JP2009098158A - Substrate for liquid crystal display unit and liquid crystal display unit equipped with the substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate for a liquid crystal display unit provided with a projection for controlling orientation having a satisfactory cross sectional shape for achieving excellent electric characteristics for preventing the occurrence of an afterimage and a wide angle of visibility and to provide the liquid crystal display unit equipped with this substrate. <P>SOLUTION: In this substrate for the liquid crystal display unit provided with a light transmissive raw material and the projection for controlling liquid crystal splitting orientation, the projection is formed by the alkaline development type photosensitive resin composition prepared by mixing photopolymerization initiator with the alkaline development resin composition having dielectric loss tangent of 0.008 or less in any frequency of 10-50 Hz. This alkaline development resin composition is prepared by containing a photopolymerization unsaturated compound having a chemical structure obtained by esterifying polybasic acid anhydride with epoxy additive having a chemical structure obtained by adding unsaturated-basic acid to epoxy resin. The epoxy resin has a structure obtained by copolymerizing the epoxy compound expressed in a formula (I) and polyhydroxy aromatic compound alternately. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a substrate for a liquid crystal display device comprising a specific photopolymerizable unsaturated compound and having a protrusion for controlling liquid crystal split alignment using an alkali-developable resin composition having a low dielectric loss tangent, and the liquid crystal display device The present invention relates to a liquid crystal display device including a substrate.

  An alkali-developable photosensitive resin composition containing an alkali-soluble binder resin having an ethylenically unsaturated bond, a photopolymerization initiator, and a solvent is a key component of color liquid crystal display devices, image sensors, and the like. Widely used in In recent years, particularly liquid crystal displays have been used for color televisions, and the use of alignment division 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. Here, the excellent electrical characteristics 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 semi-elliptical shape, with no flat portion on the upper surface, and a lower portion becomes wider. It is necessary to have such a shape.

Patent Document 1 below proposes a photopolymerizable unsaturated compound and an alkali development type photosensitive resin composition containing the compound. Patent Document 2 listed 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.
Patent Document 3 listed below proposes an alkali-soluble unsaturated resin and a radiation-sensitive resin composition containing the resin. However, since this radiation-sensitive resin composition is a positive type, in terms of electrical characteristics, Although it is advantageous, if there are minute scratches or dust on the photomask at the time of exposure and curing, there is a problem that common defects are likely to occur, which is disadvantageous in terms of cost and process.

  Patent Document 4 below discloses an epoxy resin composition containing a polyfunctional epoxy resin obtained by reacting a bisphenol with a bifunctional epoxy resin having a bisphenol skeleton, etc. Discloses an epoxy resin composition containing an epoxy resin having two epoxy groups in one molecule and an epoxy resin obtained by alternately copolymerizing a compound containing a phenolic hydroxyl group in the molecule. However, there is no description or suggestion that these epoxy resin compositions are used in alkali-developable photosensitive resin compositions.

Japanese Patent No. 3148429 JP 2003-107702 A JP 2003-89716 A Japanese Examined Patent Publication No. 7-45561 JP 2004-217774 A

  Accordingly, an object of the present invention is to provide an alignment control protrusion having an excellent electrical characteristic capable of preventing the occurrence of an afterimage and a good cross-sectional shape capable of realizing a wide viewing angle, and at the time of forming the alignment control protrusion. To provide a substrate for a liquid crystal display device that does not cause problems with the developability and adhesion of the alkali development type photosensitive resin composition used for the formation, and a liquid crystal display device including the substrate for a liquid crystal display device It is in.

  The present invention includes at least a translucent substrate and a liquid crystal split orientation control protrusion, and the liquid crystal split orientation control protrusion has a dielectric loss tangent of 0.008 or less at any frequency in the frequency range of 10 to 50 Hz. And an alkali-developable photosensitive resin composition obtained by further adding a photopolymerization initiator to the epoxy-resin (A). A photopolymerizable unsaturated compound having a structure obtained by esterifying a polybasic acid anhydride (C) to an epoxy adduct having a structure obtained by adding a saturated monobasic acid (B), and the epoxy resin (A) is a structure obtained by alternately copolymerizing an epoxy compound represented by the following general formula (I) and a polyhydroxy aromatic compound (excluding a bisphenol compound represented by the following general formula (II)). By providing a substrate for a liquid crystal display device characterized by having, in which to achieve the above objects.

  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.

According to the present invention, by using a specific alkali development type photosensitive resin composition, a liquid crystal display substrate substrate having a liquid crystal split alignment control protrusion having excellent electrical characteristics and a good cross-sectional shape is provided. In the formation of the liquid crystal split alignment control protrusion, the developability and adhesion of the alkali development type photosensitive resin composition are good. The substrate for a liquid crystal display device can be suitably used for an MVA liquid crystal display device.
Further, according to the present invention, by using the substrate for a liquid crystal display device, it is possible to provide a liquid crystal display device that has a wide viewing angle and does not generate an afterimage.

  Hereinafter, a substrate for a liquid crystal display device and a liquid crystal display device of the present invention will be described in detail based on preferred embodiments.

The alkali-developable photosensitive resin composition used for forming the liquid crystal split alignment control protrusion provided on the liquid crystal display device substrate of the present invention comprises an alkali-developable resin composition, a photopolymerization initiator (hereinafter referred to as photopolymerization start). (Also referred to as agent (F)).
The alkali developable resin composition is obtained by esterifying a polybasic acid anhydride (C) to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to an epoxy resin (A). A photopolymerizable unsaturated compound having a structure (hereinafter also referred to as a photopolymerizable unsaturated compound (L)) is contained. The photopolymerizable unsaturated compound (L) was obtained by further adding an epoxy compound (D) to the reaction product obtained by esterifying the polybasic acid anhydride (C) with the epoxy adduct. It may be a photopolymerizable unsaturated compound (M) having a structure, and a polybasic acid anhydride (E) is further added to the epoxy addition product obtained by adding the epoxy compound (D) to the reaction product. It may be a photopolymerizable unsaturated compound (Z) having a structure obtained by esterification.

