce the amount of coating composition significantly, preferred mould is coated with method.

The coating weight of composition (amount of coating) changes with purposes.For example in the situation of sept, in drying layer thickness, this amount is generally 0.5 μ m or greater than 0.5 μ m, preferred 1 μ m or greater than 1 μ m, and be generally 10 μ m or less than 10 μ m, preferred 8 μ m or less than 8 μ m, preferred especially 5 μ m or less than 5 μ m.Importantly the height of the thickness of desciccator diaphragm or the sept that obtains is uniform on whole base plate.If it changes significantly, the product liquid crystal board will have uneven defective.

(3-2) drying means

After being applied to photosensitive polymer combination on the substrate, the preferred employing uses the drying means of electric hot plate, infrared-ray oven or convection oven to carry out drying.Can use the drying under reduced pressure method of in vacuum chamber (temperature does not raise) in combination.Select drying condition suitably according to performance of the exsiccator of the kind of solvent composition and use etc.Performance according to the kind of solvent composition and the exsiccator of use etc. is selected drying time suitably.General under 40～100 ℃ temperature dry 15 second～5 minute, dry 30 second～3 minute under preferred 50～90 ℃ temperature.

(3-3) exposure method

The negativity mask pattern is overlapped on the coated film of photosensitive color resin combination, apply for example light of light source such as ultraviolet ray and visible light, perhaps carry out the exposure of pattern by laser scanning exposure by mask pattern.If desired, expose after for example on the optical polymerism layer, forming oxygen separation layer such as polyvinyl alcohol layer, to prevent the photonasty of optical polymerism layer being reduced because of the effect of oxygen.Being used in light source in the pattern exposure comprises but is not defined in especially: lamp source, for example xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc lamp and fluorescent light; LASER Light Source, for example Argon ion laser, YAG laser instrument, excimer laser, nitrogen laser, helium cadmium laser, blue violet semiconductor laser and near infrared semiconductor laser.For the irradiation of the light of using specific wavelength, can use optical filter.

(3-4) developing method

After carrying out above-mentioned exposure, can use the aqueous solution or the organic solvent that contain surfactant and alkali compounds to develop, thereby on substrate, form the pattern of image.Described aqueous solution can also comprise organic solvent, buffering agent, complexing agent, dyestuff and/or pigment.

The example of alkali compounds is: inorganic alkaline compound, for example NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide; Organic basic compound, for example monoethanolamine, diethanolamine or triethanolamine, monomethyl amine, dimethylamine or trimethylamine, monoethyl amine, diethylamine or triethylamine, Mono Isopropylamine or diisopropylamine, n-butylamine, an isopropanolamine, diisopropanolamine or triisopropanolamine, ethylene imine, ethylenediamine, tetramethyl ammonium hydroxide (TMAH) and choline.Can be used as potpourri and use these alkali compounds in combination.

The example of surfactant is: non-ionic surfactant, for example polyethylene oxide alkyl ethers, polyoxyethylene alkyl aryl ether, polyoxyethylene Arrcostab, alkyl sorbitol dehydration ester and monoglyceride Arrcostab; Anionic surfactant, for example alkyl benzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl sulfonate and sulfosuccinate ester salt; And amphoteric surfactant, for example alkyl betaine and amino acid.

Representative examples of organic is isopropyl alcohol, benzylalcohol, ethyl Cellosolve, butyl Cellosolve, phenyl Cellosolve, propylene glycol and diacetone alcohol.Can be individually or use described organic solvent with the potpourri of aqueous solution.

(3-5) thermal curing methods

Substrate after the development preferably carries out heat curing.About the condition of heat curing, temperature is selected from the scope at 100～280 ℃, and preferred 150～250 ℃, thermal curing time is selected from the scope at 5～60 minutes.

