JP4675246B2 - Colored alkali development type photosensitive resin composition and color filter using the same - Google Patents

Description

  The present invention relates to a colored alkali-developable photosensitive resin composition suitably used for producing a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a video camera and the like, and the colored alkali-developable photosensitive resin composition The present invention relates to a color filter using an object.

  The colored alkali-developable photosensitive resin composition comprises an alkali-developable resin composition containing a specific compound having an ethylenically unsaturated bond, a coloring material such as a pigment or a dye, and a photopolymerization initiator. It is. Since this colored alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, it is used in photocurable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like. ing. Recently, with the progress of miniaturization and high functionality of electronic devices, it is desired to form fine patterns with high accuracy.

  Regarding the alkali-developable resin composition and the alkali-developable photosensitive resin composition, the following Patent Document 1 proposes a photosensitive resin composition containing a prepolymer having an ethylenically unsaturated bond. Patent Document 2 below proposes a photosensitive resin composition containing an unsaturated group-containing polycarboxylic acid resin. However, these known alkali-developable photosensitive resin compositions have insufficient resolution and developability, and are suitable for colored alkali-developable photosensitive resin compositions using these alkali-developable photosensitive resin compositions. It was difficult to obtain pattern shapes and fine patterns. Therefore, a colored alkali development type photosensitive resin composition that is excellent in resolution and developability and can form a fine pattern with high accuracy has been desired.

JP 2000-235261 A JP 2000-355621 A

  As described above, the problem to be solved is that, as described above, there has not been a colored alkali development type photosensitive resin composition capable of obtaining an appropriate pattern shape and fine pattern with high resolution and excellent developability. is there.

  Accordingly, an object of the present invention is to provide a colored alkali-developable photosensitive resin composition that is excellent in sensitivity, resolution, developability, etc., and can form a fine pattern with high accuracy, and a color using the colored alkali-developable photosensitive resin composition. To provide a filter.

  In the present invention, polybasic acid anhydride (C) is esterified to an epoxy adduct having a structure in which unsaturated monobasic acid (B) is added to epoxy compound (A) represented by the following general formula (I). Containing the photopolymerizable unsaturated compound (X) having a structure obtained by adding the epoxy compound (D) to the reaction product obtained by the polymerization and further esterifying the polybasic acid anhydride (E) The object was achieved by providing a colored alkali-developable photosensitive resin composition characterized by further containing a photopolymerization initiator (F) and a colorant (G) in the alkali-developable resin composition. Is.

（式中、Ｃｙは炭素原子数３〜１０のシクロアルキル基を示し、Ｘは水素原子、フェニル基又は炭素原子数３〜１０のシクロアルキル基を示し、前記フェニル基又は炭素原子数３〜１０のシクロアルキル基は、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基若しくはハロゲン原子により置換されていてもよく、Ｙ及びＺは、それぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を示し、アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｎは０〜１０の数を示し、ｐは０〜４の数を示し、ｒは０〜４の数を表す。）

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group, or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group or 3 to 10 carbon atoms. The cycloalkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and Y and Z are each independently 1 carbon atom. Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted with a halogen atom, n represents a number from 0 to 10, p represents a number from 0 to 4, and r represents a number from 0 to 4.)

Further, the present invention is obtained by repeatedly adding the epoxy compound (D) to the photopolymerizable unsaturated compound (X) and then esterifying the polybasic acid anhydride (E) one or more times. A colored alkali development type characterized by further containing a photopolymerization initiator (F) and a colorant (G) in an alkali developable resin composition containing a photopolymerizable unsaturated compound (Y) having a structure as described above The above object is achieved by providing a photosensitive resin composition.
Moreover, this invention achieves the said objective by providing the color filter using the said colored alkali development type photosensitive resin composition.

  The colored alkali development type photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and developability, can form a fine pattern with high accuracy, and is suitable as a color filter.

  Hereinafter, the colored alkali development type photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

  The colored alkali-developable photosensitive resin composition of the present invention includes a photopolymerization initiator (F), a pigment, a dye, and the like in an alkali-developable resin composition containing the photopolymerizable unsaturated compound (X) or (Y). In particular, the epoxy compound (D) is further added to the photopolymerizable unsaturated compound (X) or the photopolymerizable unsaturated compound (X). Subsequently, the content of the photopolymerizable unsaturated compound (Y) having a structure obtained by repeating the esterification of the polybasic acid anhydride (E) at least once is determined by the above-described colored alkali development type photosensitive resin composition. 1 to 70% by mass in the product, and the content of the photopolymerization initiator (F) is 0.1 to 30% by mass in the colored alkali development type photosensitive resin composition. The content of G) is a solvent from the colored alkali development type photosensitive resin composition It is 0.5 to 70% by mass in the total solid components excluding.

