JP5112948B2 - Colored alkali-developable photosensitive resin composition, color filter using the same, liquid crystal split alignment control projection-provided substrate, and liquid crystal display device including the substrate - 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 A liquid crystal display substrate having protrusions for liquid crystal split alignment control formed using an alkali developing photosensitive resin composition containing a specific photopolymerizable unsaturated compound having a low dielectric loss tangent, and a color filter using The present invention relates to a liquid crystal display device including a substrate for a liquid crystal display device.

  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, photocurable inks, photosensitive printing plates, printed wiring plates, various photoresists, color liquid crystal displays Widely used in the manufacture of color filters, which are key parts of devices and image sensors. In recent years, 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, developability, electrical characteristics, etc., and colored alkali-developable photosensitive resin compositions using these alkali-developable photosensitive resin compositions It was difficult to obtain an appropriate pattern shape and fine pattern. Therefore, there has been a demand for a colored alkali development type photosensitive resin composition that is excellent in resolution, developability, and electrical characteristics and that can form a fine pattern with high accuracy.

  In recent years, particularly, liquid crystal displays have been used for color televisions, and the use of alignment-divided vertical alignment (MVA) type liquid crystal displays with a high contrast ratio and a wide viewing angle is increasing. However, in the MVA type liquid crystal display, if a voltage is applied for a long time, there is a problem that charges are accumulated on the surface of the alignment control protrusion and an afterimage is generated. In order to prevent this, the orientation control protrusion is required to have excellent electrical characteristics. The excellent electrical characteristics here mean that the dielectric relaxation characteristics are close to those of the liquid crystal and the alignment film, and no surface charge remains. In addition, in order to increase the viewing angle, the cross-sectional shape (vertical cross-sectional shape) of the orientation control protrusion has an arc shape, that is, a semicircular shape or a semielliptical shape, and there is no flat portion on the upper surface, and the lower portion becomes wider. It is necessary to have such a shape.

Patent Document 3 below proposes a photopolymerizable unsaturated compound and an alkali-developable photosensitive resin composition containing the compound. Patent Document 4 below proposes a resin composition containing a polycarboxylic acid resin and a photosensitive resin composition containing the resin composition. However, the alignment control protrusions formed using these photosensitive resin compositions may have a flat portion on the upper surface, and the electrical characteristics are not satisfactory.
In Patent Document 5 below, an alkali-soluble unsaturated resin and a radiation-sensitive resin composition containing the resin are proposed. If there are minute scratches or dust on the mask, common defects are likely to occur, which is disadvantageous in terms of cost and process.

JP 2000-235261 A JP 2000-355621 A Japanese Patent No. 3148429 JP 2003-107702 A JP 2003-89716 A

  Therefore, an object of the present invention is formed using a colored alkali-developable photosensitive resin composition that is excellent in resolution, developability, and electrical characteristics and that can form a fine pattern with high accuracy, and the colored alkali-developable photosensitive resin composition. It is to provide a color filter. Another object of the present invention is to provide an alkali-developable photosensitive resin composition that has excellent electrical characteristics and provides a good cross-sectional shape for alignment control projections, a liquid crystal display device substrate, and the liquid crystal display device substrate. Another object is to provide a liquid crystal display device.

  The present inventors have used a compound (X) having a structure obtained by reacting a polyfunctional epoxy compound (A) with an unsaturated monobasic acid (B) as a resin component of a (colored) alkali development type photosensitive resin composition. And a compound (Y) having a structure obtained by reacting an epoxy compound (D) with a polyhydroxy aromatic compound (C) and having a structure obtained by crosslinking with a polybasic acid anhydride (E) The inventors have found that the above two problems can be solved by using the compound (Z), and have reached the present invention.

  That is, the present invention relates to a colored alkali development type photosensitive resin composition comprising a colorant (G) in an alkali development type photosensitive resin composition, wherein the alkali development type photosensitive resin composition comprises a compound (Z ) And a photopolymerization initiator (F), and the compound (Z) has a structure obtained by reacting an unsaturated monobasic acid (B) with the polyfunctional epoxy compound (A); And having a structure obtained by crosslinking a compound (Y) having a structure obtained by reacting an epoxy compound (D) with a polyhydroxy aromatic compound (C) with a polybasic acid anhydride (E). The above-described problems have been achieved by providing a colored alkaline development type photosensitive resin composition that is characterized.

  Moreover, this invention achieves the said objective by providing the color filter using the said colored alkali development type photosensitive resin composition.

  Further, the present invention provides a liquid crystal display device substrate comprising at least a translucent substrate and a liquid crystal split alignment control protrusion, wherein the liquid crystal split alignment control protrusion includes a compound (Z) and a photopolymerization initiator ( It consists of the hardened | cured material formed using the alkali image development type photosensitive resin composition containing F), and this compound (Z) makes an unsaturated monobasic acid (B) react with a polyfunctional epoxy compound (A). The compound (X) having a structure obtained by the above and the compound (Y) having a structure obtained by reacting the polyhydroxy aromatic compound (C) with the epoxy compound (D) are converted into a polybasic acid anhydride (E). The above object is achieved by providing a substrate for a liquid crystal display device characterized by having a structure obtained by crosslinking with.

  Moreover, this invention achieves the said objective by providing the liquid crystal display device provided with the said board | substrate for liquid crystal display devices.

  The colored alkali-developable 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. Further, by using the alkali developing type photosensitive resin composition according to the present invention, it is possible to form a liquid crystal split alignment control projection having excellent electrical characteristics and a good alignment control projection cross-sectional shape, in particular MVA. It can be suitably used for forming a liquid crystal split alignment control protrusion used in a liquid crystal display device of the type.

  Hereinafter, the colored alkali-developable photosensitive resin composition, color filter, substrate for liquid crystal display device and liquid crystal display device of the present invention will be described in detail based on preferred embodiments.

  The colored alkali-developable photosensitive resin composition of the present invention comprises a colorant (G) contained in an alkali-developable photosensitive resin composition. The alkali development type photosensitive resin composition contains a compound (Z) and a photopolymerization initiator (F). The compound (Z) includes a compound (X) having a structure obtained by reacting an unsaturated monobasic acid (B) with a polyfunctional epoxy compound (A), and an epoxy compound (C) with a polyhydroxy aromatic compound (C). It has a structure obtained by crosslinking the compound (Y) having a structure obtained by reacting D) with a polybasic acid anhydride (E). The content of the compound (Z) is preferably 1 to 70% by mass in the colored alkali development type photosensitive resin composition, and the content of the photopolymerization initiator (F) is the colored alkali development type. In the photosensitive resin composition, preferably 0.1 to 30% by mass, and the content of the coloring material (G) is preferably in the total solid content excluding the solvent from the colored alkali development type photosensitive resin composition. Is 0.5-70 mass%.