[4] rib wall (projection that liquid crystal is cut apart and is orientated)

Rib wall (projection that liquid crystal is cut apart and is orientated) is meant the projection that is arranged on the transparency electrode with the visual angle of improving LCD.They use the inclined-plane of projection that liquid crystal is tilted partly, thereby cut apart liquid crystal on a plurality of directions in a pixel.At length explain the method that forms the rib wall below.

(4-1) coating and developing method

More than Zhi Bei optical transparent substrate generally has the thickness of 0.1mm～2mm, is loaded with black matrix" and redness, blueness and green color filter, has the ITO layer of the thick 150nm that vapour deposition forms on black matrix" and color filter.For example using, spinner, the excellent spreader that winds the line, showering device, mould are coated with apparatus for coating such as device, print roll coating device or sprayer photosensitive polymer combination of the present invention are applied on the ITO layer.Said composition generally is applied to the layer thickness of 0.5 μ m～5 μ m.The formed coated film of dry said composition is placed on photomask on the dry film, carries out the imaging exposure by photomask.After exposure, remove unexposed and uncured part by development, thereby form pixel.The pattern that obtains as developing result must have 5 μ m～wide line reproducibility of 20 μ m, in order to obtain having the display of high image quality, tends to require to have meticulousr line reproducibility.Preferably, in order stably to reproduce fine rule accurately, the section of the thread pattern after the development is at the tangible rectangle of the contrast of non-pattern part and pattern part.This rectangular cross section shape shows wide development nargin (margin) over time with on the physical stimulation of development sprinkler at development time, developer solution.

(4-2) heating means

According to the present invention, the pattern after the development has approximate section configuration apart from shape.In order to obtain the arcuate rib wall, make pattern generally at 150 ℃ or be higher than under 150 ℃ the temperature and heat-treat, preferred 180 ℃ or be higher than 180 ℃, more preferably 200 ℃ or be higher than 200 ℃, and general 400 ℃ or be lower than 400 ℃, preferred 300 ℃ or be lower than 300 ℃, more preferably 280 ℃ or be lower than 280 ℃, heat treatment time was generally 10 minutes or greater than 10 minutes, preferred 15 minutes or greater than 15 minutes, more preferably 20 minutes or greater than 20 minutes, and be generally 120 minutes or be lower than 120 minutes, preferred 60 minutes or be lower than 60 minutes, more preferably 40 minutes or be lower than 40 minutes.Like this, the section configuration of rectangle is deformed into arc, thereby obtains having the rib wall of the height of the width of 0.5 μ m～20 μ m and 0.2 μ m～5 μ m.Distortion when composition by regulating photosensitive polymer combination and heating condition are controlled heating, make that the W1/W2 ratio is 1.2 or greater than 1.2, preferred 1.3 or greater than 1.3, more preferably 1.5 or greater than 1.5, and be generally 10 or less than 10, preferred 8 or less than 8, wherein W1 is the contact angle that forms between the side of the thread pattern (pattern with rectangular cross section shape) before the heating and the base plan; W2 is the contact angle that forms between the side of thread pattern after the heating and the base plan.Deformation ratio raises with heating-up temperature or increases heat time heating time.On the contrary, deformation ratio reduces or reduces heat time heating time with heating-up temperature.

[LCD]

Generally by forming oriented layer on color filter, arrangement interval thing on oriented layer is attached to this substrate and forms liquid crystal cell on the opposing substrate, with liquid crystal filling liquid crystal box be connected on the electrode of opposite, thereby prepares the product LCD.Oriented layer is preferably for example film of resin such as polyimide.Generally form the oriented layer of tens nanometer thickness by photogravure and/or hectographic printing.Fire by heating oriented layer is solidified, carry out for example ultraviolet ray irradiation or with surface treatments such as cleaning wiping cloth processing, so that have the surface that to control the liquid crystal gradient.

Sept should have the size corresponding to the gap between filter substrate and the opposing substrate (slit), preferably has the size of general 2 μ m～8 μ m.Can use with above-mentioned same way as, on filter substrate, form the light spacer (PS) of optical clear resin molding, replace described sept with this light spacer by photoetching.Described opposing substrate is generally array (array) substrate, preferred TFT (thin film transistor (TFT)) substrate.