The colored alkali-developable photosensitive resin composition of the present invention comprises an unsaturated monobasic acid (B) and an epoxy group of the epoxy compound (A) represented by the epoxy compound (A) represented by the general formula (I). Polybasic acid anhydride (C) with respect to an epoxy adduct having a structure in which a carboxyl group of the unsaturated monobasic acid (B) is added at a ratio of 0.1 to 1.0 with respect to one At a ratio of 0.1 to 1.0 acid anhydride structure with respect to one hydroxyl group of the epoxy adduct, and then the epoxy compound (D) to one hydroxyl group of the epoxy adduct. An epoxy group is added at a ratio of 0.1 to 1.0, and then the polybasic acid anhydride (E) is added in an acid anhydride structure of 0.1 to 1 with respect to one hydroxyl group of the epoxy compound. Contains a photopolymerizable unsaturated compound having a structure esterified at a ratio of 0.0 That.
The ratio of the carboxyl group of the unsaturated monobasic acid (B) to one epoxy group of the epoxy compound (A) is preferably 0.4 to 1.0. The ratio of the acid anhydride structure of the polybasic acid anhydride (C) to one hydroxyl group of the epoxy compound is preferably 0.3 to 0.95, and the epoxy group of the epoxy compound (D) The ratio of is preferably 0.3 to 0.9, and the ratio of the acid anhydride structure of the polybasic acid anhydride (E) is preferably 0.3 to 0.7.

In the general formula (I), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. .
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as the cycloalkyl group having 3 to 10 carbon atoms represented by Cy. As the phenyl group represented by X or the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the halogen atom which may be substituted with the cycloalkyl group having 3 to 10 carbon atoms, What is illustrated later as what is shown by Y and Z is mentioned.
Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl Octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y and Z include methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxy And propyl. Examples of the alkenyl group having 2 to 10 carbon atoms represented by Y and Z include vinyl, allyl, butenyl, propenyl, etc. Examples of the halogen atom represented by Y and Z include fluorine, chlorine, bromine and iodine. It is done.
In addition, the above-mentioned alkyl group and alkoxy group which may be substituted for the phenyl group represented by X and the cycloalkyl group having 3 to 10 carbon atoms, and the above-described alkyl group, alkoxy group and alkenyl group represented by Y and Z May be substituted with a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. For example, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl etc. are mentioned as a C1-C10 alkyl group substituted by the fluorine atom.

  The colored alkali-developable photosensitive resin composition of the present invention has an epoxy compound (A) used for its preparation having a triarylmonocycloalkylmethane skeleton, whereby the adhesion of the cured product to the substrate, alkali resistance, Since processability, strength, and the like are excellent, it is considered that a clear image can be formed with high accuracy even if the pattern is a fine pattern when the uncured portion is developed and removed. As the epoxy compound (A), in general formula (I), those in which Cy is cyclohexyl; those in which X is a phenyl group; those in which p and r are 0; those in which n is 0 to 5 are preferable. .

  Specific examples of the epoxy compound (A) represented by the general formula (I) include the following compound Nos. 1-No. 9 compounds are mentioned. However, the present invention is not limited by the following compounds.

A reaction product having a structure in which (C) component is esterified with respect to an epoxy adduct having a structure in which (B) component is added to (A) component contained in the alkali-developable resin composition. Further, the photopolymerizable unsaturated compound (X) having a structure obtained by further adding the component (D) and then esterifying the component (E) is produced, for example, by the method represented by the following reaction formula [Chemical Formula 11] can do.
First, the unsaturated monobasic acid (2) as the component (B) is added to the epoxy compound (1) as the component (A) to obtain a resin composition containing the compound (3) as an epoxy adduct. . The addition reaction of the component (B) to the component (A) can be carried out according to a conventional method, but is preferably performed at 90 to 150 ° C. for 5 to 30 hours.
Subsequently, the compound (3) which is an epoxy adduct is reacted with the polybasic acid anhydride (4) which is the component (C) to carry out an esterification reaction, and a resin composition containing the compound (5) which is an ester compound Get things. The esterification reaction between the epoxy adduct and the component (C) can be carried out according to a conventional method, but is preferably performed at 30 to 150 ° C. for 5 to 30 hours.
Subsequently, the compound (5) which is an ester compound is further subjected to an addition reaction with the compound (6) which is an epoxy compound of the component (D) to obtain a compound (7). The addition reaction between the ester compound and the component (D) can be carried out according to a conventional method, but the reaction is preferably carried out at 50 to 150 ° C. for 2 to 30 hours.
Subsequently, the compound (7) is further reacted with the compound (8) which is a polybasic acid anhydride of the component (E) for esterification, and the target reaction product compound (9) [photopolymerizable property] A resin composition containing the unsaturated compound (X)] can be obtained. The esterification reaction between the compound (7) and the component (E) can be performed according to a conventional method, but the reaction is preferably performed at 30 to 150 ° C. for 2 to 10 hours.
In addition, the photopolymerizable unsaturated compound (X) has a structure obtained by further adding an epoxy compound (D) and then esterifying the polybasic acid anhydride (E) one or more times. The photopolymerizable unsaturated compound (Y) can be produced in the same manner.