As the polyfunctional epoxy compound (A), for example, polyglycidyl ether of polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of polybasic acid, cyclohexene ring or cyclopentene ring-containing compound is epoxidized with an oxidizing agent. The cyclohexene oxide or cyclopentene oxide-containing compound obtained by the above can be used, and specific examples include the following compounds.
Bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resin, Alkylidene bisphenol polyglycidyl ether type epoxy resin such as bisphenol Z type epoxy resin; hydrogenated bisphenol type diglycidyl ether obtained by hydrogenating the above alkylidene bisphenol polyglycidyl ether type epoxy resin; ethylene glycol diglycidyl ether, 1,3- Propylene glycol diglycidyl ether, 1,2-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 (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane, glycerol triglyceride Glycidyl ethers of aliphatic polyhydric alcohols such as dil ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether; two or more kinds of polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ether of polyether polyol obtained by adding alkylene oxide; phenol novolac type epoxy compound, biphenyl novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, dicyclopentadiene novolak type epoxy compound, etc. A novolak-type epoxy compound; 3,4-epoxy-3-methylcyclohexylmethyl-3,4- Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4- Epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, Methylenebis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate) Alicyclic epoxy compounds such as 1,2-epoxy-2-epoxyethylcyclohexane; glycidyl esters of dibasic acids such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer; tetraglycidyl diaminodiphenylmethane; Glycidylamines such as triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dicyclopentadiene dioxide And the like; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like.

  Commercially available compounds can be used as the polyfunctional epoxy compound (A). For example, BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), Adeka Resin EP -4000, Adeka Resin EP-4003S, Adeka Resin EP-4080, Adeka Resin EP-4085, Adeka Resin EP-4088, Adeka Resin EP-4100, Adeka Resin EP-4900, Adeka Resin ED-505, Adeka Resin ED-506, Adeka Resin KRM-2110, Adeka Resin K -2199, Adeka Resin KRM-2720 (Asahi Denka Kogyo Co., Ltd.), R-508, R-531, R-710 (Mitsui Chemicals), Epicoat 190P, Epicoat 191P, Epicoat 604, Epicoat 801, Picoat 828, Epicoat 871, Epicoat 872, Epicoat 1031, Epicoat RXE15, Epicoat YX-4000, Epicoat YDE-205, Epicoat YDE-305 (manufactured by Japan Epoxy Resin Co., Ltd.), Sumiepoxy ELM-120, Sumiepoxy ELM-434 (Sumitomo Chemical Co., Ltd.) Manufactured), Denacol EM-150, Denacol EX-201, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-322, Denacol EX-411, Denacol EX-421, Denacol EX -512, Denacol EX-521, Denacol EX-614, Denacol EX-711, Denacol EX-721, Denacol EX-731, Denacol EX-811, Denaco Le EX-821, Denacol EX-850, Denacol EX-851, Denacol EX-911 (manufactured by Nagase ChemteX), Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 80 MF, Epolite 100 MF, Epolite 1500 NP, Epolite 1600, Epolite 3002, Epolite 4000, Epolite FR-1500, Epolite M-1230, Epolite EHDG-L (Kyoeisha Chemical Co., Ltd.), SB-20 (Okamura Oil Co., Ltd.), Epiklon 720 (Dainippon Ink Chemical Co., Ltd.), UVR-6100, UVR-6105, UVR-6110, UVR-6200, UVR-6228 (Union Carbide), Ceroxa Id 2000, Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, Epolide 403 HD300, EHPE-3150, ETHB, Epo Blend (manufactured by Daicel Chemical), PY-306, 0163, DY-022 (manufactured by Ciba Specialty Chemicals), Santo Tote ST0000, Epototo YD-011, Epototo YD-115, Epototo YD-127, Epotot YD-134, Epotot YD-172, Epotot YD-6020, Epotot YD-716, Epotot D-7011R, EPOTOHTO YD-901, EPOTOHTO YDPN-638, EPOTOHTO YH-300, Neototo PG-202, Neototo PG-207 (manufactured by Tohto Kasei Co., Ltd.), include Blemmer G (manufactured by NOF Corporation) and the like.

  Among the polyfunctional epoxy compounds (A), polyfunctional epoxy compounds represented by the following general formula (I) are preferable.

（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、該フェニル基及び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、該アルキル基、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、ｐは０〜４の数を示し、ｒは０〜４の数を示す。）

(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 and the cycloalkyl group are carbon atoms. May be substituted with an alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and Y and Z are each independently an alkyl group having 1 to 10 carbon atoms, carbon An alkoxy group having 1 to 10 atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and p is 0 to 4; And r represents a number from 0 to 4.)

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 polyfunctional epoxy compound represented by the above general formula (I) has a triarylmonocycloalkylmethane skeleton, so that the cured product prepared using the polyfunctional epoxy compound has adhesion to a substrate and processability. Since the strength and the like are excellent, it is considered that a clear image can be accurately formed even if the pattern is a fine pattern when the uncured portion is developed and removed.

  Specific examples of the polyfunctional epoxy compound represented by the above 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.

  Among the polyfunctional epoxy compounds represented by the general formula (I), a compound in which Cy is cyclohexyl, X is a phenyl group, and p and r are 0 was prepared using the polyfunctional epoxy compound. It is preferable from the viewpoint of adhesion of the cured product to the substrate and availability of raw materials.

  Examples of the unsaturated monobasic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, and hydroxypropyl acrylate. -Malate, dicyclopentadiene maleate, or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups.

  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-No. 14 can be mentioned.

  Examples of the polyhydroxy aromatic compound (C) include 4,4-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2- Bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 4,4 ′-(1-α-methylbenzylidene) bisphenol 4,4 ′-(1-α-ethylbenzylidene) bisphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, α, α′-bis (4 -Hydroxyphenyl) -1,4-diisopropylbenzene, hydrogenated bisphenol compound, resorcinol Examples include hydroquinone, 2,5-di-tert-butylhydroquinone, 1,4-dihydroxynaphthalene, 1,2,4-trihydroxybenzene, 2- [bis (4-hydroxyphenyl) methyl] benzyl alcohol, salicylic acid, and the like. .

  As the polyhydroxy aromatic compound (C), an adduct of the polyfunctional epoxy compound (A) and the compound exemplified above as the polyhydroxy aromatic compound can also be used.

  Among the polyhydroxy aromatic compounds (C), a bisphenol compound represented by the following general formula (II) is reactive with the epoxy compound (D), and a base material for a cured product prepared using the polyhydroxy compound. It is preferable from the viewpoint of the adhesion to the surface.

（式中、Ｃｙ、Ｘ、Ｙ、Ｚ、ｐ及びｒは、上記一般式（Ｉ）と同じである。）

(In the formula, Cy, X, Y, Z, p and r are the same as those in the general formula (I).)

  Specific examples of the bisphenol compound represented by the general formula (II) include the following compound Nos. 15-No. 23 compounds are mentioned. However, the present invention is not limited by the following compounds.

  Among the bisphenol compounds represented by the general formula (II), a compound in which Cy is cyclohexyl, X is a phenyl group, and p and r are 0 is a base material of a cured product prepared using the bisphenol compound. It is preferable from the viewpoint of adhesion to the material and availability of raw materials.

  As said epoxy compound (D), 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, allylglycid Ether, 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, 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- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, Things No. 24-No. 26 etc. are mentioned. Among them, glycidyl methacrylate, allyl glycidyl ether and the following compound No. 24-No. No. 26 is preferable because it has a double bond at the terminal and can improve sensitivity.

  As the polyfunctional epoxy compound, the compounds exemplified as the polyfunctional epoxy compound (A) can be used.

