JP4572664B2 - Photosensitive composition for liquid crystal split alignment protrusion and liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive composition for liquid crystal split alignment protrusions used for manufacturing a liquid crystal display device, and a liquid crystal display device using the same.

  On the other hand, in recent years, a technology of a liquid crystal television that uses a thin liquid crystal display device with low power consumption for a large screen television has been put into practical use, and the market is about to rise rapidly. Accordingly, there is a strong demand for improvement in the low viewing angle of a liquid crystal television, which is inferior to a television using a conventional cathode ray tube. As an attempt to improve the viewing angle of a liquid crystal display device, there is a method in which a protrusion is formed on a transparent electrode, the liquid crystal is locally tilted using the slope of this protrusion, and the liquid crystal is divided and aligned in multiple directions within one pixel. . The projections on the transparent electrode are preferably arched, and a pattern is usually formed with a positive resist and reflowed by heat melting to obtain an arched shape (Patent Document 1). However, when the positive resist is heated, there is a problem that the unreacted quinonediazite and the novolak resin undergo a coupling reaction to cause the resist to turn red. Further, since a positive resist generally requires a higher strength alkaline developer than a negative resist, deterioration due to oxygen in the air is remarkably difficult to manage the liquid. Furthermore, the positive resist develops a difference in solubility in the alkali developer between the exposed and unexposed areas due to the alkali-soluble carboxylic acid generated by photolysis of quinonediazide. Compared to negative resists that generate a difference in solubility, the margin of development conditions is narrow, and it is affected by development deterioration due to oxygen in the air, making it difficult to manage the development state. For this reason, a negative resist has been strongly desired as a technique for replacing the conventional positive resist for the liquid crystal split alignment protrusion.

On the other hand, as a technique using a negative resist, by selecting and applying a specific photopolymerization initiator, an arch-shaped liquid crystal alignment protrusion is formed regardless of heat melting, and a color liquid crystal alignment alignment protrusion is provided. A filter is described in Patent Document 2. However, when trying to obtain arch-shaped split liquid crystal alignment protrusions without relying on heating and melting, it is necessary to selectively rub a specific part of the resist in the alkali development process, which narrows the margin of development conditions. Was a problem.
JP-A-7-92689 JP 2003-330011 A

  The present invention is for solving such problems, and forms liquid crystal split alignment protrusions that are not colored, have excellent transmittance, and have a stable shape such as height and angle of contact with the substrate. It is an object of the present invention to provide a photosensitive composition for liquid crystal split alignment protrusions.

As a result of intensive studies on the above problems, the present inventors have found that a specific photosensitive composition can achieve the above object, and have completed the present invention. That is, the gist of the present invention is as follows.
(1) In the photosensitive composition for liquid crystal split alignment protrusions mainly composed of an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin, the weight ratio of alkali-soluble resin / ethylenically unsaturated compound is 1.5 or more. In addition, the photosensitive layer coated with the photosensitive composition with a film thickness of 1.7 μm is irradiated with ultraviolet light with a wavelength of 365 nm at 50 mJ / cm ² through a mask having a fine line pattern with a line width of 15 μm. The contact angle formed from the side of the fine line image obtained by the shower development process at 23 ° C. and the water pressure of 0.25 MPa and the substrate plane is (W1), and the fine line image is further heated at 230 ° C. for 30 minutes. A photosensitive composition for liquid crystal split alignment protrusions, wherein (W2) is a contact angle formed from the side surface of the liquid crystal split alignment protrusion-like thin line image and the substrate plane.
W1 / W2 ≧ 1.2
(2) A liquid crystal display device comprising a liquid crystal split alignment protrusion formed using the photosensitive composition as described in (1) above.

  According to the present invention, there is provided a photosensitive composition for liquid crystal split alignment protrusions that can form liquid crystal split alignment protrusions that are not colored, have excellent transmittance, and have a stable shape such as height and angle of contact with a substrate. In addition, it is possible to provide a high-quality liquid crystal display device.

The invention of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and is not specified in these contents.
First, the photosensitive composition for liquid crystal split alignment protrusions of the first aspect of the present invention (hereinafter sometimes simply referred to as photosensitive composition) will be described in detail.
[A] Constituent Component of Photosensitive Composition for Liquid Crystal Split Alignment Protrusion of the Present Invention The photosensitive composition of the present invention must have an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin as constituent components. To do. Hereinafter, each component which comprises the photosensitive composition of this invention is demonstrated.