  Moreover, the method of obtaining the compound (3) which is an epoxy adduct having a structure in which the component (B) is added to the component (A) is not limited to the method described above in [Chemical Formula 11]. For example, when n in compound (3) is 0, as shown in the following reaction formula [Chemical Formula 12], compound (10) is reacted with a monoepoxy compound containing bisphenol (10) and glycidyl methacrylate (11). 3) can also be obtained.

  Examples of the unsaturated monobasic acid (B) used for the preparation of the colored alkali development type photosensitive resin composition of the present invention include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate, Malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups Etc.

  The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups has, for example, one hydroxyl group and two or more (meth) acryloyl groups in one molecule. It can be obtained by reacting a polyfunctional (meth) acrylate with a dibasic acid anhydride or carboxylic acid.

  Examples of the polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups include the following compound Nos. 10-14 can be mentioned.

  Examples of the polybasic acid anhydride (C) used for the preparation of the colored alkali development type photosensitive resin composition of the present invention include succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride. 2,2'-3,3'-benzophenone tetracarboxylic acid anhydride, 3,3'-4,4'-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimelli Tate, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2, 5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-di Carboxylic acid anhydride, trialkyl tetrahydrophthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid. Among these, succinic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride are preferable.

As an epoxy compound (D) used for preparation of the colored alkali development type photosensitive resin composition of this invention, a monofunctional or polyfunctional epoxy compound is mentioned.
Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the following compounds No. 15 to No .18 etc.

As the polyfunctional epoxy compound, bisphenol type epoxy compounds and glycidyl ethers can be used.
As the bisphenol type epoxy compound, an alkylidene bisphenol polyglycidyl ether type epoxy resin represented by the above general formula (I) can be used, for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used. Can do.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri ( Glycidyl oxy methyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.

  Other polyfunctional epoxy compounds include other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3 , 4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1-epoxyethyl -Alicyclic epoxy compounds such as 3,4-epoxycyclohexane; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester, etc. Glycidyl esters; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline; complex such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate Cyclic epoxy compounds; Dioxide compounds such as dicyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, and the like can be used.

As the polybasic acid anhydride (E) used for the preparation of the colored alkali development type photosensitive resin composition of the present invention, those mentioned as the polybasic acid anhydride (C) can be used.
An epoxy compound (D) is further added to a photopolymerizable unsaturated compound having a structure obtained by reacting each component of (A) to (E), and then a polybasic acid anhydride (E) is esterified. Or a polybasic acid anhydride after adding an epoxy compound (D) to a photopolymerizable unsaturated compound having a structure obtained by reacting the components (A) to (E). Instead of (E), a lactone compound may be esterified.

  The photopolymerizable unsaturated compound (X) obtained by reacting the components (A) to (E), the photopolymerizable unsaturated compound (X), and the epoxy compound (D) are added, The photopolymerizable unsaturated compound (Y) having a structure obtained by esterifying the basic acid anhydride (E) one or more times has a content of 1 in the alkali-developable resin composition. It is preferable that it is -70 mass%, especially 3-30 mass%, and it is preferable that the acid value of solid content is 35-120 mg / KOH, Especially it is the range of 40-100 mg / KOH.

  In addition to the photopolymerizable unsaturated compound (X) or (Y), the alkali-developable resin composition may contain a solvent. For example, the content of the photopolymerizable unsaturated compound may be set as described above. In the preferred range, a solvent can be used for the remainder other than the photopolymerizable unsaturated compound. Specific examples of the solvent include those exemplified as the solvent used in the colored alkali development type photosensitive resin composition described later. Moreover, you may make it contain in the alkali developable resin composition of this invention as it is, without removing the solvent used when synthesize | combining the said photopolymerizable unsaturated compound (X) or (Y).