  The dielectric loss tangent of the alkali developable resin composition is 0.008 or less and preferably 0.007 or less at any frequency in the frequency range of 10 to 50 Hz. When the dielectric loss tangent of the alkali-developable resin composition is 0.008 or less, the substrate for a liquid crystal display device of the present invention in which the protrusion for controlling the liquid crystal split alignment is formed by the alkali-developable resin composition is used for a liquid crystal display device. In such a case, a highly reliable liquid crystal display device in which display burn-in or the like does not occur can be obtained. The dielectric loss tangent is a value measured according to a conventional method using a cured product of the alkali-developable resin composition according to the present invention as a measurement sample.

One method of setting the dielectric loss tangent of the alkali-developable resin composition according to the present invention to 0.008 or less at any frequency in the frequency range of 10 to 50 Hz is not particularly limited. Increasing the molecular weight of the photopolymerizable unsaturated compounds (L), (M), and (Z). The molecular weight is preferably 2000 to 10,000 in terms of weight average molecular weight Mw, and preferably 1000 to 5000 in terms of number average molecular weight Mn. As a preferable method for increasing the molecular weight of the photopolymerizable unsaturated compounds (L), (M) and (Z), for example, the following methods may be mentioned.
The photopolymerizable unsaturated compound (L) has the following structure. That is, the above epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to an epoxy resin (A) is converted into an unsaturated monobasic acid (B) for one epoxy group of the epoxy resin (A). In such a structure that the carboxyl group is added at a ratio of 0.1 to 1.0, and the acid anhydride structure is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct, It is set as the structure obtained by esterifying a polybasic acid anhydride (C) with respect to this epoxy adduct. In addition, the photopolymerizable unsaturated compound (M), the photopolymerizable unsaturated compound (L) having the above structure, the epoxy compound (D), one hydroxyl group of the photopolymerizable unsaturated compound (L) A structure obtained by adding 0.1 to 1.0 epoxy groups to the epoxy resin. Further, the photopolymerizable unsaturated compound (Z), the photopolymerizable unsaturated compound (M) having the above structure, and a polybasic acid anhydride (E) are further added to the photopolymerizable unsaturated compound (M). It is set as the structure obtained by making it esterify in the ratio from which the acid-anhydride structure will be 0.1-1.0 with respect to one hydroxyl group.
Further, as a preferred method for increasing the molecular weight of the photopolymerizable unsaturated compounds (L), (M) and (Z), increasing the molecular weight of the polyhydroxy aromatic compound can be mentioned. 1000 is preferred.

  When the dielectric loss tangent of the alkali-developable resin composition according to the present invention is set to 0.008 or less at any frequency in the frequency range of 10 to 50 Hz, the unsaturated one with respect to one epoxy group of the epoxy resin (A) is used. The ratio of the carboxyl groups of the basic acid (B) is more preferably 0.3 to 1.0. The ratio of the acid anhydride structure of the polybasic acid anhydride (C) to one hydroxyl group of the epoxy adduct is more preferably 0.3 to 0.95, and the epoxy compound (D) The ratio of the epoxy group 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.

  The alkali-developable photosensitive resin composition contains a photopolymerization initiator (F) in an alkali-developable resin composition containing a photopolymerizable unsaturated compound (L), (M) or (Z). Preferably, the content of the photopolymerizable unsaturated compound (L), (M) or (Z) in the alkali development type photosensitive resin composition is 1 to 70% by mass, particularly 3 to 30%. The content of the photopolymerization initiator (F) is 0.1 to 30% by mass, particularly 0.5 to 5% by mass.

The epoxy resin (A) is an alternating copolymer of the epoxy compound represented by the general formula (I) and the polyhydroxy aromatic compound (excluding the bisphenol compound represented by the general formula (II)). It has the structure made to do. In the alternating copolymerization, the epoxy compound represented by the general formula (I) and the polyhydroxy aromatic compound have 0.1 to 0.3 hydroxyl groups of the latter with respect to one epoxy group of the former. It is preferable to use in a ratio.
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 and the like. Examples of the halogen atom represented by Y and Z include fluorine, chlorine, bromine and iodine.

  The above-mentioned alkyl group and alkoxy group which may substitute 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 are: The halogen atom may be substituted, 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 cycloalkyl group represented by Cy, the cycloalkyl group represented by X, the alkyl group and alkoxy group which may be substituted for the phenyl group or cycloalkyl group represented by X, and the alkyl represented by Y and Z When the group, alkoxy group and alkenyl group have more than 10 carbon atoms, it is difficult to synthesize a photopolymerizable unsaturated compound and costs are increased.

  The alkali-developable photosensitive resin composition according to the present invention contains a photopolymerizable unsaturated compound having a triarylmonocycloalkylmethane skeleton derived from an epoxy compound represented by the above general formula (I), Since the cured product has excellent adhesion to the base material, processability, strength, and the like, it is considered that a clear image can be formed with high precision even when the non-cured portion is developed and removed. In the general formula (I), Cy is preferably cyclohexyl, X is a phenyl group, and p and r are each preferably 0.

  Specific examples of the epoxy compound 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.

  Examples of the polyhydroxy aromatic compound constituting the epoxy resin (A) together with the epoxy compound represented by the general formula (I) include 4,4-biphenol and 1,1-bis (4-hydroxyphenyl). Ethane, 2,2-bis (4-hydroxyphenyl) propane, 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)- , 4-diisopropylbenzene, hydrogenated bisphenol compound, resorcinol, 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, an adduct of a polyfunctional epoxy compound described later and the compound exemplified above as the polyhydroxy aromatic compound can also be used.

  In the alkali-developable photosensitive resin composition according to the present invention, the unsaturated monobasic acid (B) improves the sensitivity of the alkali-developable photosensitive resin composition. For example, acrylic acid, methacrylic acid, croton Acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate, or one carboxyl group and two or more ( And polyfunctional (meth) acrylates having a (meth) acryloyl group.

  The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups is, 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 having a dibasic acid anhydride or a 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.