And the gap that forms between the opposing substrate changes with the purposes of LCD, generally selects in the scope of 2 μ m～8 μ m.With opposing substrate with after filter substrate aligns, with the other parts beyond the encapsulant encapsulated liquid crystals inlets such as for example epoxy resin.With ultraviolet ray (UV) irradiation and/or heating encapsulant is solidified, thus the periphery of encapsulated liquid crystals box.

The liquid crystal cell that will have seal perimeter cuts into display board, and each display board reduces pressure in vacuum chamber, and inlet is immersed in the liquid crystal, vacuum chamber is leaked, thereby liquid crystal is injected liquid crystal cell.Decompression in the liquid crystal cell is generally 1 * 10 ^-2～1 * 10 ^-7Pa, and be preferably 1 * 10 ^-3～1 * 10 ^-6Pa.Preferably decompression under heating of liquid crystal cell, heating-up temperature is generally at 30～100 ℃, more preferably 50～90 ℃.Liquid crystal cell is generally under reduced pressure kept heating 10～60 minutes, is immersed in the liquid crystal then.The uv curing resin of the inlet of the liquid crystal cell that injects liquid crystal is solidified, sealing, thus obtain product LCD (plate).

There is no particular limitation on type for liquid crystal, can be selected from conventional liquid crystal, and for example aromatic series, aliphatics or fused ring compound can be any in lyotropic liquid crystal and the thermotropic liquid crystal for example.Known thermotropic liquid crystal comprises nematic crystal, smectic crystal and cholesteryl liquid crystal, can use any here.

[embodiment]

Explain the present invention in more detail below with reference to synthesis example, embodiment and Comparative Examples, but as long as without departing from the spirit and scope of the present invention, the present invention is in no way limited to following examples.After this, all " parts " are meant " weight portion ".

[synthesizing of alkali solubility unsaturated polyester]

＜synthesis example 1 〉

The flask that thermometer, condenser pipe and stirrer are housed is carried out nitrogen purging, and with 100 part 5,5 '-(1-methyl ethidine) two [2-cyclohexylphenol] (following formula (1)) and 700 portions of chloropropylene oxides are placed on wherein, form solution.This solution is heated to 65 ℃, with adding 11 parts of NaOH in 90 minutes several times, then 65 ℃ of reactions 2 hours and 70 ℃ of reactions 1 hour down down.After reaction is finished, under 130 ℃, steam chloropropylene oxide, wash residue with water three times, thereby obtain the epoxy compound of following formula (2) expression.The epoxy compound that obtains is a white powder, has the epoxide equivalent of 257g/eq.

Formula (1)

Formula (2)

In a reactor, put into the epoxy compound for preparing above 100 parts, 29 parts of acrylic acid, 0.06 part of p methoxy phenol, 2.6 parts of triphenylphosphines and 126 parts of propylene glycol methyl ether acetates, down stirred these potpourris 2 hours at 120 ℃, stir down up to reaction mixture at 95 ℃ again and have 5mg-KOH/g or less than the acid value of 5mg-KOH/g.Reaction mixture need reach this target acid value (acid value: 4.0) in 10 hours.

＜synthesis example 2 〉

In the reaction mixture that 257 parts of synthesis examples 1 obtain, add 60 parts of propylene glycol methyl ether acetates and 10.7 parts of hexamethylene diisocyanates successively, then reacted 3 hours down at 90 ℃.Reaction mixture mixes with 28.5 parts of trihemellitic acid acid anhydrides again, then 90 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-I), the weight-average molecular weight of 2580 the usefulness polystyrene conversion that it has that 96 acid value and GPC measure.