[1] Ethylenically unsaturated compound The ethylenically unsaturated compound constituting the photosensitive composition of the present invention means a compound having at least one ethylenically unsaturated bond in the molecule. And a compound having two or more ethylenically unsaturated bonds in the molecule from the viewpoint that the difference in developer solubility between the exposed portion and the non-exposed portion can be expanded. The bond is more preferably an acrylate compound derived from a (meth) acryloyloxy group.

  Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like (in the present invention, “(meth) acryl” means “acryl and / or methacryl”; the same shall apply hereinafter). .

  Typically, compounds having two or more ethylenically unsaturated bonds include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

[1-1] Esters of unsaturated carboxylic acid and polyhydroxy compound Specific examples of esters of unsaturated carboxylic acid and polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.

Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.

Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, etc.

In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.
[1-2] (Meth) acryloyloxy group-containing phosphates (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing a (meth) acryloyloxy group. What is represented by (A-1) or (A-2) is preferable.

(In formulas (A-1) and (A-2), Rz represents a hydrogen atom or a methyl group, j is an integer of 1 to 25, and k is 1, 2, or 3.)
Here, j is preferably 1 to 10, particularly 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) Examples thereof include acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

[1-3] Urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound As urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound, for example, hydroxymethyl (meta) ) Hydroxy (meth) acrylate compounds such as acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, and aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, Cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycl With polyisocyanate compounds such as cycloaliphatic polyisocyanates such as loheptane triisocyanate, aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate, tris (isocyanatophenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, etc. Examples include reactants. For example, trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.

  Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly Compound (i-1) obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, Alternatively, for compounds having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, and “Duranate” manufactured by Asahi Kasei Kogyo Co., Ltd. Biuret such as “18H-70B” Compounds having three or more isocyanate groups in one molecule, such as adduct types such as Yup, "Duranate P-301-75E", "Duranate E-402-90T", and "Duranate E-405-80T" 4 or more in one molecule, such as compound (i-2) obtained by polymerizing, or compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, Preferably, compounds having 6 or more isocyanate groups, such as “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. , 1 1 or more hydroxyl groups and 2 or more in a molecule can preferably be obtained by a compound having three or more (meth) acryloyloxy groups and (ii), is reacted.

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, and particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

  In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene and ethyl acetate. It can be produced by a method of reacting at a molar ratio of 1/10 to 10/1 at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate as necessary. it can.

[1-4] Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound Epoxy (meth) acrylate of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound ) Acrylates include, for example, (meth) acrylic acid or hydroxy (meth) acrylate compounds as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol Polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethy Aliphatic polyepoxy compounds such as roll propane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) Aromatic polyepoxy compounds such as cresol novolac polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, etc. And a reaction product with a polyepoxy compound such as a heterocyclic polyepoxy compound.

[1-5] Other ethylenically unsaturated compounds As other ethylenically unsaturated compounds, in addition to the above, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, Vinyl group-containing compounds such as divinyl phthalate, ether bond of ether bond-containing ethylenically unsaturated compound, thioether bond-containing compounds having improved crosslinking speed by sulfidation with phosphorus pentasulfide and the like to change to thioether bond, and For example, a polyfunctional (meth) acrylate compound and a silica sol having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (manufactured by Nissan Chemical Co., Ltd., “IPA” -ST "), methyl ethyl ketone dispersion Ganosilica sol (“MEK-ST” manufactured by Nissan Chemical Co., Ltd.), methylisobutylketone-dispersed organosilica sol (“MIBK-ST” manufactured by Nissan Chemical Co., Ltd.), etc.] are bonded using an isocyanate group or mercapto group-containing silane coupling agent. Examples thereof include compounds whose strength and heat resistance as a cured product are improved by reacting and bonding silica sol with an ethylenically unsaturated compound via a silane coupling agent.