  Content of the said photopolymerizable unsaturated compound (X) or (Y) makes the said alkali developable resin composition contain color materials (G), such as a photoinitiator (F) and a pigment or dye. It is preferable that it is 1-70 mass% in the colored alkali development type photosensitive resin composition obtained, especially 3-30 mass%, and the acid value of solid content is 35-120 mg / KOH, especially 40-100 mg / KOH. A range is preferred.

  As the photopolymerization initiator (F) used in the colored alkali development type photosensitive resin composition of the present invention, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1 -Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholy-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1- Chlor-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- ( '-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2 '-Morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, the following compounds No. 19, No. 20 and the like. . Among these, benzophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferable.

（式中、Ｘ¹はハロゲン原子又はアルキル基を表し、Ｒ¹はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ²はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＮＲＲ’を表し、Ｒ³はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＮＲＲ’を表し、Ｒ及びＲ’は、アルキル基、アリール基、アラルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、ｍは０〜５である。）

(Wherein X ¹ represents a halogen atom or an alkyl group, R ¹ represents R, OR, COR, SR, CONRR ′ or CN, R ² represents R, OR, COR, SR, NRR ′, R ³ represents R, OR, COR, SR, NRR ′, R and R ′ represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which are substituted with a halogen atom and / or a heterocyclic group. Of these, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and R and R ′ together form a ring. (M may be 0 to 5).

（式中、Ｘ¹、Ｒ¹、Ｒ²、Ｒ³、Ｒ及びＲ’は上記化合物No.20と同様であり、Ｘ¹’はハロゲン原子又はアルキル基を表し、Ｚは酸素原子又は硫黄原子を表し、ｓ及びｔはそれぞれ１〜４の数を表し、Ｒ¹’はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ²’はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＮＲＲ’を表し、Ｒ³’はそれぞれＲ、ＯＲ、ＣＯＲ、ＳＲ、ＮＲＲ’を表し、Ｒ⁴はジオール残基又はジチオール残基を表す。）

(Wherein X ¹ , R ¹ , R ² , R ³ , R and R ′ are the same as in the above compound No. 20, X ¹ ′ represents a halogen atom or an alkyl group, and Z represents an oxygen atom or a sulfur atom) S and t each represent a number from 1 to 4, R ¹ ′ represents R, OR, COR, SR, CONRR ′ or CN, R ² ′ represents R, OR, COR, SR, NRR ′. R ³ ′ represents R, OR, COR, SR, NRR ′, and R ⁴ represents a diol residue or a dithiol residue.)

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is 0.1 to 30% by mass, particularly 0.5 in the colored alkali-developable photosensitive resin composition. -5 mass% is preferable.

  The solvent used in the present invention is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl Ketones such as ketone and cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n- Ester solvents such as propyl, isopropyl acetate, n-butyl acetate; Cellsolv solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate; methanol Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); tetrachloride Halogenated aliphatic hydrocarbon solvents such as carbon, chloroform, trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, Tetrahydrofuran, N, - dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used as one or a mixture of two or more.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the solvent is such that the total solid concentration in the colored alkali-developable photosensitive resin composition is 5 to 40% by mass, particularly 15 to 30% by mass. It is good to adjust so that it becomes.

  Examples of the color material (G) used in the colored alkali development type photosensitive resin composition of the present invention include pigments and dyes. Which is added is not particularly limited, and either one of a pigment and a dye may be used, or both may be used in combination.

As the pigment used as the coloring material in the colored alkali development type photosensitive resin composition of the present invention, any of the known pigments used in the production of conventional color filters can be used. Below, the specific example of an organic pigment is shown with a curry index (CI) number. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from numbers.
・ Pigment Blue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62
・ Pigment Green:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ Pigment Red
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ Pigment Violet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175

  Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBl ack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, Pr, 140, etc.

  Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination.

  The dyes that can be used as the colorant include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine Examples thereof include dyes such as dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These may be used alone or in combination.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the color material (G) is 0. 0% in the total mass of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. 5 to 70%, particularly 5 to 60% by mass is preferable.

  The colored alkali development type photosensitive resin composition of the present invention may further contain a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like.

  Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Lithol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate and the like.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is 0% of the total mass of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. 0.01 to 20% by mass, particularly 0.1 to 10% by mass is preferable.

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercaptov Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  In the colored alkali development type photosensitive resin composition of the present invention, the properties of the cured product can be improved by further using a thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  In addition, the colored alkali development type photosensitive resin composition of the present invention, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filling Conventional additives such as an agent, an antifoaming agent, a dispersant, a leveling agent, and a silane coupling agent can be added.