＜synthesis example 3 〉

In the reaction mixture that 80 parts of synthesis examples 1 obtain, add 15 parts of propylene glycol methyl ether acetates and 9.6 parts of biphenyltetracarboxyacid acid dicarboxylic anhydrides successively, then reacted 2 hours down at 120 ℃.Reaction mixture mixes with 5 parts of tetrabydrophthalic anhydrides again, then 95 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-II), 3700 the weight-average molecular weight by polystyrene conversion that it has that 106 acid value and GPC measure.

＜synthesis example 4 〉

In a reactor, put into 100 parts of bisphenol-A epoxy compounds (following formula (3), the epoxide equivalent of 186g/eq), 40 parts of acrylic acid, 0.06 part of p methoxy phenol, 2.4 parts of triphenylphosphines and 126 parts of propylene glycol methyl ether acetates, stir down up to reaction mixture at 95 ℃ and to have 5mg-KOH/g or less than the acid value of 5mg-KOH/g.Reaction mixture need reach target acid value (acid value: 1.0) in 10 hours.Then, reaction mixture mixes with 40 parts of propylene glycol methyl ether acetates, mixes with 19.5 parts of isophorone diisocyanate then, then reacts 3 hours down at 90 ℃.Reaction mixture mixes with 39.3 parts of trihemellitic acid acid anhydrides again, then 90 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-III), 2400 the weight-average molecular weight by polystyrene conversion that it has that 113 acid value and GPC measure.

Formula (3)

＜synthesis example 5 〉

In a reactor, put into 100 parts of bisphenol-A epoxy compounds (following formula (3), the epoxide equivalent of 186g/eq), 40 parts of acrylic acid, 0.06 part of p methoxy phenol, 2.4 parts of triphenylphosphines and 126 parts of propylene glycol methyl ether acetates, stir down up to reaction mixture at 95 ℃ and to have 5mg-KOH/g or less than the acid value of 5mg-KOH/g.Reaction mixture need reach target acid value (acid value: 1.0) in 10 hours.Then, this reaction mixture mixes with 40 parts of propylene glycol methyl ether acetates and 17.5 parts of isophorone diisocyanate successively, then reacts 3 hours down at 90 ℃.Reaction mixture mixes with 46.8 parts of trihemellitic acid acid anhydrides again, then 90 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-IV), 2840 the weight-average molecular weight by polystyrene conversion that it has that 136 acid value and GPC measure.

＜synthesis example 6 〉

In a reactor, put into 100 parts of fluorenes bisphenol epoxies compound (following formulas (4), 90.5), 0.19 part of p methoxy phenol, 7.4 parts of triphenylphosphines and 368 parts of propylene glycol methyl ether acetates the epoxide equivalent of 231g/eq), (acid value:, stir down up to reaction mixture at 90 ℃ and to have 5mg-KOH/g or of the reaction mixture between 273.2 parts succinic anhydride and three (acryloyl-oxy ylmethyl) ethanol less than the acid value of 5mg-KOH/g.Reaction mixture need reach target acid value (acid value: 1.0) in 10 hours.Then, in 80 parts of reaction mixtures that obtain, add 6 parts of propylene glycol methyl ether acetates and 2.6 parts of isophorone diisocyanate successively, then reacted 3 hours down at 90 ℃.Reaction mixture mixes with 4.1 parts of trihemellitic acid acid anhydrides again, then 90 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-V), 2949 the weight-average molecular weight by polystyrene conversion that it has that 57 acid value and GPC measure.

Formula (4)

＜synthesis example 7 〉

In a reactor, put into 100 parts of fluorenes bisphenol epoxies compound (following formulas (4), 90.5), 0.19 part of p methoxy phenol, 7.4 parts of triphenylphosphines and 368 parts of propylene glycol methyl ether acetates the epoxide equivalent of 231g/eq), (acid value:, stir down up to reaction mixture at 90 ℃ and to have 5mg-KOH/g or of the reaction mixture between 273.2 parts succinic anhydride and three (acryloyl-oxy ylmethyl) ethanol less than the acid value of 5mg-KOH/g.Reaction mixture need reach target acid value (acid value: 1.0) in 10 hours.Then, in 80 parts of reaction mixtures that obtain, add 6 parts of propylene glycol methyl ether acetates and 1.9 parts of hexamethylene diisocyanates successively, then reacted 3 hours down at 90 ℃.Reaction mixture mixes with 3.8 parts of trihemellitic acid acid anhydrides again, then 90 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-VI), 3113 the weight-average molecular weight by polystyrene conversion that has that 52 acid value and GPC measure.