  Examples of the polybasic acid anhydride (E) 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′-benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, hexahydro Phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Things, trialkyl tetrahydrophthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid. Among these, biphenyltetracarboxylic dianhydride is preferable.

The compound (Z) according to the present invention can be produced from the above-described components (A) to (E), for example, by the method represented by the following reaction formula [Chemical 29]. The method will be described in detail below with reference to [Chemical 29].
First, an unsaturated monobasic acid (B) is esterified with the polyfunctional epoxy compound (A) to obtain a compound (X). This esterification reaction can be carried out according to a conventional method, but is preferably performed at 40 to 150 ° C. for 5 to 15 hours. Separately, the polyhydroxy aromatic compound (C) is etherified with the epoxy compound (D) to obtain the compound (Y). This etherification reaction can be carried out according to a conventional method, but is preferably carried out at 80 to 150 ° C. for 5 to 30 hours. The resulting compound (X) and compound (Y) are subjected to a crosslinking reaction using polybasic acid anhydride (E) to obtain compound (Z). This cross-linking reaction can be carried out according to a conventional method, but is preferably performed at 80 to 130 ° C. for 1 to 10 hours.

  In the esterification reaction, the ratio of the carboxyl group of the unsaturated monobasic acid (B) to one epoxy group of the polyfunctional epoxy compound (A) is preferably 0.3 to 1.0. In the etherification reaction, the ratio of the epoxy group of the epoxy compound (D) to one hydroxyl group of the polyhydroxy aromatic compound (C) is preferably 0.3 to 0.9. In the crosslinking reaction, the ratio of the acid anhydride structure of the polybasic acid anhydride (E) to one total of the hydroxyl groups of the compound (X) and the compound (Y) is preferably 0.3 to 0.00. There are 95.

  The compound (Z) may be further added with an epoxy compound (D) and then esterified with a polybasic acid anhydride (E), and the compound (Z) may be further added with an epoxy compound. After adding (D), the lactone compound may be esterified instead of the polybasic acid anhydride (E).

  The colored alkali-developable photosensitive resin composition of the present invention further contains a colorant (G) in the alkali-developable photosensitive resin composition containing the compound (Z) and the photopolymerization initiator (F). It is obtained.

  The content of the compound (Z) is preferably 1 to 70% by mass, particularly preferably 3 to 30% by mass in the (colored) alkali development type photosensitive resin composition. The content of the compound (Z) is 50 to 90% by mass, particularly 60 to 80% by mass, based on the total mass of the total solid content excluding the solvent from the (colored) alkali development type photosensitive resin composition. % Is preferred. Moreover, it is preferable that the acid value of solid content exists in the range of 35-120 mgKOH / g, especially 50-110 mgKOH / g.

  As the photopolymerization initiator (F), 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-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butyl Rubenzoyltrichloromethane, 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 compound No. 27, no. 28 etc. are mentioned. 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又はＮＲＲ’を表し、Ｒ³はＲ、ＯＲ、ＣＯＲ、ＳＲ又は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、チオエーテル結合又は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 or NRR ′, R ³ represents R, OR, COR, SR or 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. Among them, 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．２７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又はＮＲＲ’を表し、Ｒ³’はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ⁴はジオール残基又はジチオール残基を表す。）

(In the formula, X ¹ , R ¹ , R ² , R ³ , R and R ′ are the same as in the above compound No. 27, 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 or NRR ′. R ³ 'represents R, OR, COR, SR or NRR', and R ⁴ represents a diol residue or a dithiol residue.)

  The content of the photopolymerization initiator (F) is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 5% by mass in the (colored) alkali development type photosensitive resin composition.

  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 (G) 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 the 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, 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 may contain a solvent. For example, when the content of each of the above components is within the above preferred range, a solvent is contained in the balance other than these components. Can be used. Such a solvent is not particularly limited as long as it is a solvent that can dissolve or disperse each of the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, Ketones such as 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-propyl, Ester solvents such as isopropyl acetate and n-butyl acetate; Cellsolv solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate; methanol, ethanol Alcohol 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 spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride Halogenated aliphatic hydrocarbon solvents such as chloroform, trichloroethylene and methylene chloride; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, tetrahydrofuran , N, N-dimethyl Formamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used as one or a mixture of two or more. The solvent may be contained in the (colored) alkali development type photosensitive resin composition as it is without removing the solvent used in the synthesis of the compound (Z).
The content of the solvent is preferably adjusted so 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.

  In the (colored) alkali development type photosensitive resin composition, a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like can be used in combination.

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, pentae Sri tall tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate and the like.
The content of the monomer having an unsaturated bond is 0.01 to 20% by mass, particularly 0.1% in terms of the total mass of the total solid content excluding the solvent from the (colored) alkali development type photosensitive resin composition. -10 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, mercapto 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.

  The properties of the cured product can be improved by further using a thermoplastic organic polymer in the (colored) alkali development type photosensitive resin composition. 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 includes, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; Conventional additives such as an agent, an antifoaming agent, a dispersant, a leveling agent, a silane coupling agent, and a flame retardant 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, a spacer, a substrate with projections for controlling liquid crystal division alignment, etc. used in liquid crystal displays, plasma displays, electroluminescence panels, video cameras, etc. .

  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.

  The color filter of the present invention is the same as the conventional color filter except that the colored alkaline development type photosensitive resin composition of the present invention is used for forming a pixel portion such as a multi-color pixel pattern and / or a black matrix. It has different components depending on the application and can be used for various applications. Further, the color filter of the present invention can be produced by a conventional method.

The substrate for a liquid crystal display device of the present invention (substrate with projections for liquid crystal split alignment control) is at least a liquid crystal display device substrate including a translucent base material and liquid crystal split alignment control protrusions. The projection for forming is made of a cured product formed using an alkali development type photosensitive resin composition, and the alkali development type photosensitivity according to the present invention is used for the formation of the liquid crystal split alignment control projection. Except for using the resin composition, a conventional substrate for a liquid crystal display device can be obtained.
The alkali-developable photosensitive resin composition contains a compound (Z) and a photopolymerization initiator (F), and the compound (Z) is an unsaturated monobasic acid (B) in the polyfunctional epoxy compound (A). A compound (X) having a structure obtained by reacting a polyhydroxy aromatic compound (C) with a compound (Y) having a structure obtained by reacting an epoxy compound (D) with a polyhydroxy aromatic compound (C) It has a structure obtained by crosslinking in (E). Further, the content of the compound (Z) is preferably 1 to 70% by mass, particularly preferably 3 to 30% by mass in the alkali developing photosensitive resin composition, and the content of the photopolymerization initiator (F). Is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 5% by mass, in the alkali development type photosensitive resin composition.

  The dielectric loss tangent of the alkali-developable photosensitive resin composition is preferably 0.006 or less, particularly preferably 0.005 or less, at any frequency in the frequency range of 10 to 50 Hz. When the dielectric loss tangent of the alkali-developable photosensitive resin composition is 0.006 or less, the substrate for a liquid crystal display device of the present invention in which the liquid crystal split alignment control protrusion is formed by the alkali-developable photosensitive resin composition When used in a display device, a highly reliable liquid crystal display device in which display burn-in or the like does not occur can be obtained. In addition, the said dielectric loss tangent is the value measured in accordance with the conventional method using the hardened | cured material of the composition (henceforth an alkali developable resin composition) containing the said compound (Z) as a measurement sample.