The above ethylenically unsaturated compounds may be used alone or in combination of two or more.
In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and ester (meth) acrylates are more preferable. Among the ester (meth) acrylates, ester (meth) acrylates containing 3 or more (meth) acryloyloxy groups such as dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

The content of the ethylenically unsaturated compound in the photosensitive composition of the present invention is usually 1% by weight or more with respect to the total amount of components of the photosensitive composition excluding the solvent (hereinafter referred to as total solid content). Preferably it is 2 weight% or more, Usually 60 weight% or less, Preferably it is 40 weight% or less. If the amount of the ethylenically unsaturated compound is too small, the sensitivity and the development dissolution rate are liable to be lowered, and if too large, the reproducibility of the image cross-sectional shape is liable to be lowered and the resist film is liable to be thin.
[2] Photopolymerization initiator Any known photopolymerization initiator that constitutes the photosensitive composition of the present invention can be used to generate radicals that polymerize ethylenically unsaturated groups by ultraviolet rays. And a compound capable of generating an acid by ultraviolet rays.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine,
Halomethylated oxadiazole derivatives,
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (
o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole Imidazole derivatives such as dimers,
Benzoin such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzoin alkyl ethers,

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone,
Benzanthrone derivatives,
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone,
2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(
Acetophenone derivatives such as methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1, -trichloromethyl- (p-butylphenyl) ketone,
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone,
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate,

Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine,
Phenazine derivatives such as 9,10-dimethylbenzphenazine,
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-
Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6 Pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro Titanocene derivatives such as -3- (pyr-1-yl) -phen-1-yl,

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

  1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl]-, 1- (O-acetyloxime), etc., described in JP-A 2000-80068, JP-A 2001-233842, JP-A 2001-235858, and WO 02/00903 Examples thereof include oxime derivatives represented by the compounds described above.

These photopolymerization initiators are used alone or in combination. Examples of the combination are described in, for example, JP-B-53-12802, JP-A-1-279903, JP-A-2-48664, JP-A-4-164902, or JP-A-6-75373. And a combination of initiators.
The content of the photopolymerization initiator in the photosensitive composition of the present invention is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less, based on the total solid content. Preferably it is 30 weight% or less. If the amount of the ethylenically unsaturated compound is too small, the sensitivity tends to decrease, and if it is too large, the background stain (development solubility) tends to decrease.

[3] Alkali-soluble resin The alkali-soluble resin constituting the photosensitive composition of the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include the following compounds. (Meth) acrylic acid, (meth) acrylic acid ester, maleic acid, vinyl acetate, maleimide, etc., unsaturated group and carboxyl group-containing epoxy resin, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (Meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide and the like, a hydroxyl group or carboxyl group-containing vinyl resin containing a hydroxyl group or a carboxyl group, and polyamide, polyester, polyether, polyurethane, polyvinyl butyral, Polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose and the like can be mentioned. Of these, unsaturated group and carboxyl group-containing epoxy resins and carboxyl group-containing vinyl resins are preferred from the viewpoints of alkali developability and image formability.

[3-1] Unsaturated Group and Carboxy Group-Containing Epoxy Resin As the unsaturated group and carboxyl group-containing epoxy resin according to the present invention, an α, β-unsaturated group-containing carboxylic acid adduct of an epoxy resin is used as a polyvalent carboxylic acid. An epoxy resin containing an unsaturated group and a carboxyl group to which an acid and / or its anhydride is added, that is, formed by ring-opening addition of a carboxyl group of an α, β-unsaturated monocarboxylic acid to an epoxy group of an epoxy resin. In addition, an ethylenically unsaturated bond is added via an ester bond (—COO—), and an ester bond formed by reacting a carboxyl group of the polyvalent carboxylic acid or its anhydride with the resulting hydroxyl group. It is essential to include those to which a remaining carboxyl group is added.
Hereinafter, the constituent components of the unsaturated group- and carboxyl group-containing epoxy resin will be described in detail.

[3-1-1] Epoxy resin Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclo Examples thereof include a polymerized epoxy resin with pentadiene, among which a phenol novolac epoxy resin, a cresol novolac epoxy resin, and a polymerized epoxy resin with phenol and dicyclopentadiene are preferable.

[3-1-2] α, β-Unsaturated monocarboxylic acid Examples of α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. And pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta ( (Meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth) acrylic acid and ε-caprolactone, etc., among them (meth) acrylic acid Is preferred.