  In the alkali-developable photosensitive resin composition according to the present invention, the polybasic acid anhydride (C) increases the acid value of the alkali-developable photosensitive resin composition to improve the pattern shape, developability and development speed. For example, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, 3,3'- 4,4′-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, itacon Acid anhydride, nadic acid anhydride, methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl anhydride Highmic acid etc. are mentioned. Among these, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride, succinic anhydride, and trimellitic anhydride are preferable.

Examples of the epoxy compound (D) in the alkali development type photosensitive resin composition according to the present invention include monofunctional or polyfunctional epoxy compounds.
The monofunctional epoxy compound is for adjusting the acid value of the alkali development type photosensitive resin composition. For example, 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 glycidyl 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, methylstyreneoxy , Cyclohexene oxide, propylene oxide, include the following compounds No.15~No.18 like.

The polyfunctional epoxy compound is for adjusting the development speed by increasing the molecular weight of the photopolymerizable unsaturated compound. For example, polyglycidyl ether of polyhydric alcohol or its alkylene oxide adduct, polybasic acid Examples thereof include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidizing a polyglycidyl ester, a cyclohexene ring or a cyclopentene ring-containing compound with an oxidizing agent, and specific examples thereof 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.

  A commercially available thing can also be used as said polyfunctional epoxy compound, for example, BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT (made by Nippon Kayaku Co., Ltd.), Adeka Resin EP-4000. Adeka Resin EP-4003, 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-1 Adeka Resin KRM-2720 (made by ADEKA), R-508, R-531, R-710 (made by Mitsui Chemicals), Epicoat 190P, Epicoat 191P, Epicoat 604, Epicoat 801, Epi 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) 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, Denacol X-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 80MF Epolite 100MF, Epolite 1500NP, Epolite 1600, Epolite 3002, Epolite 4000, Epolite FR-1500, Epolite M-1230, Epolite EHDG-L (manufactured by Kyoeisha Chemical Co., Ltd.), SB-20 (Okamura Oil Co., Ltd.), Epiklon 720 ( Dainippon Ink and Chemicals), UVR-6100, UVR-6105, UVR-6110, UVR-6200, UVR-6228 (Union Carbide), Celoxide 2000, Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Cyclomer A200, Cyclomer A400, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 401 403, Epolide HD300, EHPE-3150, ETHB, Epoblend (manufactured by Daicel Chemical), PY-306, 0163, DY-022 (manufactured by Ciba Specialty Chemicals), Santo Tote ST0000, Epototo YD-011, Epototo YD- 115, Epotot YD-127, Epotot YD-134, Epotot YD-172, Epotot YD-6020, Epotot YD- 16, Epototo YD-7011R, Epotot YD-901, Epototo YDPN-638, Epotot YH-300, Neotote PG-202, Neototo PG-207 (manufactured by Toto Kasei), Bremer G (manufactured by Nippon Oil & Fats), etc. .

  Examples of the polybasic acid anhydride (E) in the alkali development type photosensitive resin composition according to the present invention include those mentioned as the polybasic acid anhydride (C).

A polybasic acid anhydride (C) is added to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to an epoxy resin (A), which is contained in the alkali development type photosensitive resin composition according to the present invention. ) Is esterified with a photopolymerizable unsaturated compound (L) having a structure obtained by esterifying a polybasic acid anhydride (C), and then added with an epoxy compound (D). The photopolymerizable unsaturated compound (M) having the structure obtained by adding the photopolymerizable unsaturated compound (M) and the epoxy compound (D) and then esterifying the polybasic acid anhydride (E) ( Z) can be produced, for example, by the method represented by the following reaction formula [Chemical Formula 21]. The method will be described in detail below with reference to the reaction formula of [Chemical Formula 21].
First, the compound (1) which is an epoxy compound represented by the above general formula (I) and the compound (2) which is a polyhydroxy aromatic compound are alternately copolymerized to obtain a compound ( 3) is obtained. This alternating copolymerization reaction can be carried out according to a conventional method, but is preferably carried out at 50 to 150 ° C. for 5 to 15 hours.
Then, the compound (4) which is an unsaturated monobasic acid (B) is added to the compound (3) which is an epoxy resin (A), and the resin composition containing the compound (5) which is an epoxy adduct is obtained. obtain. 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 (5) which is an epoxy adduct is reacted with the compound (6) which is a polybasic acid anhydride (C) to carry out an esterification reaction, whereby the compound (7) which is an ester compound [photopolymerizability] A resin composition containing an unsaturated compound (L)] is obtained. The esterification reaction between the epoxy adduct and the component (C) can be performed according to a conventional method, but is preferably performed at 50 to 150 ° C. for 5 to 10 hours.
Subsequently, the compound (7), which is an ester compound, is further subjected to an addition reaction with the compound (8), which is an epoxy compound (D), to obtain a compound (9) [photopolymerizable unsaturated compound (M)]. 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 (9) is further reacted with a compound (10) which is a polybasic acid anhydride (E) for esterification to contain the compound (11) [photopolymerizable unsaturated compound (Z)]. A resin composition can be obtained. The esterification reaction between the compound (9) and the polybasic acid anhydride (E) can be carried out according to a conventional method, but the reaction is preferably carried out at 50 to 150 ° C. for 3 to 10 hours.

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

  The alkali-developable resin composition containing the photopolymerizable unsaturated compound (L), (M) or (Z) has an acid value of 35 to 120 mg / KOH, particularly 50 to 110 mg / KOH. Is preferred.

  In addition to the photopolymerizable unsaturated compounds (L), (M) and (Z), the alkali-developable resin composition may contain a solvent. Specific examples of the solvent include those exemplified as the solvent used in the alkali development type photosensitive resin composition described later. In addition, the solvent used when synthesizing the photopolymerizable unsaturated compounds (L), (M), and (Z) may not be removed and may be contained in the alkali-developable resin composition according to the present invention as it is. . The content of the photopolymerizable unsaturated compound and the solvent in the alkali-developable resin composition is preferably the content of the photopolymerizable unsaturated compound in the alkali-developable photosensitive resin composition described above. It selects from the range which can satisfy | fill a preferable range.