  An alignment film layer and a transparent conductive film layer are formed on at least one of the substrates constituting the liquid crystal display device of the present invention. The transparent conductive film layer is usually formed immediately below the alignment film or the liquid crystal split alignment control protrusion, and in the case of a color filter substrate, it is formed on the color filter layer or the protective film layer. The transparent conductive film layer is formed as a thin film of ITO (indium and tin composite oxide), IZO (indium and zinc composite oxide) or the like by a method such as sputtering or vacuum deposition.

  In the formation of the liquid crystal split alignment control projection, first, the alkali development type photosensitive resin composition according to the present invention is applied by a known means such as a spin coater, a roll coater, or a curtain coater. Also, instead of coating on a substrate, a method of coating an alkali development type photosensitive resin composition on a transfer support such as a so-called blanket or film once supported by a cylindrical transfer cylinder, and transferring this to the substrate You may take Next, exposure is performed through a photomask having a predetermined pattern, and an unexposed portion is removed with an alkaline aqueous solution such as sodium carbonate and developed. In addition, since the alkali development type photosensitive resin composition according to the present invention has good exposure sensitivity, it is not necessary to form an oxygen-blocking film. A step of forming a blocking film may be provided.

  Furthermore, by performing a thermal process as necessary after development, curing of the liquid crystal split alignment control protrusions can be accelerated, and the solvent resistance, heat resistance, and adhesion to the substrate can be improved. In addition, the shape can be made smooth by heat shrinkage or reflow, and the orientation of the liquid crystal molecules can be further improved.

  The liquid crystal division alignment control protrusions thus formed are preferably regularly arranged on the substrate in the form of dots, stripes, or zigzags, and the cross-sectional shape thereof is semicircular or semicircular. An elliptical shape is preferable.

  For the alignment layer formed as necessary, a liquid crystal compound is vertically aligned and a transparent and insulating material is used. Usually, a polyimide resin solution, a polyamic acid solution, or the like is formed by a known coating method or printing method, and then fired.

  The substrate with projections for controlling liquid crystal split alignment of the present invention can be applied to a liquid crystal display device in the same manner as the substrate with protrusions for controlling liquid crystal split alignment.

The substrate with protrusions for controlling liquid crystal split alignment according to the present invention is provided with a color filter layer on a translucent substrate, and for controlling liquid crystal split alignment with the alkali development type photosensitive resin composition according to the present invention on the color filter layer. Protrusions can be formed and used as a color filter for liquid crystals.
Hereinafter, this case will be described. However, this does not mean that the substrate with liquid crystal division alignment control protrusions or the liquid crystal display device of the present invention must necessarily include a color filter layer.

  In general, a color filter layer is a layer in which a black matrix for improving contrast and then a colored pixel layer of red, green, and blue are formed. A substrate for a liquid crystal display device including the color filter layer is an MVA type liquid crystal display. When used in an apparatus, the liquid crystal split alignment control protrusion is laminated on the color filter layer via a hard coat layer and a transparent conductive film as necessary, and further the liquid crystal split alignment control protrusion as required. An alignment film is laminated on the substrate.

  The black matrix constituting the color filter layer can be formed using a known method. For example, a method of patterning a thin film of a metal or metal oxide such as chromium or titanium by etching, a coloring material such as carbon black or pigment is mixed in the photosensitive resin composition, and this is coated on the substrate with the photosensitive resin layer Can be formed by photolithography, or a method in which two or more colored pixel layers to be described later are stacked and formed. However, any method may be used in the present invention.

  The colored pixel layer is provided in the opening of the black matrix, and examples of the forming method include known methods such as a pigment dispersion method, a dye method, an electrodeposition method, a printing method, a transfer method, and an ink jet method. In the invention, it may be formed by any method.

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 3 show production examples of Compound (X), Production Examples 4 to 13 show production examples of Compound (Y), and Production Examples 14 to 25 show alkali development containing Compound (Z). Resin Composition No. 1-No. No. 12 production examples are shown, and Production Examples 26 to 37 are the same as the alkali developable resin composition Nos. Obtained in Production Examples 14 to 25. 1-No. 12, an alkali development type photosensitive resin composition No. obtained by mixing a photopolymerization initiator (F) and a solvent. 1-No. No. 12 preparation examples are shown, and Examples 1 to 13 show the alkali-developable resin composition Nos. Obtained in Production Examples 14 to 25. 1-No. No. 12, a photo-polymerization initiator (F), and a colored alkali developing type photosensitive resin composition No. obtained by mixing a pigment and a solvent as a coloring material (G). 1-No. 13 preparation examples are shown, and Example 14 shows a production example of a substrate for a liquid crystal display device and a liquid crystal display device.

[Production Example 1] Production of compound (X) -1 Hydrogenated bisphenol A diglycidyl ether (epoxy equivalent 215, trade name Denacol EX-252, manufactured by Nagase ChemteX Corporation, hereinafter also referred to as compound a-1) 417 g, acrylic 142 g of acid (hereinafter also referred to as compound b), 3.5 g of tetrabutylammonium acetate, 2.5 g of 2,6-di-tert-butyl-p-cresol and 684 g of propylene glycol-1-monomethyl ether-2-acetate The mixture was stirred at 120 ° C. for 18 hours to obtain a compound (X) -1 as a propylene glycol-1-monomethyl ether-2-acetate solution.
The compound (X) -1 is obtained by esterifying one epoxy group of the compound a-1 which is the component (A) at a ratio of one carboxyl group of the compound b which is the component (B). Has a structure.

[Production Example 2] Production of Compound (X) -2 Bis [4- (2,3-epoxypropyloxy) phenyl] -4-biphenylyl (cyclohexyl) methane (epoxy equivalent 277, n = 0, hereinafter, compound a- 2) 1090 g, acrylic acid (compound b) 290 g, tetrabutylammonium acetate 7.1 g, 2,6-di-tert-butyl-p-cresol 8.4 g and propylene glycol-1-monomethyl ether-2-acetate 926 g was added and stirred at 120 ° C. for 14 hours to obtain Compound (X) -2 as a propylene glycol-1-monomethyl ether-2-acetate solution.
Compound (X) -2 is obtained by esterifying one epoxy group of compound a-2 as component (A) with one carboxyl group of compound b as component (B). Has a structure.

[Production Example 3] Production of Compound (X) -3 334 g of bisphenol A diglycidyl ether (epoxy equivalent 187, trade name Adeka Resin EP-4100E, manufactured by ADEKA, hereinafter also referred to as Compound a-3), acrylic acid (Compound b) 131 g, tetrabutylammonium acetate 3.2 g, 2,6-di-tert-butyl-p-cresol 2.5 g and propylene glycol-1-monomethyl ether-2-acetate 569 g were added and stirred at 120 ° C. for 15 hours. Compound (X) -3 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution.
The compound (X) -3 is obtained by esterifying the carboxyl group of the compound b as the component (B) at a ratio of one to the epoxy group of the compound a-3 as the component (A). Has a structure.