＜synthesis example 8 〉

In a reactor, put into " XD-1000 " (poly epihydric alcohol base ether of the polymerizate between dicyclopentadiene and the phenol of 75.1 parts of Japanese chemical drug society systems, have 700 weight-average molecular weight and the epoxide equivalent of 252g/eq), bisphenol epoxies compound (formula (2)), 43.8 parts of acrylic acid, 0.06 part of p methoxy phenol, 2.4 parts of triphenylphosphines and 136.8 parts of propylene glycol methyl ether acetates of 76 parts of synthesis examples 1 synthetic preparations, stir down up to reaction mixture at 100 ℃ and to have 3.0mg-KOH/g or less than the acid value of 3.0mg-KOH/g.Reaction mixture need reach target acid value (acid value: 2) in 12 hours.Then, this reaction mixture mixes with 197 parts of propylene glycol methyl ether acetates, 22.6 parts of isophorone diisocyanate and 0.02 part of dibutyl tin laurate successively, then reacts 3 hours down at 90 ℃.Reaction mixture mixes with 29.4 parts of tetrabydrophthalic anhydrides and 33.7 parts of trihemellitic acid acid anhydrides again, then reacted 4 hours down at 90 ℃, thereby obtain alkali solubility unsaturated polyester (A-VII), 4000 the weight-average molecular weight that it has that 100 acid value and GPC measure by polystyrene conversion.

＜synthesis example 9 〉

In a reactor, put into bis-phenol (following formula (1)), 56.6 parts of glycidyl methacrylate, 0.06 part of p methoxy phenol, 2.6 parts of triphenylphosphines and 126 parts of propylene glycol methyl ether acetates of 77.7 parts synthesis example 1 use, then reacted 15 hours down, obtain reaction mixture at 100 ℃.

In 263 parts of reaction mixtures, add 60 parts of propylene glycol methyl ether acetates and 10.7 parts of hexamethylene diisocyanates successively, then reacted 3 hours down at 90 ℃.Reaction mixture mixes with 28.5 parts of trihemellitic acid acid anhydrides again, then 90 ℃ of reactions 3 hours down, thereby obtains alkali solubility unsaturated polyester (A-VIII), 2300 the weight-average molecular weight by polystyrene conversion that it has that 95 acid value and GPC measure.

[evaluation that black matrix" forms]

＜embodiment 1 〉

With 218 weight portion propylene glycol methyl ether acetates and 60 weight portions (in solids content, 30 weight portions) solution of the alkali solubility unsaturated polyester (A-I) of synthesis example 1 preparation, 10 weight portion dipentaerythritol acrylates, 4 weight portions " CGI-242 " (can obtain from Ciba SpecialtyChemicals, have following structural) and 224 parts use the nitrogen containing polymer polyurethane dispersants (can obtain from BYK-Chemie Japan K.K., commodity are called " Disperbyk 182 ") carbon black dispersion liquid that disperses is (in solids content, 56 weight portions, comprise 43 weight portion carbon blacks and 13 weight portion macromolecule dispersing agents) mix the preparation photosensitive black-colored resin composition.

Described CGI-242 structure is as follows:

Use spin-coating method the photosensitive black-colored resin composition for preparing above to be applied on the square glass substrate of 10cm, on electric hot plate 90 ℃ of following dry 150 seconds.Dry layer has the thickness of 1 μ m.Then, use high-pressure sodium lamp to make this sample carry out the imaging exposure, be that the potassium hydroxide aqueous solution of 0.1 weight % carries out spray development with concentration under 23 ℃, thereby obtain black picture element (black matrix") by mask.