  The alkali-developable photosensitive resin composition according to the present invention contains the photopolymerizable unsaturated compound (L), (M) or (Z), and has the above-mentioned specific dielectric loss tangent. The product further contains a photopolymerization initiator (F). 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-butylben Zoyltrichloromethane, 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.

The alkali development type photosensitive resin composition according to the present invention may contain a solvent. The solvent 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 ketone, cyclohexanone, etc. Ketones; 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, isopropyl acetate , Ester solvents such as n-butyl acetate; cellsolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate; methanol, ethanol, iso Or alcohol solvents such as 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 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, chloroform, Halogenated aliphatic hydrocarbon solvents such as trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, tetrahydrofuran, N, N-dimethylform Bromide, 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 alkali-developable photosensitive resin composition according to the present invention, the content of the solvent is such that the total solid concentration in the alkali-developable photosensitive resin composition is 5 to 40% by mass, particularly 15 to 30% by mass. It is good to adjust as follows.

  In the alkali development type photosensitive resin composition according to the present invention, 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 , Methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate , Tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, etc. .
In the alkali-developable photosensitive resin composition according to the present invention, the content of the monomer having an unsaturated bond is 0. 0% in the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. 01-20 mass%, especially 0.1-10 mass% are 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 alkali development type photosensitive resin composition according to 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 alkali development type photosensitive resin composition according to the present invention 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, and a silane coupling agent can be added.

  Moreover, as the light source of the active light used when curing the alkali developing photosensitive resin composition according to the present invention, a light source 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 substrate for a liquid crystal display device of the present invention is a substrate for a liquid crystal display device comprising at least a translucent substrate and a liquid crystal split alignment control protrusion. The liquid crystal split alignment control protrusion is an alkali development according to the present invention. The photosensitive resin composition is a cured product of the conventional photosensitive resin composition, except that the alkali-developable photosensitive resin composition according to the present invention is used for forming the liquid crystal split alignment control projection. A substrate for a liquid crystal display device can be obtained.

The said translucent base material should just be a plate-shaped material which has translucency, and can use what was used conventionally, such as a transparent glass substrate and a transparent plastic substrate.
In the substrate for a liquid crystal display device of the present invention, a transparent conductive film layer is formed on at least one side of the front and back surfaces of the translucent substrate. The transparent conductive film layer is usually formed directly below the alignment film layer provided as necessary, or the liquid crystal split alignment control protrusion. When the substrate for a liquid crystal display device of the present invention is a color filter substrate described in detail later, the transparent conductive film layer is formed on the color filter layer or the protective film layer. The transparent conductive film layer can be formed as a thin film of, for example, ITO (composite oxide of indium and tin), IZO (composite oxide of indium and zinc) or the like by a technique such as sputtering or vacuum deposition.

  In the formation of the liquid crystal splitting alignment control protrusion, first, the alkali development type photosensitive resin composition according to the present invention is usually applied by a known means such as a spin coater, a roll coater, a curtain coater, various printing, dipping or the like. , Applied to the transparent conductive layer. Further, instead of the transparent conductive film layer or the like, an alkali development type photosensitive resin composition is once applied on a transfer support such as a so-called blanket or film that is supported by a cylindrical transfer cylinder, and this is applied to the transparent conductive film. A method of transferring to the film layer may be taken. 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, the curing of the liquid crystal 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 smoothed by heat shrinkage and reflow, and the orientation of 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.

  In the alignment film layer formed as necessary, a liquid crystal compound can be vertically aligned and a transparent and insulating material is used. Usually, it forms by applying a polyimide resin solution, a polyamic acid solution, etc. by the well-known coating method or the printing method, and baking after that.

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

The substrate with protrusions for controlling liquid crystal splitting alignment of the present invention is provided with a color filter layer on the translucent substrate, and liquid crystal splitting alignment control is performed on the color filter layer by the alkali developing type photosensitive resin composition according to the present invention. It is also possible to form a projection for use as a color filter for liquid crystal.
Hereinafter, this case will be described, but this does not mean that the substrate for a liquid crystal display device or the liquid crystal display device of the present invention must necessarily have 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 colorant 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 formation method thereof include already known methods such as a pigment dispersion method, a dye method, an electrodeposition method, a printing method, a transfer method, and an inkjet method. In the present 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 etc. In the following examples and the like, “%” means mass%.
In Production Examples 1 to 7, an alkali developable resin composition was prepared. In Production Examples 1 to 3 and 7, using the components (A) to (C), an alkali developable resin composition containing the photopolymerizable unsaturated compound (L) was prepared. In Production Examples 4 and 6, an alkali-developable resin composition containing the photopolymerizable unsaturated compound (M) was prepared using the components (A) to (D). In Production Example 5, an alkali-developable resin composition containing the photopolymerizable unsaturated compound (Z) was prepared using the components (A) to (E).
In Comparative Production Examples 1 to 5, comparative alkali-developable resin compositions were prepared. In Comparative Production Examples 1 and 5, the comparative epoxy resin and the components (B) and (C) according to the present invention were used. In Comparative Production Examples 2 to 4, the comparative epoxy resin and the present invention (B) to ( Each component D) was used to prepare an alkali developable resin composition containing a photopolymerizable unsaturated compound.
In Production Examples 8 to 14 and Comparative Production Examples 6 to 10, the alkali-developable photosensitive resin compositions obtained in Production Examples 1 to 7 and Comparative Production Examples 1 to 5 were used, respectively. Prepared.
In Examples 1 to 7 and Comparative Examples 1 to 5, substrates for liquid crystal display devices were prepared using the alkali developing photosensitive resin compositions obtained in Production Examples 8 to 14 and Comparative Production Examples 6 to 10, respectively. A liquid crystal display device was prepared using the liquid crystal display device substrate.