[Production Example 4] Production of Compound (Y) -1 2,229 g of 2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as Compound c-1), 248 g of styrene oxide (hereinafter also referred to as Compound d-1) Then, 3.6 g of tetrabutylammonium acetate and 126 g of propylene glycol-1-monomethyl ether-2-acetate were added, stirred at 90 ° C. for 1 hour, further stirred at 120 ° C. for 9 hours, and propylene glycol-1-monomethyl ether-2. -Compound (Y) -1 was obtained as an acetate solution.

In addition, the compound (Y) -1 is etherified with a ratio of one epoxy group of the compound d-1 as the component (D) to one hydroxyl group of the compound c-1 as the component (C). It has the resulting structure.

[Production Example 5] Production of Compound (Y) -2 351 g of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter also referred to as Compound c-2), 248 g of styrene oxide (Compound d-1), Triphenylphos The fin 1.8g was prepared and it stirred at 90 degreeC for 1 hour, and also it stirred at 120 degreeC for 9 hours, and obtained compound (Y) -2.
In addition, compound (Y) -2 is etherified at a ratio of one epoxy group of compound d-1 as component (D) to one hydroxyl group of compound c-2 as component (C). It has the resulting structure.

[Production Example 6] Production of compound (Y) -3 2,269 g of 2-bis (4-hydroxyphenyl) cyclohexane (hereinafter also referred to as compound c-3), 248 g of styrene oxide (compound d-1), tetrabutylammonium 3.7 g of acetate and 130 g of propylene glycol-1-monomethyl ether-2-acetate were added, stirred at 90 ° C. for 1 hour, and further stirred at 120 ° C. for 9 hours to obtain a propylene glycol-1-monomethyl ether-2-acetate solution. Compound (Y) -3 was obtained.
In addition, the compound (Y) -3 is obtained by etherifying one epoxy group of the compound d-1 as the component (D) with one hydroxyl group of the compound c-3 as the component (C). It has the resulting structure.

[Production Example 7] Production of Compound (Y) -4 Bis [4-hydroxyphenyl] -4-biphenylyl (cyclohexyl) methane (hereinafter also referred to as Compound c-4) 434 g, styrene oxide (Compound d-1) 248 g, 3.7 g of tetrabutylammonium acetate and 171 g of propylene glycol-1-monomethyl ether-2-acetate were added, and the mixture was stirred at 90 ° C. for 1 hour, further stirred at 120 ° C. for 9 hours, and propylene glycol-1-monomethyl ether-2- Compound (Y) -4 was obtained as an acetate solution.
In addition, the compound (Y) -4 is obtained by etherifying the epoxy group of the compound d-1 as the component (D) to one hydroxyl group of the compound c-4 as the component (C). It has the resulting structure.

[Production Example 8] Production of compound (Y) -5 434 g of bis [4-hydroxyphenyl] -4-biphenylyl (cyclohexyl) methane (compound c-4), 266 g of butyl glycidyl ether (hereinafter also referred to as compound d-2) Then, 3.6 g of tetrabutylammonium acetate and 175 g of propylene glycol-1-monomethyl ether-2-acetate were added, stirred at 90 ° C. for 1 hour, further stirred at 120 ° C. for 9 hours, and propylene glycol-1-monomethyl ether-2. -Compound (Y) -5 was obtained as an acetate solution.
In addition, compound (Y) -5 is etherified at a ratio of one epoxy group of compound d-2 as component (D) to one hydroxyl group of compound c-4 as component (C). It has the resulting structure.

[Production Example 9] Production of compound (Y) -6 2,2-bis (4-hydroxyphenyl) propane (compound c-1) 172 g, 3- (2-xenyloxy) -1,2-epoxypropane (trade name) OPP-G (manufactured by Sanko Co., Ltd., hereinafter also referred to as compound d-3), 347 g, tetrabutylammonium acetate 1.9 g and propylene glycol-1-monomethyl ether-2-acetate 132 g were charged and stirred at 90 ° C. for 1 hour. The mixture was further stirred at 120 ° C. for 9 hours to obtain Compound (Y) -6 as a propylene glycol-1-monomethyl ether-2-acetate solution.
In addition, compound (Y) -6 is etherified at a ratio of one epoxy group of compound d-3 as component (D) to one hydroxyl group of compound c-1 as component (C). It has the resulting structure.

[Production Example 10] Production of Compound (Y) -7 2,229 g of 2-bis (4-hydroxyphenyl) propane (Compound c-1), 232 g of Compound d-3, allyl glycidyl ether (hereinafter referred to as Compound d-4) 117 g), tetrabutylammonium acetate 3.7 g and propylene glycol-1-monomethyl ether-2-acetate 145 g were charged, stirred at 90 ° C. for 1 hour, further stirred at 120 ° C. for 9 hours, and propylene glycol-1- Compound (Y) -7 was obtained as a monomethyl ether-2-acetate solution.
In addition, compound (Y) -7 has one total epoxy group of compound d-3 and compound d-4 as component (D) for one hydroxyl group of compound c-1 as component (C). Having a structure obtained by etherification at a ratio of

[Production Example 11] Production of compound (Y) -8 2,343 g of 2-bis (4-hydroxyphenyl) propane (compound c-1), phenylglycidyl ether (epoxy equivalent 153, trade name Denacol EX-141, Nagase Chem) Tex Corporation, hereinafter also referred to as compound d-5), 469 g, tetrabutylammonium acetate 3.8 g and propylene glycol-1-monomethyl ether-2-acetate 149 g were charged, stirred at 90 ° C. for 1 hour, and further at 120 ° C. The mixture was stirred for 9 hours to obtain Compound (Y) -8 as a propylene glycol-1-monomethyl ether-2-acetate solution.
In addition, compound (Y) -8 is etherified at a ratio of one epoxy group of compound d-5 as component (D) to one hydroxyl group of compound c-1 as component (C). It has the resulting structure.

[Production Example 12] Production of compound (Y) -9 228 g of compound c-1 and 4-tert-butylphenylglycidyl ether (epoxy equivalent 227, trade name Denacol EX-146, manufactured by Nagase ChemteX Corporation, hereinafter, compound d -6 4), 2.5 g of tetrabutylammonium acetate and 130 g of propylene glycol-1-monomethyl ether-2-acetate, and stirred at 90 ° C. for 1 hour and further stirred at 120 ° C. for 9 hours. Compound (Y) -9 was obtained as a 1-monomethyl ether-2-acetate solution.
In addition, compound (Y) -9 is etherified with a ratio of one epoxy group of compound d-6 as component (D) to one hydroxyl group of compound c-1 as component (C). It has the resulting structure.

[Production Example 13] Production of compound (Y) -10 2,5-di-tert-butylhydroquinone (hereinafter also referred to as compound c-5) 222 g, compound d-6 464 g, tetrabutylammonium acetate 2.6 g and Propylene glycol-1-monomethyl ether-2-acetate (121 g) was charged, stirred at 90 ° C. for 1 hour, and further stirred at 120 ° C. for 9 hours to obtain a propylene glycol-1-monomethyl ether-2-acetate solution as compound (Y)- 10 was obtained.
In addition, compound (Y) -10 is etherified at a ratio of one epoxy group of compound d-6 as component (D) to one hydroxyl group of compound c-5 as component (C). It has the resulting structure.