＜embodiment 2 〉

Program with embodiment 1 prepares photosensitive black-colored resin composition and forms black picture element, and different is to use alkali solubility unsaturated polyester (A-III) to replace alkali solubility unsaturated polyester (A-I).

＜embodiment 3 〉

Program with embodiment 1 prepares photosensitive black-colored resin composition and forms black picture element, and different is to use alkali solubility unsaturated polyester (A-VII) to replace alkali solubility unsaturated polyester (A-I).

＜embodiment 4 〉

Program with embodiment 1 prepares photosensitive black-colored resin composition and forms black picture element, and different is to use alkali solubility unsaturated polyester (A-VIII) to replace alkali solubility unsaturated polyester (A-I).

＜Comparative Examples 1 〉

Program with embodiment 1 prepares photosensitive black-colored resin composition and forms black picture element, and different is to use alkali solubility unsaturated polyester (A-II) to replace alkali solubility unsaturated polyester (A-I).

Estimate embodiment 1～4 and the photosensitive black-colored resin composition of Comparative Examples 1 preparation and the following performance of pixel, the result is illustrated in the table 1.

＜adhesiveness 〉

Under 200 times multiplying power, observe minimum pattern size with microscope at following the discernmible sample resist of exposure of the mask pattern that verily reproduces 20 μ m.Minimum pattern is of a size of 10 μ m or is evaluated as good adhesion less than the sample of 10 μ m, and it is inferior that the sample that the minimum pattern size surpasses 10 μ m is evaluated as adhesiveness.

＜pixel resolution 〉

Under 1000 times multiplying power, observe shape with microscope at following the discernmible sample fine rule black picture element of exposure of the mask pattern that verily reproduces 20 μ m.It is good that sample with satisfied rectilinear form is evaluated as pixel resolution, has projection and/or irregular sample resist pattern evaluation is that pixel resolution is inferior.

＜storage stability 〉

The sample photosensitive black-colored resin composition stored for 2 week under two different conditions of 35 ℃ and 10 ℃.The time of the film development of contrast unexposed portion.Development time changes 10% or to be evaluated as storage stability greater than 10% sample inferior, and development time changes that to be evaluated as storage stability less than 5% sample good, and development time changes that to be evaluated as storage stability less than 1% sample fine.

Table 1

Sample	The alkali solubility unsaturated polyester	Adhesiveness	Pixel resolution	Storage stability
					Embodiment 1	A-I	Well	Well	Fine
Embodiment 2	A-III	Well	Well	Fine
					Embodiment 3	A-VII	Fine	Well	Fine
Embodiment 4	A-VIII	Well	Well	Fine
					Comparative Examples 1	A-II	Well	Well	Inferior

Table 1 expression is used the photosensitive color resin combination of the present invention of specific alkali solubility unsaturated polyester to have excellent storage stability and to the adhesiveness of substrate, can be formed the pixel with good edge shape.

[evaluation that light spacer forms]

＜embodiment 5～9 and Comparative Examples 2 〉

(1) preparation of photosensitive polymer combination

In the alkali solubility unsaturated polyester that 100 parts of (solids content) tables 2 are listed, add 80 parts of dipentaerythritol acrylates (" KAYARADDPHA " of Japanese chemical drug (strain) system), the 3 parts of 2-methyl as light trigger-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone (from " Irgacure 907 " that Ciba-Geigy obtains), 0.01 part of fluorine surfactant (from Dainippon Ink as surfactant as polymerizable monomer; " the Magafac F475 " that Chemicals, Inc. obtain) and 5 parts of 3-glycidoxypropyltrimewasxysilane (from DowCorning Toray Co., " SH 6040 " that Ltd. obtains) as silane coupling agent.This potpourri is dissolved in the propylene glycol methyl ether acetate solid concentration to 35 weight %, filters with Millipore filtrator (0.2 μ m), thereby obtain photosensitive polymer combination.