[Production Example 1] Alkali developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 1 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound No. 1; epoxy equivalent 278; hereinafter also referred to as epoxy compound 1) 278 g, resorcinol 27.5 g (hereinafter also referred to as polyhydroxy aromatic compound 1), tetrabutylammonium acetate 2.41 g and propylene glycol-1-monomethyl ether-2-acetate 204 g, charged at 90 ° C. for 2 hours, 110 The mixture was stirred at 5 ° C. for 5 hours to alternately copolymerize the epoxy compound 1 and the polyhydroxy aromatic compound 1. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-1) solution having an epoxy equivalent of 1110 was obtained. This was charged with 33.2 g of acrylic acid (hereinafter also referred to as compound b), 1.29 g of 2,6-di-tert-butyl-p-cresol, and 22.1 g of propylene glycol-1-monomethyl ether-2-acetate. And stirred at 120 ° C. for 15 hours. After cooling to room temperature, 126 g of propylene glycol-1-monomethyl ether-2-acetate and 91.3 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound c-1) were added and stirred at 100 ° C. for 5 hours. Further, 174 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained. The obtained alkali developable resin composition No. 1 contained a photopolymerizable unsaturated compound having Mw = 4660 and Mn = 2580, and the acid value (solid content) was 80 mgKOH / g.
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound 1 contains a compound (A) which is a component a-1 and a compound b which is a component (B), with one hydroxyl group of an epoxy adduct having a structure ( C) The acid anhydride structure of compound c-1 as the component was obtained by reacting the epoxy adduct with compound c-1 at a ratio of 0.6. The compound a-1 has a structure in which one hydroxyl group of the epoxy compound 1 is alternately copolymerized at a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 1.

[Production Example 2] Alkali developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 2 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1) 139 g, 1,1-bis (4 -Hydroxyphenyl) cyclohexane 33.6 g (hereinafter also referred to as polyhydroxy aromatic compound 2), tetrabutylammonium acetate 1.2 g and propylene glycol-1-monomethyl ether-2-acetate 115 g were charged at 90 ° C. for 1 hour. The mixture was stirred at 120 ° C. for 5 hours to alternately copolymerize epoxy compound 1 and polyhydroxy aromatic compound 2. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-2) solution having an epoxy equivalent of 1170 was obtained. This was charged with 17.8 g of acrylic acid (compound b), 0.7 g of 2,6-di-tert-butyl-p-cresol, and 11.9 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 15 hours. After cooling to room temperature, 60.1 g of propylene glycol-1-monomethyl ether-2-acetate and 38.0 g of tetrahydrophthalic anhydride (compound c-1) were added and stirred at 100 ° C. for 3 hours. Further, 92.6 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. 2 was obtained. The obtained alkali developable resin composition No. 2 contained a photopolymerizable unsaturated compound having Mw = 5260 and Mn = 2320, and the acid value (solid content) was 63 mgKOH / g.
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 2 is a compound (A) which is a compound a-2 and a compound b which is a component (B), with one hydroxyl group of an epoxy adduct having a structure ( Compound C-1 was obtained by reacting the epoxy adduct with compound c-1 at a ratio of 0.5 in the acid anhydride structure of compound c-1. The compound a-2 has a structure in which the hydroxyl group of the polyhydroxy aromatic compound 2 is alternately copolymerized at a ratio of 0.5 to one epoxy group of the epoxy compound 1.

[Production Example 3] Alkali developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 3 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1) 278 g, 2,2-bis (4 -Hydroxyphenyl) propane 57.1 g (hereinafter also referred to as polyhydroxy aromatic compound 3), tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 223 g were charged at 90 ° C. for 1 hour. The mixture was stirred at 120 ° C. for 5 hours to alternately copolymerize epoxy compound 1 and polyhydroxy aromatic compound 3. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-3) solution having an epoxy equivalent of 1130 was obtained. This was charged with 35.7 g of acrylic acid (compound b), 1.3 g of 2,6-di-tert-butyl-p-cresol, and 23.8 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 15 hours. After cooling to room temperature, 119 g of propylene glycol-1-monomethyl ether-2-acetate and 76.1 g of tetrahydrophthalic anhydride (compound c-1) were added and stirred at 100 ° C. for 5 hours. Further, 181 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 3 was obtained. The obtained alkali developable resin composition No. 3 contained a photopolymerizable unsaturated compound having Mw = 4830 and Mn = 2700, and the acid value (solid content) was 75 mgKOH / g.
In addition, alkali developable resin composition No. 3 is a photopolymerizable unsaturated compound containing one compound (A) compound a-3 and one compound (B) component (b) having a structure in which an epoxy adduct has a structure ( Compound C-1 was obtained by reacting the epoxy adduct with compound c-1 at a ratio of 0.5 in the acid anhydride structure of compound c-1. Further, the compound a-3 has a structure in which the hydroxyl group of the polyhydroxy aromatic compound 3 is alternately copolymerized at a ratio of 0.5 to one epoxy group of the epoxy compound 1.

[Production Example 4] Alkali developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 4 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1) 278 g, 2,2-bis (4 -Hydroxyphenyl) propane 57.1 g (polyhydroxyaromatic compound 3), tetrabutylammonium acetate 2.4 g, and propylene glycol-1-monomethyl ether-2-acetate 223 g were charged at 90 ° C. for 2 hours and at 120 ° C. for 5 hours. Stirring for a time, the epoxy compound 1 and the polyhydroxy aromatic compound 3 were alternately copolymerized. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-4) solution having an epoxy equivalent of 1120 was obtained. This was charged with 36.1 g of acrylic acid (compound b), 1.4 g of 2,6-di-tert-butyl-p-cresol, and 24.1 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 15 hours. After cooling to room temperature, 131 g of propylene glycol-1-monomethyl ether-2-acetate and 91.3 g of tetrahydrophthalic anhydride (Compound c-1) were added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 14.4 g of glycidyl methacrylate (hereinafter also referred to as compound d-1) was added and stirred at 120 ° C. for 8 hours. After cooling to room temperature, 205 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. The obtained alkali developable resin composition No. 4 contained a photopolymerizable unsaturated compound having Mw = 5440 and Mn = 2290, and the acid value (solid content) was 61 mgKOH / g.
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 4 is a compound (A) which is a compound a-4, and a compound b which is a component (B) is added to one hydroxyl group of an epoxy adduct having a structure ( C) The compound c-1 as the component has an acid anhydride structure in a ratio of 0.6, and the compound d-1 as the component (D) has a ratio of 0.1 epoxy groups in the epoxy adduct and the compound. It was obtained by reacting c-1 and compound d-1. The compound a-4 has a structure in which the hydroxyl group of the polyhydroxy aromatic compound 3 is alternately copolymerized at a ratio of 0.5 to one epoxy group of the epoxy compound 1.