  The colored alkali-developable photosensitive resin composition of the present invention is applied onto a support substrate such as metal, paper, or plastic by a known means such as a roll coater, curtain coater, various printing, or immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The use of the colored alkali development type photosensitive resin composition of the present invention is not particularly limited, and is used for various applications such as a photocurable coating, a photocurable adhesive, a printing plate, and a photoresist for a printed wiring board. However, it is particularly suitable for use in forming a pixel portion of a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a video camera or the like.

  A color filter using the colored alkali development type photosensitive resin composition of the present invention can be produced by a conventional method.

  Moreover, as the light source of the active light used when curing the colored alkali development type photosensitive resin composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used. Mercury vapor arc, carbon arc, xenon arc, etc. can be used.

EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following examples and the like, “%” means mass%.
Production Examples 1 to 8 show the production of a photopolymerizable unsaturated compound and an alkali developable resin composition No. 1 containing the photopolymerizable unsaturated compound. 1-No. Comparative Production Examples 1 and 2 show the production of a comparative photopolymerizable unsaturated compound and comparative alkaline developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. 9 and no. 10 preparations are shown. Examples 1-8 are the alkali-developable resin composition Nos. Obtained in Production Examples 1-8. 1-No. 8 is obtained by mixing a photopolymerization initiator, a coloring material and a solvent with a colored alkali development type photosensitive resin composition No. 1-No. 8 and Comparative Examples 1 and 2 are comparative alkali-developable resin composition Nos. Obtained in Comparative Production Examples 1 and 2. 9 or No. No. 10, a comparative colored alkali development type photosensitive resin composition No. obtained by mixing a photopolymerization initiator, a coloring material and a solvent, respectively. 9 and no. 10 preparations are shown.

[Production Example 1] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 1 377 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, hereinafter also referred to as compound a-1), acrylic acid (Hereinafter also referred to as compound b) 98.1 g, 2,6-di-tert-butyl-p-cresol 1.6 g, tetrabutylammonium acetate 2.5 g and propylene glycol-1-monomethyl ether-2-acetate 318 g The mixture was charged and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 177 g of propylene glycol-1-monomethyl ether-2-acetate, 128 g of succinic anhydride (hereinafter also referred to as compound c) and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Furthermore, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (hereinafter also referred to as compound d-1) and 2,6-di-tert- 1.6 g of butyl-p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. After cooling to room temperature, 40 g of succinic anhydride (hereinafter also referred to as compound e-1) was added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, and 472 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developing resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained (Mw = 12000, Mn = 3600, acid value (solid content) 56 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 1 represents (C) for one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound (a-1) as component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure was obtained by reacting an epoxy adduct with compound c and compound d-1, followed by compound e-1 at a ratio of 0.29. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Production Example 2] Production of photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 2 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 377 g, acrylic acid 98.1 g ( Compound b), 1.6 g of 2,6-di-tert-butyl-p-cresol, 2.5 g of tetrabutylammonium acetate and 318 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. did. After cooling to room temperature, 177 g of propylene glycol-1-monomethyl ether-2-acetate, 128 g of succinic anhydride (compound c) and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Further, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl-p- 1.6 g of cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 64 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, 502 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developing resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 2 was obtained (Mw = 12000, Mn = 3800, acid value (solid content) 71 mgKOH / g).
In addition, alkali developable resin composition No. 2 includes a photopolymerizable unsaturated compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound a-1 as component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure was obtained by reacting an epoxy adduct with compound c and compound d-1, followed by compound e-1 at a ratio of 0.47. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a.

[Production Example 3] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of Compound No. 3 which is an epoxy compound 1 (epoxy equivalent 610, n = 1.5, hereinafter also referred to as compound a-2) 364 g, acrylic acid (compound b) 43.0 g, 2,6-di-tert-butyl-p-cresol 1.3 g, Tetrabutylammonium acetate 3.3 g and propylene glycol-1-monomethyl ether-2-acetate 266 g were charged and stirred at 120 ° C. for 10 hours. After cooling to room temperature, 126 g of propylene glycol-1-monomethyl ether-2-acetate and 79 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. Further, 106 g of glycidyl methacrylate (hereinafter also referred to as compound d-2) and 1.3 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 90 ° C. for 1 hour and at 120 ° C. for 10 hours. After cooling to room temperature, 98 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound e-2) was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 357 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 3 was obtained (Mw = 5300, Mn = 3200, acid value (solid content) 62 mgKOH / g).
In addition, alkali developable resin composition No. 3 contains a photopolymerizable unsaturated compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound a-2 as component (A). Compound c, which is the component (c), has a ratio of 0.75 acid anhydride structures, and the compound (d), which is the component d-2, has a ratio of 0.7, and the compound e, which is the component (E). -2 acid anhydride structure is obtained by esterifying the epoxy adduct, compound c and compound d-2, and then compound e-2 at a ratio of 0.6. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-2.