(2) formation of spacer patterns

Use spinner this resin combination to be applied on the ITO film that is formed on the glass substrate, on electric hot plate 80 ℃ of following heat dryings 3 minutes to form film.In air atmosphere, use mask with predetermined pattern, use 32mW/cm in the distance of 365nm ²This film is shone in the ultraviolet ray of intensity, with 100mJ/cm ²Exposure.Then, the film of this irradiation carries out spray development with 0.1% potassium hydroxide aqueous solution under 23 ℃, and development time is the time of minimum development time twice, cleans 1 minute with pure water.Here " minimum development time " is meant the consoluet time of unexposed portion under identical development conditions.Remove unwanted part with these operations, thereby obtain the long and wide spacer patterns of 10 μ m of 10 μ m.Substrate with spacer patterns heats the resin solidification that made spacer patterns in 30 minutes down at 235 ℃ in baking oven.Like this, make the spacer patterns of height with 4 μ m.

[3] response rate and flexible evaluation

Use the dynamic ultra micro sclerometer in Tianjin, island (Shimadzu Dynamic Ultra Micro HardnessTester) " DUH-W201S ", determine the loading of the spacer patterns of preparation in " spacer patterns forms (2) " and the response rate of unloading by the loading-unloading test.In this test, use the plane pressure head of diameter with 50 μ m, with constant rate of speed (0.22gf/sec (gram force/second)) load is imposed on the sample room parting, pressure head was kept for 5 seconds under the load of 5gf, removed load with identical speed.This test is carried out under 23 ℃ temperature.Determine maximum displacement H[max shown in Figure 1 by this test] and last displacement H[last], calculate definite response rate according to following equation:

Response rate (%)=(H[max]-H[last])/H[max] * 100

The result is illustrated in the table 2.

In addition, the load N (gf) the when displacement under the load is 0.25 μ m is defined as elastic index, and the result is illustrated in the table 2.

The evaluation of load N (gf) when (4) displacement under the load is 0.25 μ m

The photosensitive polymer combination for preparing above stores 72 hours at 70 ℃ of lower seals, determines viscosity variation between the sample that this sample and room temperature place according to following equation.

Change (%)=[(70 ℃ of viscosity that store 72 hours sample down)-(viscosity of the sample of room temperature storage)]/[viscosity of the sample of room temperature storage] * 100

It is fine that change absolute value is evaluated as storage stability less than 3% sample, and it is good that change absolute value is evaluated as storage stability less than 5% sample, and change absolute value is 5% or to be evaluated as storage stability greater than 5% sample inferior.Storage stability descends with the increase of this changing value.

Table 2

Sample	The alkali solubility unsaturated polyester	Response rate (%)	Load N (gf) when the displacement under the load is 0.25 μ m	Storage stability
					Embodiment 5	A-I	49	0.45	Well
Embodiment 6	A-III	53	0.43	Well
					Embodiment 7	A-IV	47	0.34	Fine
Embodiment 8	A-V	56	0.53	Fine
					Embodiment 9	A-VI	51	0.52	Fine
Comparative Examples 2	A-II	49	0.45	Inferior

Table 2 expression uses the photosensitive polymer combination of the present invention of specific alkali solubility unsaturated polyester to have excellent storage stability, can obtain the sept that has excellent operability after the standing storage.

Although at length explained the present invention with reference to specific embodiments,, those skilled in the art can easily carry out many modifications and variations within the spirit and scope of the present invention.

The present invention is based on Japanese Patent Application 2004-272372 number and Japanese Patent Application 2005-208750 number of submission on July 19th, 2005 submitting on August 9th, 2004, and require to enjoy their right of priority, integrally introduce their disclosure here by reference.