[Production Example 14] Alkali-developable resin composition No. Production of 1 {Compound (X) -1} 125 g obtained in Production Example 1, 60.5 g of {Compound (Y) -1} obtained in Production Example 4, biphenyltetracarboxylic dianhydride (hereinafter referred to as Compound) e) 34.7 g and propylene glycol-1-monomethyl ether-2-acetate 32.9 g were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 14.3 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained (Mw = 3300, Mn = 1600, acid value (solid content) 107 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) 1 contains an acid anhydride structure of compound (e), which is component (E), of 0.6 for a total of one hydroxyl group of compound (X) -1 and compound (Y) -1. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 15] Alkali-developable resin composition No. Production of 2 {Compound (X) -1} 148 g obtained in Production Example 1, 60.0 g of {Compound (Y) -2} obtained in Production Example 5, biphenyltetracarboxylic dianhydride (Compound e) 37.9 g and 53.2 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 7 hours. After cooling to room temperature, 17.1 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. 2 (Mw = 3500, Mn = 1700, acid value (solid content) 96 mgKOH / g).
In addition, alkali developable resin composition No. The compound (Z) 2 contains a compound (X) -1 and a compound (Y) -2 having a total of one hydroxyl group, and the acid anhydride structure of the compound e as the component (E) is 0.6. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 16] Alkali-developable resin composition No. Production of 3 {Compound (X) -1} 132 g obtained in Production Example 1, 65.0 g of {Compound (Y) -3} obtained in Production Example 6, biphenyltetracarboxylic dianhydride (Compound e) 35.8 g and 34.5 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 7 hours. After cooling to room temperature, 15.2 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 3 was obtained (Mw = 3400, Mn = 1600, acid value (solid content) 104 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) 3 contains an acid anhydride structure of compound (e), which is component (E), of 0.6 for a total of one hydroxyl group of compound (X) -1 and compound (Y) -3. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 17] Alkali-developable resin composition No. Production of 4 {Compound (X) -1} 166 g obtained in Production Example 1, {Compound (Y) -4} 86.8 g obtained in Production Example 7, biphenyltetracarboxylic dianhydride (Compound e) 40.4 g and 42.1 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 19.1 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 (Mw = 3400, Mn = 1700, acid value (solid content) 93 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) 4 contains an acid anhydride structure of Compound (E) as the component (E) with respect to one total of hydroxyl groups of Compound (X) -1 and Compound (Y) -4. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 18] Alkali-developable resin composition No. Production of 5 {Compound (X) -1} 166 g obtained in Production Example 1, 87.7 g of {Compound (Y) -5} obtained in Production Example 8, biphenyltetracarboxylic dianhydride (Compound e) 40.4 g and 42.1 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 5 hours. The mixture was cooled to room temperature, 19.2 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 5 (Mw = 3400, Mn = 1600, acid value (solid content) 90 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) contained in Compound 5 has an acid anhydride structure of Compound (e) as the component (E) with respect to a total of one hydroxyl group of Compound (X) -1 and Compound (Y) -5. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 19] Alkali-developable resin composition No. Production of 6 {Compound (X) -1} 125 g obtained in Production Example 1, 65.1 g of {Compound (Y) -6} obtained in Production Example 9, biphenyltetracarboxylic dianhydride (Compound e) 30.3 g and 31.5 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 14.3 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 6 (Mw = 3800, Mn = 1700, acid value (solid content) 89 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) 6 contains an acid anhydride structure of compound e which is component (E) of 0.6 for a total of one hydroxyl group of compound (X) -1 and compound (Y) -6. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 20] Alkaline-developable resin composition No. Production of 7 {Compound (X) -1} 144 g obtained in Production Example 1, {Compound (Y) -7} 68.9 g obtained in Production Example 10, biphenyltetracarboxylic dianhydride (Compound e) 37.3 g and 37.8 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 16.6 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. 7 (Mw = 3300, Mn = 1700, acid value (solid content) 100 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) 7 contains an acid anhydride structure of Compound (E) as the component (E) with respect to one total of hydroxyl groups of Compound (X) -1 and Compound (Y) -7. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 21] Alkaline-developable resin composition No. Production of 8 {Compound (X) -1} 205 g obtained in Production Example 1, {Compound (Y) -8} 96.3 g obtained in Production Example 11, biphenyltetracarboxylic dianhydride (Compound e) 54.6 g and 58.4 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 5 hours. The mixture was cooled to room temperature, 237 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 8 was obtained (Mw = 3500, Mn = 1800, acid value (solid content) 100 mgKOH / g).
In addition, alkali developable resin composition No. The compound (Z) contained in 8 has an acid anhydride structure of the compound e as the component (E) of 0.6 with respect to a total of one hydroxyl group of the compound (X) -1 and the compound (Y) -8. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 22] Alkali-developable resin composition No. Preparation of 9 {Compound (X) -1} 165 g obtained in Production Example 1, {Compound (Y) -9} 82.3 g obtained in Production Example 12, biphenyltetracarboxylic dianhydride (Compound e) 40.4 g and 47.3 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 191 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. 9 was obtained (Mw = 3800, Mn = 2100, acid value (solid content) 91 mgKOH / g).

In addition, alkali developable resin composition No. The compound (Z) contained in 9 has an acid anhydride structure of the compound e as the component (E) of 0.6 for a total of one hydroxyl group of the compound (X) -1 and the compound (Y) -9. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 23] Alkali-developable resin composition No. Production of 10 {Compound (X) -1} 165 g obtained in Production Example 1, 80.8 g of {Compound (Y) -10} obtained in Production Example 13, biphenyltetracarboxylic dianhydride (Compound e) 40.2 g and 47.1 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 5 hours. The mixture was cooled to room temperature, 190 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 10 was obtained (Mw = 4800, Mn = 2400, acid value (solid content) 81 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) contained in Compound 10 has an acid anhydride structure of Compound (e), which is the component (E), of 0.6 for a total of one hydroxyl group of Compound (X) -1 and Compound (Y) -10. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 24] Alkali-developable resin composition No. Production of 11 {Compound (X) -2} 232 g obtained in Production Example 2, {Compound (Y) -1} 96.2 g obtained in Production Example 4, biphenyltetracarboxylic dianhydride (Compound e) 61.2 g and 123 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 5 hours. The mixture was cooled to room temperature, 114 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 11 (Mw = 3500, Mn = 1700, acid value (solid content) 93 mgKOH / g).

In addition, alkali developable resin composition No. The compound (Z) contained in 11 has an acid anhydride structure of the compound e as the component (E) of 0.6 relative to a total of one hydroxyl group of the compound (X) -2 and the compound (Y) -1. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Production Example 25] Alkali-developable resin composition No. Production of 12 {Compound (X) -3} 104 g obtained in Production Example 3, 60.5 g of {Compound (Y) -1} obtained in Production Example 4, biphenyltetracarboxylic dianhydride (Compound e) 33.4 g and 35.4 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 5 hours. The mixture was cooled to room temperature, 133 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 12 (Mw = 3400, Mn = 1500, acid value (solid content) 110 mgKOH / g).
In addition, alkali developable resin composition No. Compound (Z) 12 contains a compound (X) -3 and compound (Y) -1 having a total of one hydroxyl group, and the acid anhydride structure of compound (e) as the component (E) is 0.6. It has a structure obtained by a cross-linking reaction at a ratio of 1 piece.