[Production Example 5] Alkali developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 5 1,2-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1) 278 g, 2,2-bis (4 -Hydroxyphenyl) propane 57.1 g (hereinafter referred to as polyhydroxy aromatic compound 3), tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 223 g were charged at 90 ° C. for 2 hours, 120 ° C. Then, the epoxy compound 1 and the polyhydroxy aromatic compound 3 were alternately copolymerized. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-5) solution having an epoxy equivalent of 1130 was obtained. This was charged with 35.7 g of acrylic acid (compound b), 1.6 g of 2,6-di-tert-butyl-p-cresol, and 23.8 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 15 hours. After cooling to room temperature, 157 g of propylene glycol-1-monomethyl ether-2-acetate and 123 g of hexahydrophthalic anhydride (hereinafter also referred to as compound c-2) were added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 28.7 g of glycidyl methacrylate (Compound d-1) was added, and the mixture was stirred at 120 ° C. for 7 hours. After cooling to room temperature, 14.8 g of phthalic anhydride (hereinafter also referred to as compound e) was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 230 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. The obtained alkali developable resin composition No. 5 contained a photopolymerizable unsaturated compound having Mw = 5990 and Mn = 2800, and the acid value (solid content) was 73 mgKOH / g.
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 5 is a compound (A) which is a compound a-5 which is a component (B) and a compound b which is a component (B). C) The acid anhydride structure of compound c-2 which is component is 0.8 ratio, the epoxy group of compound d-1 which is (D) component is 0.2 ratio, and (E) component is A certain compound e is obtained by reacting an epoxy adduct with compound c-2, compound d-1 and compound e in a ratio of 0.1. The compound a-5 has a structure in which the hydroxyl group of the polyhydroxy aromatic compound 3 is alternately copolymerized at a ratio of 0.5 to one epoxy group of the epoxy compound 1.

[Production Example 6] Alkali-developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 6 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1) 278 g, 2,2-bis (4 -Hydroxyphenyl) propane 34.3 g (polyhydroxy aromatic compound 3), tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 208 g were charged, and the mixture was charged at 100 ° C. for 1 hour and at 120 ° C. for 5 hours. Stirring for a time, the epoxy compound 1 and the polyhydroxy aromatic compound 3 were alternately copolymerized. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-6) solution having an epoxy equivalent of 758 was obtained. This was charged with 49.7 g of acrylic acid (compound b), 1.5 g of 2,6-di-tert-butyl-p-cresol, and 33.1 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 14 hours. After cooling to room temperature, 131 g of propylene glycol-1-monomethyl ether-2-acetate and 92.5 g of tetrahydrophthalic anhydride (Compound c-1) were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 18.2 g of 3,4-epoxycyclohexylmethyl acrylate (Compound d-2) was added and stirred at 120 ° C. for 7 hours. After cooling to room temperature, 210 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. 6 was obtained. The obtained alkali developable resin composition No. 6 contained a photopolymerizable unsaturated compound having Mw = 2990 and Mn = 1680, and the acid value (solid content) was 70 mgKOH / g.
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound 6 contains a hydroxyl group of an epoxy adduct having a structure obtained by adding the compound (b) as the component (B) to the compound a-6 as the component (A) ( C) Compound c-1 as the component has an acid anhydride structure in a ratio of 0.6, and component (D) as a component in compound d-2 has a ratio of 0.1 to the epoxy adduct and compound. It is obtained by reacting c-1 and compound d-2. The compound a-6 has a structure in which the hydroxyl group of the polyhydroxy aromatic compound 3 is alternately copolymerized at a ratio of 0.3 to one epoxy group of the epoxy compound 1.

[Production Example 7] Alkaline-developable resin composition No. 1 containing a photopolymerizable unsaturated compound. Preparation of 7 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1) 278 g, 2,2-bis (4 -Hydroxyphenyl) propane 57.1 g (polyhydroxy aromatic compound 3), tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 223 g were charged, and the mixture was charged at 100 ° C. for 1 hour and at 120 ° C. for 5 hours. Stirring for a time, the epoxy compound 1 and the polyhydroxy aromatic compound 3 were alternately copolymerized. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-7) solution having an epoxy equivalent of 1150 was obtained. This was charged with 35.1 g of acrylic acid (compound b), 1.3 g of 2,6-di-tert-butyl-p-cresol, and 23.4 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 15 hours. After cooling to room temperature, 102 g of propylene glycol-1-monomethyl ether-2-acetate and 56.0 g of itaconic anhydride (hereinafter also referred to as compound c-3) were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 173 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 was obtained. The obtained alkali developable resin composition No. 7 contained a photopolymerizable unsaturated compound having Mw = 4640 and Mn = 2230, and the acid value (solid content) was 70 mgKOH / g.
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 7 is a compound (A) which is a compound a-7 and a compound b which is a component (B) is added to one hydroxyl group of an epoxy adduct having a structure ( Compound C-3 was obtained by reacting the epoxy adduct with compound c-3 at a ratio of 0.5 in the ratio of the acid anhydride structure of compound c-3. The compound a-7 has a structure in which one hydroxyl group of the epoxy compound 1 is alternately copolymerized at a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 3.