Claims (18)

1. photosensitive polymer combination that comprises organic bond, wherein said organic bond comprises the alkali solubility unsaturated polyester, described alkali solubility unsaturated polyester be the epoxy compound (a) of per molecule with at least two epoxy radicals and the carboxylic acid (b) that contains unsaturated group reaction product with have the reaction product of the compound (c) of at least one isocyanate groups.

2. photosensitive polymer combination as claimed in claim 1, wherein said epoxy compound (a) comprise the compound of following general formula (I-a) expression:

Wherein, the X in the general formula (I-a) is represented by following general formula (II):

Wherein, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶Represent hydrogen atom independently of one another, have the alkyl of 1～12 carbon atom or have or do not have substituent phenyl, wherein, work as R ¹With R ²Be all alkyl and/or R ³With R ⁴When being all alkyl, R ¹With R ²And/or R ³With R ⁴Be combined into ring or be not combined into ring; N represents 0 or 1.

3. photosensitive polymer combination as claimed in claim 1, wherein said compound (c) has two or more isocyanate groups in per molecule.

4. photosensitive polymer combination as claimed in claim 2, the X in the wherein said general formula (I-a) be following general formula (IIA), (IIB) and (IIC) in any:

Wherein, at general formula (IIA), (IIB) with (IIC), R ¹～R ¹⁶With the n definition in the general formula (II) as described.

5. photosensitive polymer combination as claimed in claim 4, wherein said general formula (IIA) be following general formula (IIAa) and (IIAb) in one:

Wherein at general formula (IIAa) with (IIAb), R ¹And R ²Definition in the general formula (II) as described.

6. photosensitive polymer combination as claimed in claim 1, described photosensitive polymer combination also comprises light trigger.

7. photosensitive polymer combination as claimed in claim 1, described photosensitive polymer combination also comprises coloured material.

8. color filter, described color filter adopt the described photosensitive polymer combination of claim 1 to form.

9. LCD, described LCD has the parts that formed by the described photosensitive polymer combination of claim 1.

10. photosensitive polymer combination that comprises organic bond, wherein said organic bond comprises the alkali solubility unsaturated polyester, described alkali solubility unsaturated polyester be per molecule have the compound that contains phenolic hydroxyl (f) of at least two phenolic hydroxyls and contain unsaturated group epoxy compound (g) reaction product with have a reaction product of the compound (c) of at least one isocyanate groups.

11. photosensitive polymer combination as claimed in claim 10, the wherein said compound (f) that contains phenolic hydroxyl comprise the compound of following general formula (I-f) expression:

HO-X-OH …(I-f)

Wherein, the X in the general formula (I-f) is represented by following general formula (II):

Wherein, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵And R ¹⁶Represent hydrogen atom independently of one another, have the alkyl of 1～12 carbon atom or have or do not have substituent phenyl, wherein, work as R ¹With R ²Be all alkyl and/or R ³With R ⁴When being all alkyl, R ¹With R ²And/or R ³With R ⁴Be combined into ring or be not combined into ring; N represents 0 or 1.

12. photosensitive polymer combination as claimed in claim 10 has two or more isocyanate groups in wherein said compound (c) per molecule.

13. photosensitive polymer combination as claimed in claim 11, the X in the wherein said general formula (I-f) be following general formula (IIA), (IIB) and (IIC) in any:

Wherein at general formula (IIA), (IIB) with (IIC), R ¹～R ¹⁶With the definition in n such as the general formula (II).

14. photosensitive polymer combination as claimed in claim 13, wherein said general formula (IIA) be following general formula (IIAa) and (IIAb) in one:

Wherein at general formula (IIAa) with (IIAb), R ¹And R ²As the definition in the general formula (II).

15. photosensitive polymer combination as claimed in claim 10, described photosensitive polymer combination also comprises light trigger.

16. photosensitive polymer combination as claimed in claim 10, described photosensitive polymer combination also comprises coloured material.

17. a color filter, described color filter adopt the described photosensitive polymer combination of claim 10 to form.

18. a LCD, described LCD have the parts that formed by the described photosensitive polymer combination of claim 10.