[Comparative Production Example 1] Comparative alkali-developable resin composition No. Preparation of 13 Hydrogenated bisphenol A diglycidyl ether (compound a-1) 90.0 g, acrylic acid (compound b) 30.7 g, tetrabutylammonium acetate 0.75 g, 2,6-di-tert-butyl-p- 0.47 g of cresol and 148 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 18 hours. The mixture was cooled to room temperature, 36.9 g of biphenyltetracarboxylic dianhydride (Compound e) was added, and the mixture was stirred at 120 ° C. for 5 hours. After cooling to room temperature, 145 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the comparative alkali-developable resin composition no. 13 was obtained (Mw = 3300, Mn = 1500, acid value (solid content) 99 mgKOH / g).

[Comparative Production Example 2] Comparative alkali-developable resin composition No. Preparation of 14 Bis [4- (2,3-epoxypropyloxy) phenyl] -4-biphenylyl (cyclohexyl) methane (compound a-2) 66.5 g, acrylic acid (compound b) 17.7 g, tetrabutylammonium acetate 0.44 g, 2,6-di-tert-butyl-p-cresol 0.32 g and propylene glycol-1-monomethyl ether-2-acetate 103 g were charged and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 21.3 g of biphenyltetracarboxylic dianhydride (compound e) was added and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 93.0 g of propylene glycol-1-monomethyl ether-2-acetate was added, and a comparative alkali-developable resin composition No. 1 as a target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 14 was obtained (Mw = 3800, Mn = 1700, acid value (solid content) 88 mgKOH / g).

[Comparative Production Example 3] Comparative alkali-developable resin composition No. Production of 15 Bisphenol A diglycidyl ether (compound a-3) 60.0 g, acrylic acid (compound b) 23.3 g, tetrabutylammonium acetate 0.57 g, 2,6-di-tert-butyl-p-cresol 0 .33 g and 102 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 28.0 g of biphenyltetracarboxylic dianhydride (compound e) was added and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 105 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the comparative alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 15 (Mw = 3300, Mn = 1500, acid value (solid content) 106 mgKOH / g).

The alkali-developable resin composition No. prepared in the above Production Examples 14-25. 1-No. 12 and Comparative Alkali Developable Resin Composition No. 1 prepared in Comparative Production Examples 1-3. 13-No. The measurement of 15 dielectric loss tangents was performed as follows.
That is, an electrode was formed by depositing aluminum on a glass plate having a thickness of 0.7 mm so as to have a thickness of 100 angstrom through a metal mask having an electrode pattern by a general vacuum deposition method. Subsequently, the alkali-developable resin composition No. 1-No. 12 and comparative alkali development type photosensitive resin composition no. 13-No. 15 was applied by spin coating to a thickness of about 2 μm, dried at 80 ° C. for 10 minutes, then unnecessary portions other than those on the aluminum electrode were removed, and heated at 230 ° C. for 30 minutes using a hot air dryer A test piece was prepared by drying and further forming an aluminum electrode in the same manner as described above. The test piece has a structure in which a cured product of the alkali-developable resin composition according to the present invention is sandwiched between 10 mm × 10 mm square aluminum electrodes with a thickness of about 1.5 μm. About the obtained test piece, the value of the dielectric loss tangent at 30 Hz was measured. The results are shown in [Table 1].

  As apparent from [Table 1], the alkali-developable resin composition Nos. Obtained in the above Production Examples 14 to 25 were used. 1-No. No. 12 has a low dielectric loss tangent at 30 Hz of the cured product, while the comparative alkaline developable resin composition No. 1 obtained in Comparative Production Examples 1 to 3 above. 13-No. No. 15 had a large dielectric loss tangent at 30 Hz of the cured product.

[Production Examples 26 to 37 and Comparative Production Examples 4 to 6] Alkali-developable photosensitive resin composition No. 1-No. 12 and comparative alkali development type photosensitive resin composition no. 13-No. Production of No. 15 Alkali-developable resin composition No. obtained in Production Examples 14-25. 1-No. 12 and Comparative Alkali Developable Resin Composition Nos. 13-No. 15 to 14 g, trimethylolpropane triacrylate 6.3 g, benzophenone 2.1 g and propylene glycol-1-monomethyl ether-2-acetate 78 g as a photopolymerization initiator (F) were added and stirred well, and alkali developing type Photosensitive resin composition No. 1-No. 12 and comparative alkali development type photosensitive resin composition no. 13-No. 15 was obtained.

The alkali development type photosensitive resin composition No. prepared in the above Production Examples 26 to 37 was prepared. 1-No. Evaluation of 12 was performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the alkali-developable photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds and dried. I let you. After pre-baking at 70 ° C. for 20 minutes, a 5% 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, developed by immersing in a 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, and washed thoroughly 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 2].

<Sensitivity>
During exposure, what exposure was sufficient 100 mJ / cm ² a, insufficient in 100 mJ / cm ^2, those exposed at 130 mJ / cm ² b, insufficient in 130mJ / cm ^2, 160mJ / cm ^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.
<Adhesion>
Observe the peeling of the pattern obtained by development visually, ○ if the pattern peeling was not observed at all, △ if the pattern peeling was partially observed, what the pattern peeling was observed on the entire surface X.
<Alkali resistance>
The heat-treated coating film was a) 5% NaOH aq. For 24 hours, b) 4% KOH aq. 10 min at 50 ° C., c) 1% NaOH aq. It was immersed for 5 minutes at a medium temperature of 80 ° C., and the appearance after immersion was visually evaluated. The case where the appearance was not changed and the resist was not peeled off was rated as “◯”.

Moreover, the pattern shape was evaluated according to the following method.
That is, the alkali-developable photosensitive resin composition was spin-coated (600 rpm, 7 seconds) on a glass substrate, air-dried for 10 minutes, and then heated on a hot plate at 90 ° C. for 2 minutes. Next, using a mask with a pixel size of 30 μm × 100 μm, using a super-high pressure mercury lamp as a light source, exposing it to light, developing it with a 2.5% aqueous sodium carbonate solution, thoroughly washing it with water, and baking it at 230 ° C. for 30 minutes. Fixed. The pattern shape was observed about the obtained pattern using the scanning electron microscope (SEM). A pattern having a forward taper was indicated by ◯, a pattern having a vertical shape by Δ, and a pattern having an overhang (reverse taper) by ×. The results are shown in [Table 2].

  The alkali development type photosensitive resin compositions of Production Examples 26 to 37 were excellent in resolution, developability, adhesion and alkali resistance, and had a good pattern shape.

[Examples 1 to 12] Colored alkali-developable photosensitive resin composition No. 1-No. Production of Alkali Developable Resin Composition Nos. Obtained in Production Examples 14 to 25 1-No. 12 to 12 g, trimethylolpropane triacrylate 8.0 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1.8 g as a photopolymerization initiator (F), and carbon black (Mitsubishi Chemical Corporation) as a coloring material (G) “MA100” (produced by “MA100”) and 75 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred well. 1-No. 12 was obtained.