[Production Example 4] Production of a photopolymerizable unsaturated compound and an alkali developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 4 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 368 g, acrylic acid (compound b) 95.7 g, 2,6-di-tert-butyl-p-cresol 1.7 g, tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 310 g were charged and stirred at 120 ° C. for 15 hours. did. After cooling to room temperature, 158 g of propylene glycol-1-monomethyl ether-2-acetate, 106 g of succinic anhydride (compound c) and 5.6 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 5 hours. Further, 147 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, n = 0, compound d-1) and 2,6- Di-tert-butyl-p-cresol (1.7 g) and propylene glycol-1-monomethyl ether-2-acetate (68 g) were added, and the mixture was stirred at 100 ° C. for 3 hours. After cooling to room temperature, 76 g of glycidyl methacrylate (Compound d-2) was added and stirred at 120 ° C. for 7 hours. Further, 86 g of succinic anhydride (Compound e-1) was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 546 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 4 was obtained (Mw = 5600, Mn = 2900, acid value (solid content) 59 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 4 is a compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which the compound b (component (B)) is added to the compound a-1 (component (A)). The component (c) is an acid anhydride structure in a ratio of 0.8, the component (D) is a compound d-1 and the compound d-2 has a ratio of 0.8 epoxy groups, and (E) Compound e-1, which is a component, has an acid anhydride structure in a ratio of 0.65, and an esterification reaction is performed between epoxy adduct, compound c, compound d-1, compound d-2, and then compound e-1. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Production Example 5] Production of a photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 5 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 782 g, acrylic acid 203 g (compound b ), 2,6-di-tert-butyl-p-cresol (3.1 g), tetrabutylammonium acetate (5.1 g) and propylene glycol-1-monomethyl ether-2-acetate (660 g), and the mixture was stirred at 120 ° C. for 13 hours. After cooling to room temperature, 335 g of propylene glycol-1-monomethyl ether-2-acetate, 226 g of succinic anhydride (compound c) and 11.9 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 5 hours. Further, 235 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl-p- Cresol 3.1g was added and it stirred at 100 degreeC for 3 hours. Further, 100 g of glycidyl methacrylate (Compound d-2) was added and stirred at 120 ° C. for 7 hours. After cooling to room temperature, 81 g of trimellitic anhydride (hereinafter also referred to as compound e-3) was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 899 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 5 was obtained (Mw = 4200, Mn = 2300, acid value (solid content) 57 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 5 is a compound (C) for one hydroxyl group of an epoxy adduct having a structure in which a compound b (B) is added to a compound a-1 (A). The component (c) is an acid anhydride structure having a ratio of 0.8, and the component (D) is a compound d-1 and the compound d-2 has an epoxy group of 0.55. Compound e-3, which is a component, has an acid anhydride structure at a ratio of 0.15, and an esterification reaction is carried out between epoxy adduct, compound c, compound d-1, compound d-2, and then compound e-3. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Production Example 6] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 6 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 566 g, acrylic acid 147 g (compound b) ), 2.3 g of 2,6-di-tert-butyl-p-cresol, 3.7 g of tetrabutylammonium acetate and 477 g of propylene glycol-1-monomethyl ether-2-acetate, and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 242 g of propylene glycol-1-monomethyl ether-2-acetate, 164 g of succinic anhydride (compound c) and 8.6 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 5 hours. Further, 151 g of neopentyl glycol diglycidyl ether (epoxy equivalent 148, hereinafter also referred to as compound d-3) and 2.3 g of 2,6-di-tert-butyl-p-cresol were added, and 90 ° C. for 1 hour, 120 ° C. For 3 hours. Further, 57.9 g of 3,4-epoxycyclohexylmethyl acrylate (epoxy equivalent 189, hereinafter also referred to as compound d-4) was added and stirred at 120 ° C. for 8 hours. After cooling to room temperature, 140 g (compound e-2) of tetrahydrophthalic anhydride was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 782 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali developing resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 6 was obtained (Mw = 4900, Mn = 2400, acid value (solid content) 59 mgKOH / g).