[Comparative Production Example 1] Alkali developable resin composition No. 1 containing a photopolymerizable unsaturated compound for comparison. Preparation of No. 8 Bisphenol A type epoxy resin (epoxy equivalent 194, hereinafter also referred to as polyfunctional epoxy compound 1) 194 g, 2,2-bis (4-hydroxyphenyl) propane 57.1 g, tetrabutylammonium acetate 2.4 g and propylene 167 g of glycol-1-monomethyl ether-2-acetate was charged and stirred at 90 ° C. for 2 hours and at 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 977 was obtained. This was charged with 31.0 g of acrylic acid, 1.2 g of 2,6-di-tert-butyl-p-cresol, and 20.7 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 130 g of propylene glycol-1-monomethyl ether-2-acetate and 107 g of tetrahydrophthalic anhydride were added and stirred at 100 ° C. for 5 hours. Further, 158 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. The obtained alkali developable resin composition No. 8 contained a photopolymerizable unsaturated compound having Mw = 5220 and Mn = 2470, and the acid value (solid content) was 103 mgKOH / g.

[Comparative Production Example 2] Alkaline-developable resin composition No. 1 containing a comparative photopolymerizable unsaturated compound for comparison. Preparation of 9 391 g of 2,2-bis (4-epoxypropyloxyphenyl) propane (epoxy equivalent 190), 95.2 g of 2,2-bis (4-hydroxyphenyl) propane, 4.9 g of tetrabutylammonium acetate and propylene glycol 328 g of -1-monomethyl ether-2-acetate was charged and stirred at 90 ° C. for 1 hour and 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 806 was obtained. This was charged with 71.1 g of acrylic acid, 1.4 g of 2,6-di-tert-butyl-p-cresol, and 47.4 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 110 ° C. for 7 hours. . After cooling to room temperature, 226 g of propylene glycol-1-monomethyl ether-2-acetate, 6.9 g of tetrabutylammonium acetate, and 177 g of tetrahydrophthalic anhydride were further added and stirred at 100 ° C. for 2 hours. Cool to room temperature, add 27.9 g of glycidyl methacrylate, 1.4 g of 2,6-di-tert-butyl-p-cresol and 22.8 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. For 4 hours. After cooling to room temperature, 280 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. The obtained alkali developable resin composition No. 9 contained a photopolymerizable unsaturated compound having Mw = 1470 and Mn = 2820, and the acid value (solid content) was 71 mgKOH / g.

[Comparative Production Example 3] Alkaline-developable resin composition No. 1 containing a comparative photopolymerizable unsaturated compound for comparison. Preparation of 10 Resorcinol diglycidyl ether (epoxy equivalent 116) 116 g, 2,2-bis (4-hydroxyphenyl) propane 57.1 g, tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 115 g was charged and stirred at 90 ° C. for 1 hour and 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 587 was obtained. This was charged with 35.7 g of acrylic acid, 1.0 g of 2,6-di-tert-butyl-p-cresol, and 23.8 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 12 hours. . After cooling to room temperature, 119 g of propylene glycol-1-monomethyl ether-2-acetate and 107 g of tetrahydrophthalic anhydride were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 14.4 g of glycidyl methacrylate was added and stirred at 120 ° C. for 4 hours. After cooling to room temperature, 146 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. 10 was obtained. The obtained alkali developable resin composition No. 10 contained a photopolymerizable unsaturated compound having Mw = 4990 and Mn = 2820, and the acid value (solid content) was 105 mgKOH / g.

[Comparative Production Example 4] An alkali developable resin composition No. 1 containing a comparative photopolymerizable unsaturated compound for comparison. Preparation of 11 Resorcinol diglycidyl ether (epoxy equivalent 116) 116 g, resorcinol 27.5 g, tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 95.7 g were charged at 90 ° C. for 2 hours. And stirred at 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 488 was obtained. This was charged with 35.7 g of acrylic acid, 0.9 g of 2,6-di-tert-butyl-p-cresol, and 23.8 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 115 g of propylene glycol-1-monomethyl ether-2-acetate and 106 g of tetrahydrophthalic anhydride were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 14.4 g of glycidyl methacrylate was added and stirred at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 122 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 was obtained. The obtained alkali developable resin composition No. 11 contained a photopolymerizable unsaturated compound having Mw = 3220 and Mn = 1810, and the acid value (solid content) was 114 mgKOH / g.

[Comparative Production Example 5] An alkali developable resin composition No. 1 containing a comparative photopolymerizable unsaturated compound for comparison. Preparation of 12 278 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 278, epoxy compound 1), 1,1-bis (4 '-Hydroxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (bisphenol compound 1) 65.1 g, tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 229 g The mixture was stirred and stirred at 90 ° C. for 2 hours and at 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 825 was obtained. This was charged with 53.3 g of acrylic acid, 1.8 g of 2,6-di-tert-butyl-p-cresol, and 35.6 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 169 g of propylene glycol-1-monomethyl ether-2-acetate and 129 g of tetrahydrophthalic anhydride were added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 45.8 g of glycidyl methacrylate was added, and the mixture was stirred at 120 ° C. for 6 hours. After cooling to room temperature, 277 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. 12 was obtained. The obtained alkali developable resin composition No. 12 contained a photopolymerizable unsaturated compound having Mw = 4000 and Mn = 2060, and the acid value (solid content) was 55 mgKOH / g.

The alkali-developable resin composition No. 1-7 and the alkali-developable resin compositions No. 1 prepared in Comparative Production Examples 1-5. Measurement of the dielectric loss tangent of 8-12 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. Any one of 1 to 12 is applied by spin coating so as to have a thickness of about 2 μm, dried at 80 ° C. for 10 minutes, unnecessary portions other than those on the aluminum electrode are removed, and a hot air dryer is used to remove 230 A test piece was prepared by heating and drying at 30 ° C. for 30 minutes, and further forming an aluminum electrode by the same method as described above. The test piece has a structure in which a cured product of an alkali-developable resin composition is sandwiched with a thickness of about 1.5 μm between 10 mm × 10 mm square aluminum electrodes. 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 is apparent from Table 1, the alkali-developable resin composition Nos. Obtained in the above Production Examples 1 to 7 were used. Nos. 1 to 7 have a dielectric loss tangent at 30 Hz of 0.008 or less, while the comparative alkaline developable resin composition Nos. 8-12 was larger than 0.008.