[3-1-3] Polyvalent carboxylic acid or anhydride thereof Examples of the polyvalent carboxylic acid or anhydride thereof include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and 3-methyltetrahydrophthalic acid. 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid 4-ethylhexahydrophthalic acid, and their anhydrides, among which maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferred, and tetrahydrophthalic anhydride is further preferable.

  In the above, in the present invention, the epoxy resin is a phenol novolac epoxy resin or a cresol novolac epoxy resin in terms of sensitivity, resolution, adhesion to a substrate, etc. as a photosensitive composition, and α, β- It is preferable that the unsaturated monocarboxylic acid is (meth) acrylic acid and the polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride. Moreover, what has an acid value of 20-200 mg-KOH / g is preferable, and what is 30-180 mg-KOH / g is still more preferable. In addition, the polystyrene-reduced weight average molecular weight (hereinafter abbreviated as “weight average molecular weight Mw by GPC measurement”) measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) is usually 1,000 or more. Preferably, it is 1,500 or more, usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less.

In the present invention, the unsaturated group- and carboxyl group-containing epoxy resin is dissolved in an organic solvent such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, or propylene glycol monomethyl ether acetate by a conventionally known method. Tertiary amines such as triethylamine, benzyldimethylamine, tribenzylamine, or quaternary ammonium such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride In the presence of catalysts such as salts, phosphorus compounds such as triphenylphosphine, or stibins such as triphenylstibine In the presence of a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone, the α, β-unsaturated monocarboxylic acid is usually added in an amount of 0.7 to 1 to 1 chemical equivalent of the epoxy group of the epoxy resin. 3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents are added, and an addition reaction is usually performed at a temperature of 60 to 150 ° C., preferably 80 to 120 ° C., followed by polyvalent carboxylic acid or an anhydride thereof. Is usually added in an amount of 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group generated in the reaction, and the reaction is carried out under the above conditions. It can be manufactured by a method such as continuing.

  Specific examples of the structural repeating unit of the above unsaturated group and carboxyl group-containing epoxy resin are shown below.

[3-2] Carboxyl group-containing vinyl resin Examples of the carboxyl group-containing vinyl resin include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and the like. Saturated carboxylic acid, styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate , Dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, ben (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl ( Examples thereof include copolymers with vinyl compounds such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and vinyl acetate. Among them, dicyclopentadienyl (meth) acrylate has a large rate of change in contact angle due to post-heating, stably forms arch-shaped liquid crystal split alignment protrusions, and has a wide latitude for development time and developer deterioration. The dicyclopentadienyl (meth) acrylate is preferably a compound provided by JP-A-2001-89533, for example, a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, a dicyclopentenyloxy. Examples thereof include (meth) acrylate having an alkyl skeleton.

Among the above copolymers, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% styrene, 10-70 mol% (meth) acrylate, 10 (meth) acrylic acid. A copolymer composed of ˜60 mol% is more preferred, and a copolymer composed of 5-25 mol% styrene, 20-60 mol% (meth) acrylate, and 15-55 mol% (meth) acrylic acid is particularly preferred. These carboxyl group-containing vinyl resins have an acid value of 30 to 250 mg-KOH / g, preferably 50 to 200 mg-KOH / g, and more preferably 70 to 150 mg-KOH / g.

  The weight average molecular weight Mw by GPC measurement is usually 1,000 or more, preferably 1500 or more, more preferably 2000 or more, usually 100,000 or less, preferably 50,000,000 or less, more preferably 20,000 or less, particularly Preferably it is 10,000 or less. When the carboxyl group-containing vinyl resin in the above range is contained, it is preferable because deformation of the photosensitive composition upon heating is large (change in contact angle is large).

  Further, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. For example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl is added to the carboxyl group-containing polymer. (Meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Saturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2 Yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate is obtained by reacting 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer. Reaction products and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl A compound having two or more unsaturated groups such as (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate , Vinyl crotonate, vinyl (meth) acrylamide The ratio of the compound having two or more kinds of unsaturated groups such as, and unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the former unsaturated group A reaction product obtained by copolymerization so as to be 10 to 90 mol%, preferably about 30 to 80 mol%, and the like can be mentioned.