In addition, alkali developable resin composition No. 6 includes a photopolymerizable unsaturated compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which the compound (b) as the component (B) is added to the compound a-1 as the component (A). The component (c) is an acid anhydride structure in a ratio of 0.8, and the component (D) is a compound d-3 and the compound d-4 has an epoxy group in a ratio of 0.65. Compound e-2, which is a component, has an acid anhydride structure at a ratio of 0.45, and an esterification reaction is performed between epoxy adduct, compound c, compound d-3, compound d-4, and then compound e-2. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Production Example 7] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 7 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 377 g, acrylic acid (compound b) 98.1 g, 1.6 g of 2,6-di-tert-butyl-p-cresol, 2.5 g of tetrabutylammonium acetate and 318 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. did. After cooling to room temperature, 177 g of propylene glycol-1-monomethyl ether-2-acetate, 128 g of succinic anhydride (compound c) and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Further, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl-p- 1.6 g of cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. Subsequently, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl- 1.6 g of p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, and 472 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developing resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 7 was obtained (Mw = 18000, Mn = 4200, acid value (solid content) 51 mgKOH / g).
In addition, alkali developable resin composition No. 7 contains a photopolymerizable unsaturated compound having one structure (C) for one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound a-1 as component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure at a ratio of 0.29, followed by a ratio of 0.6 epoxy group of the compound d-1 as the component (D), and compound e-1 as the component (E) In the ratio of 0.29 acid anhydride structures, the epoxy adduct was reacted with compound c and compound d-1, followed by compound e-1, further compound d-1, and then compound e-1. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Production Example 8] Production of a photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 8 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 377 g, acrylic acid (compound b) 98.1 g, 128 g of succinic anhydride (compound c), 1.6 g of 2,6-di-tert-butyl-p-cresol, 8.2 g of tetrabutylammonium acetate and 495 g of propylene glycol-1-monomethyl ether-2-acetate And stirred at 110 ° C. for 20 hours. Subsequently, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl- 1.6 g of p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. Subsequently, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl- 1.6 g of p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, and 472 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developing resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 8 was obtained (Mw = 11000, Mn = 3500, acid value (solid content) 57 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 8 is a compound (C) for one hydroxyl group of an epoxy adduct having a structure obtained by adding the compound (b) as the component (B) to the compound a-1 as the component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure at a ratio of 0.29, followed by a ratio of 0.6 epoxy group of the compound d-1 as the component (D), and compound e-1 as the component (E) In the ratio of 0.29 acid anhydride structures, the epoxy adduct was reacted with compound c and compound d-1, followed by compound e-1, further compound d-1, and then compound e-1. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Comparative Production Example 1] Production of a comparative photopolymerizable unsaturated compound and comparative alkaline developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of 9 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277) 377 g, acrylic acid 98.1 g, 2,6-di -1.5 g of tert-butyl-p-cresol, 2.5 g of tetrabutylammonium acetate and 318 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 161 g of propylene glycol-1-monomethyl ether-2-acetate, 109 g of succinic anhydride and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Furthermore, 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane 200 g and 2,6-di-tert-butyl-p-cresol 1.5 g, propylene 86 g of glycol-1-monomethyl ether-2-acetate was added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. After cooling to room temperature, 395 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a comparative alkali developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 9 was obtained (Mw = 7200, Mn = 2900, acid value (solid content) 30 mgKOH / g).