[Production Examples 8 to 14 and Comparative Production Examples 6 to 10]
To 44 g of the alkali-developable resin composition, 6.3 g of trimethylolpropane triacrylate, 2.1 g of benzophenone and 78 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred well to obtain an alkali-developable photosensitive resin composition. I got a thing.
In Production Examples 8 to 14, the alkali developable resin composition Nos. Obtained in Production Examples 1 to 7 were used as the alkali developable resin compositions. 1-No. No. 7, and the resulting alkali-developable photosensitive resin composition was used as an alkali-developable photosensitive resin composition No. 1-No. It was set to 7. In Comparative Production Examples 6 to 10, the alkali developable resin compositions Nos. Obtained in Comparative Production Examples 1 to 5 were used as the alkali developable resin compositions. 8-No. No. 12, and the resulting alkali-developable photosensitive resin composition was used as an alkali-developable photosensitive resin composition No. 8-No. It was set to 12.

The alkali development type photosensitive resin composition No. prepared in the above production examples 8-14. 1-No. 7 and comparative alkali development type photosensitive resin composition No. 1 prepared in Comparative Production Examples 6-10. 8-No. No. 12, evaluation of developability and adhesiveness 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, exposure was performed using a predetermined mask and an ultrahigh pressure mercury lamp as a light source, followed by development by immersing in 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washing with water. . After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. About the obtained pattern, evaluation of developability and adhesiveness was performed on the following references | standards. The results are shown in Table 2.

<Developability>
The presence or absence of a development residue remaining between 15 μm line and space lines obtained by development was observed, and “O” indicates that no residue was observed, and “X” indicates that the residue was observed.
<Adhesion>
The pattern peeling obtained by development was observed visually, ○ when the pattern peeling was not observed at all, Δ when the pattern peeling was partially observed, and one where the pattern peeling was observed over the entire surface X.

  As is apparent from Table 2, the alkali development type photosensitive resin compositions of Production Examples 8 to 14 were excellent in developability and adhesion. On the other hand, the comparative alkali development type photosensitive resin compositions of Comparative Production Examples 6 to 9 were excellent in developability but did not have good adhesion. Moreover, although the comparative alkali development type photosensitive resin composition of the comparative manufacture example 10 was excellent in adhesiveness, the developability was not good.

[Examples 1 to 7 and Comparative Examples 1 to 5] Preparation and Evaluation of Liquid Crystal Display Device Substrate and Liquid Crystal Display Device <Creation and Evaluation of Liquid Crystal Display Device Substrate>
(Creation of board 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 alignment control protrusions)
The alkali-developable photosensitive composition was applied to the ITO-coated substrate by spin coating so as to have 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 alignment control protrusions, whereby a liquid crystal display device substrate was obtained. In Examples 1 to 7, the alkaline development type photosensitive compositions Nos. 1 to 7 prepared in Production Examples 8 to 14 were used. 1-No. In Comparative Examples 1 to 5, the alkali developing type photosensitive composition No. 1 prepared in Comparative Production Examples 6 to 10 was used. 8-No. 12 was used.
About the obtained substrate for liquid crystal display devices, the cross-sectional shape of the formed liquid crystal alignment control protrusion 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. The evaluation results are shown in Table 3.

<Creation and evaluation of liquid crystal display device>
An MVA type liquid crystal display device was prepared using the obtained substrate for liquid crystal display device, 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 3.

The alkali development type photosensitive resin composition No. of manufacture example 8-14. 1-No. The substrate for a liquid crystal display device of the present invention formed using 7 is good in that the cross-sectional shape of the liquid crystal alignment control projection is semicircular or semielliptical, and the liquid crystal display device formed using these has a wide field of view. It had corners and good display characteristics without causing burn-in.
On the other hand, the alkali development type photosensitive resin composition No. of comparative manufacture examples 6-9. 8-No. The substrate for liquid crystal display device formed using 11 has an overhang shape in the cross-sectional shape of the liquid crystal alignment control protrusion, and the liquid crystal display device formed using these has a narrow viewing angle and burn-in occurred. . The alkali development type photosensitive resin composition No. The liquid crystal display device substrate formed using the liquid crystal display device 12 has a trapezoidal cross-sectional shape of the liquid crystal alignment control projection, and the liquid crystal display device formed using the liquid crystal display device cannot achieve a sufficiently wide viewing angle.

Claims (6)

At least a translucent substrate and a liquid crystal split orientation control protrusion,
Alkaline development in which the liquid crystal split orientation control protrusions further contain a photopolymerization initiator in an alkali developable resin composition having a dielectric loss tangent of 0.008 or less at any frequency in the frequency range of 10 to 50 Hz. Type photosensitive resin composition,
The alkali-developable resin composition is obtained by esterifying a polybasic acid anhydride (C) to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to an epoxy resin (A). Containing a photopolymerizable unsaturated compound having a structure;
The epoxy resin (A) is an alternating copolymer of an epoxy compound represented by the following general formula (I) and a polyhydroxy aromatic compound (excluding a bisphenol compound represented by the following general formula (II)). A substrate for a liquid crystal display device, characterized by having a structure as described above.

  2. The substrate for a liquid crystal display device according to claim 1, wherein, in the general formula (I), Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0.   The photopolymerizable unsaturated compound has a structure obtained by adding an epoxy compound (D) to a reaction product obtained by esterifying the polybasic acid anhydride (C) with the epoxy adduct. 3. The substrate for a liquid crystal display device according to claim 1, wherein the substrate is a photopolymerizable unsaturated compound (M).   The photopolymerizable unsaturated compound has a structure obtained by esterifying a polybasic acid anhydride (E) to an epoxy addition product obtained by adding the epoxy compound (D) to the reaction product. The substrate for a liquid crystal display device according to claim 3, wherein the substrate is a photopolymerizable unsaturated compound (Z).   In the alkali development type photosensitive resin composition, the content of the photopolymerizable unsaturated compound is 1 to 70% by mass, and the content of the photopolymerization initiator is 0.1 to 30% by mass. The substrate for a liquid crystal display device according to any one of claims 1 to 4.   A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 1.