[Example 13] Colored alkali-developable photosensitive resin composition No. Production of Alkaline Developable Resin Composition No. 1 obtained in Production Example 14 1, 12 g of trimethylolpropane triacrylate, 1.8 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator (F), and copper halide phthalocyanine pigment (Toyo) as a coloring material (G) Ink Co., Ltd. “6YK”) 0.6 g and ethyl cellosolve 75 g were added and stirred well, and the colored alkali-developable photosensitive resin composition no. 13 was obtained.

  The colored alkali development type photosensitive resin composition No. 1 prepared in Examples 1 to 13 above. 1-No. 13 was evaluated with respect to the above-mentioned alkali development type photosensitive resin composition No. 1-No. 12 was performed in the same manner. The results are shown in [Table 3].

Example 14 Preparation and Evaluation of Liquid Crystal Display Device Substrate and Liquid Crystal Display Device <Preparation and Evaluation of Liquid Crystal Display Device Substrate>
(Creation of substrate with ITO)
A Cr thin film was formed on a transparent glass substrate, and a black matrix was formed by a photoetching method. A red photosensitive resin composition is applied onto this to a thickness of 2 μm by spin coating, dried at 90 ° C. for 5 minutes, and then with an ultrahigh pressure mercury lamp through a photomask having a stripe pattern for colored pixels. Irradiation was 300 mJ / cm ² . After developing with a 2.5% aqueous sodium carbonate solution for 60 seconds and washing with water, post baking was performed at 230 ° C. for 30 minutes in an oven to obtain a red stripe pattern. Then, the same process was performed about the green photosensitive resin composition and the blue photosensitive resin composition, and the red, green, and blue colored pixel layer was formed.
Next, ITO was formed on the entire surface to a thickness of 1500 angstrom by a general sputtering method to form a transparent conductive layer to obtain a substrate with ITO.

(Formation of liquid crystal split alignment control projection)
On the substrate with ITO, the alkali developing type photosensitive resin composition No. 1 prepared in Production Examples 26 to 37 was prepared. 1-No. 12 and comparative alkali development type photosensitive resin composition No. 1 prepared in Comparative Production Examples 4 to 6 above. 13-No. 15 was applied by spin coating to a film thickness of 2 μm, air-dried for 10 minutes, and then heated on a hot plate at 90 ° C. for 2 minutes. After irradiation with 150 mJ / cm ² with an ultra-high pressure mercury lamp through a photomask for forming protrusions, the film was developed with 2.5% sodium carbonate solution for 50 seconds and washed thoroughly with water. After drying, post baking was performed at 230 ° C. for 30 minutes in an oven to form liquid crystal split alignment control protrusions to obtain a liquid crystal display device substrate.
About the obtained substrate for liquid crystal display devices, the cross-sectional shape of the formed protrusion for controlling liquid crystal division alignment was observed and evaluated by a scanning electron microscope (SEM). Evaluation criteria were as follows: ◯ when the cross-sectional shape was semicircular or semi-elliptical, △ when trapezoidal, and x when overhanging.

<Creation and evaluation of liquid crystal display device>
An MVA liquid crystal display device was formed using the liquid crystal display device substrate, and the image sticking characteristics after applying a voltage for 48 hours were examined. As the evaluation criteria, “O” indicates that no afterimage is generated, and “X” indicates that the image is generated. The evaluation results are shown in [Table 4].

  The alkali development type photosensitive resin composition No. of manufacture example 26-37. 1-No. 12 has a semicircular or semi-elliptical cross-sectional shape, and the liquid crystal display device formed using these has a high viewing angle and burn-in. It has good display characteristics without generating. On the other hand, the comparative alkali development type photosensitive resin composition No. of comparative manufacture examples 4-6. 13-No. The cross-sectional shape of the liquid crystal split alignment control protrusion formed using 15 is an overhang shape, and the liquid crystal display device formed using these has burned-in.

Claims (12)

  In a colored alkali development type photosensitive resin composition comprising a colorant (G) in an alkali development type photosensitive resin composition, the alkali development type photosensitive resin composition comprises a compound (Z) and a photopolymerization initiator. A compound (X) containing (F) and having a structure obtained by reacting an unsaturated monobasic acid (B) with the polyfunctional epoxy compound (A), and a polyhydroxy aromatic compound Colored alkali development characterized by having a structure obtained by crosslinking a compound (Y) having a structure obtained by reacting (C) with an epoxy compound (D) with a polybasic acid anhydride (E) Type photosensitive resin composition. The colored alkali-developable photosensitive resin composition according to claim 1, wherein the polyfunctional epoxy compound (A) is a compound represented by the following general formula (I).

(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 and the cycloalkyl group are carbon atoms. May be substituted with an alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and Y and Z are each independently an alkyl group having 1 to 10 carbon atoms, carbon An alkoxy group having 1 to 10 atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and p is 0 to 4; And r represents a number from 0 to 4.) The colored alkali-developable photosensitive resin composition according to claim 1 or 2, wherein the polyhydroxy aromatic compound (C) is a compound represented by the following general formula (II).

(In the formula, Cy, X, Y, Z, p and r are the same as those in the general formula (I).)   The general formula (I) and / or the general formula (II), wherein Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. Colored alkali development type photosensitive resin composition.   The content of the compound (Z) is 1 to 70% by mass in the colored alkali development type photosensitive resin composition, and the content of the photopolymerization initiator (F) is the colored alkali development type photosensitivity. In the resin composition, it is 0.1 to 30% by mass, and the content of the coloring material (G) is 0.5 to 70 in the total solid content excluding the solvent from the colored alkali development type photosensitive resin composition. The colored alkali-developable photosensitive resin composition according to claim 1, wherein the composition is a mass%.   A color filter comprising the colored alkali development type photosensitive resin composition according to claim 1.   In a liquid crystal display substrate comprising at least a light-transmitting substrate and a liquid crystal split alignment control protrusion, the liquid crystal split alignment control protrusion includes an alkali containing a compound (Z) and a photopolymerization initiator (F). It consists of hardened | cured material formed using the development type photosensitive resin composition, and this compound (Z) has a structure obtained by making an unsaturated monobasic acid (B) react with a polyfunctional epoxy compound (A). Obtained by cross-linking compound (X) and polyhydroxy aromatic compound (C) with compound (Y) having a structure obtained by reacting epoxy compound (D) with polybasic acid anhydride (E) A substrate for a liquid crystal display device, characterized by having a structure.   The substrate for a liquid crystal display device according to claim 7, wherein the polyfunctional epoxy compound (A) is represented by the general formula (I).   The substrate for a liquid crystal display device according to claim 7 or 8, wherein the polyhydroxy aromatic compound (C) is represented by the general formula (II).   10. The general formula (I) and / or the general formula (II), wherein Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. A substrate for a liquid crystal display device.   Content of the said compound (Z) is 1-70 mass% in the said alkali development type photosensitive resin composition, and content of the said photoinitiator (F) is the said alkali development type photosensitive resin composition. The substrate for a liquid crystal display device according to any one of claims 7 to 10, wherein the content of the substrate is 0.1 to 30% by mass.   A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 7.