[Comparative Production Example 2] Production of a comparative photopolymerizable unsaturated compound and comparative alkali-developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of Compound No. 10 which is an epoxy compound 1 (epoxy equivalent 620, n = 1.6) 364 g, acrylic acid 42.3 g, 2,6-di-tert-butyl-p-cresol 1.3 g, tetrabutylammonium acetate 3.3 g and propylene glycol-1- 266 g of monomethyl ether-2-acetate was charged and stirred at 120 ° C. for 10 hours. The mixture was cooled to room temperature, 126 g of propylene glycol-1-monomethyl ether-2-acetate and 79 g of succinic anhydride were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 106 g of glycidyl methacrylate and 1 g of 2,6-di-tert-butyl-p-cresol were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 10 hours. After cooling to room temperature, 333 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a comparative alkali developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 10 was obtained (Mw = 7800, Mn = 3000, acid value (solid content) 15 mgKOH / g).

[Examples 1 to 8 (colored alkali-developable photosensitive resin compositions No. 1 to No. 8 respectively containing alkali-developable resin compositions No. 1 to No. 8 obtained in Production Examples 1 to 8) Preparation) and Comparative Examples 1 and 2 (comparative colored alkali-developable photosensitive resin compositions No. 9 and No. 10 containing comparative alkali-developable resin composition No. 9 or 10 obtained in Comparative Production Examples 1 and 2). 10 preparation)]
Alkali-developable resin composition Nos. Obtained in Production Examples 1-8. 1 to 8 and Comparative Alkali Developable Resin Composition Nos. 1 and 2 obtained in Comparative Production Examples 1 and 2. 9 or No. 10, 12 g of trimethylolpropane triacrylate, 1.8 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3.2 g of carbon black (“MA100” manufactured by Mitsubishi Chemical Corporation) and propylene glycol-1- Monomethyl ether-2-acetate (75 g) was added and stirred well, and the colored alkali development type photosensitive resin composition No. 1-8 and comparative coloring alkali development type photosensitive resin composition No.1. 9 and no. 10 was obtained.

The colored alkali development type photosensitive resin composition No. adjusted in Examples 1 to 8 above. 1-No. 8 and comparative colored alkali-developable photosensitive resin composition No. 1 prepared in Comparative Examples 1 and 2. 9 and no. Ten evaluations were performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the above-mentioned colored alkali development type photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds. Dried. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, then developed by immersing in a 2.5% by weight sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The following evaluation was performed about the obtained pattern. The results are shown in Table 1.

<Sensitivity>
At the time of exposure, the exposure amount of 100 mJ / cm ² is sufficient for a, 100 mJ / cm ² is insufficient, b is 150 mJ / cm ² for exposure, 150 mJ / cm ² is insufficient, and 200 mJ / cm 2 ^The one exposed in ² was designated as c.
<Resolution>
At the time of exposure and development, A is good pattern formation even if the line width is 10 μm or less, B is good pattern formation if the line width is 10 to 15 μm, and good pattern formation is required unless the line width is 15 μm or more. What was not made was evaluated as C.
<Developability>
Judgment was made based on the presence or absence of a development residue remaining between 15 μm line and space lines obtained by development. A sample in which no residue was observed was marked with ◯, and a sample in which a residue was identified was marked with ×.

  In addition, the colored alkali development type photosensitive resin composition Nos. Obtained in Examples 1 to 8 were used. 1-No. When a color filter was produced according to a conventional method using 8, a good color filter was obtained.

The colored alkali-developable photosensitive resin compositions of Examples 1 to 8 had high sensitivity and excellent resolution and developability.
On the other hand, comparative coloring alkali development type photosensitive resin composition No. 1 of Comparative Examples 1-2 was used. 9 and no. No. 10 could not be formed unless the exposure amount was increased due to the low sensitivity, the resolution was lowered, the line width was not more than 15 μm, and the developability was not satisfactory.
In addition, the color filter using the colored alkali development type photosensitive resin composition of the present invention was satisfactory for practical use.

Claims (5)

Obtained by esterifying polybasic acid anhydride (C) to an epoxy adduct having a structure in which unsaturated monobasic acid (B) is added to epoxy compound (A) represented by the following general formula (I) An alkali-developable resin containing a photopolymerizable unsaturated compound (X) having a structure obtained by adding an epoxy compound (D) to the reaction product obtained and further esterifying the polybasic acid anhydride (E) A colored alkali-developable photosensitive resin composition, wherein the composition further contains a photopolymerization initiator (F) and a colorant (G).

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group, or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group or 3 to 10 carbon atoms. The cycloalkyl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and Y and Z are each independently 1 carbon atom. Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted with a halogen atom, n represents a number from 0 to 10, p represents a number from 0 to 4, and r represents a number from 0 to 4.)   Photopolymerization having a structure obtained by repeating the addition of an epoxy compound (D) to the photopolymerizable unsaturated compound (X) and then esterifying the polybasic acid anhydride (E) one or more times. A colored alkali-developable photosensitive resin composition, further comprising a photopolymerization initiator (F) and a colorant (G) in an alkali-developable resin composition containing a polymerizable unsaturated compound (Y).   The colored alkali-developable photosensitive resin composition according to claim 1 or 2, wherein, in the general formula (I), Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. .   Content of the said photopolymerizable unsaturated compound (X) or (Y) is 1-70 mass% in the said colored alkali development type photosensitive resin composition, Content of the said photoinitiator (F) However, the content of the coloring material (G) is 0.1 to 30% by mass in the colored alkali developing photosensitive resin composition, and the content of the coloring material (G) is the whole of the colored alkali developing photosensitive resin composition excluding the solvent. The colored alkali development type photosensitive resin composition according to claim 1, wherein the content is 0.5 to 70% by mass in the solid component. A color filter comprising the colored alkali development type photosensitive resin composition according to claim 1.