The content of the alkali-soluble resin in the photosensitive composition of the present invention is usually 30% by weight or more, preferably 50% by weight or more, and usually 98% by weight or less, preferably 90% by weight, based on the total solid content. It is as follows. If the amount of the ethylenically unsaturated compound is too small, the reproducibility of the image cross-sectional shape is poor and the heat resistance is lowered, and if it is too much, the sensitivity is lowered and the development dissolution rate is lowered.
The photosensitive composition of the present invention needs to increase the deformation of the resist image during heating, and the content of the alkali-soluble resin and the content of the ethylenically unsaturated compound are preferably in a specific ratio. Specifically, the weight ratio of the content of alkali-soluble resin / ethylenically unsaturated compound is usually 1.5 or more, preferably 2 or more, more preferably 3 or more, and particularly preferably 3.5 or more.

[4] Other components [4-1] Surfactant In addition to the above components, the photosensitive composition of the present invention further has coating properties as a coating liquid for the composition and developability of the photosensitive composition layer. For the purpose of improvement, nonionic, anionic, cationic, amphoteric, and fluorine based surfactants may be contained. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy And ethylene sorbite fatty acid esters.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, etc. Can be mentioned.

The cationic surfactants include quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, and the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids, and the like. Is mentioned.
In the photosensitive composition of the present invention, the surfactant content is preferably 10% by weight or less, more preferably 1 to 5% by weight, based on the total solid content.

[4-2] Other additives The photosensitive composition of the present invention has various additives, such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, in addition to the above components. 2 wt% or less of the thermal polymerization inhibitor and a plasticizer such as dioctyl phthalate, didodecyl phthalate, tricresyl phosphate or the like may be contained at a ratio of 40 wt% or less.
Furthermore, in this invention, a polymerization accelerator can also be added as needed. Specifically, for example, an ester of an amino acid such as N-phenylglycine or a dipolar compound thereof, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole Mercapto group-containing compounds such as 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol , Trifunctional thiol compounds such as trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine or Examples thereof include derivatives such as salts such as ammonium salts and sodium salts, amino acids having aromatic rings such as phenylalanine, salts such as ammonium and sodium salts, and derivatives such as esters, and derivatives thereof.
In the photosensitive composition of the present invention, the content of the polymerization accelerator is preferably 20% by weight or less, more preferably 1 to 10% by weight, based on the total solid content.

[5] Organic solvent Each of the above-described components is usually prepared by using an organic solvent so that the solid content concentration is 5 to 50% by weight, preferably 10 to 40% by weight. .
The organic solvent is not particularly limited as long as it can dissolve and disperse the above-described components and has good handleability. Specifically, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMAc”), methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, lactic acid Examples include methyl, ethyl lactate, methanol, ethanol, propanol, butanol, tetrahydrofuran, and the like. The boiling point is preferably in the range of 100 to 200 ° C, more preferably in the range of 120 to 170 ° C.

[B] Pattern formation characteristics of the photosensitive composition for liquid crystal split alignment protrusions of the present invention The photosensitive composition of the present invention is characterized by pattern formation characteristics before and after heat treatment. Specifically, the photosensitive composition of the present invention. The photosensitive layer coated with the product with a film thickness of 1.7 μm was irradiated with ultraviolet light with a wavelength of 365 nm at 50 mJ / cm ² through a mask having a fine line pattern with a line width of 15 μm, followed by 23 ° C., water pressure of 0.25 MPa. The contact angle formed from the side surface of the fine line image obtained by the shower development process and the substrate plane is (W1), and the fine line image is further subjected to a heat treatment at 230 ° C. for 30 minutes to form a fine line image having liquid crystal split alignment protrusions. When the contact angle formed from the side surface and the substrate plane is (W2), W1 / W2 needs to be 1.2 or more. W1 / W2 is preferably 1.3 or more, more preferably 1.5 or more, and is usually 10 or less, preferably 8 or less.
By using the photosensitive composition of the present invention, an arch shape necessary for the shape of the liquid crystal split alignment protrusions can be obtained by heating (see FIG. 1).

[C] Formation of Pixels Using the Photosensitive Composition for Liquid Crystal Divided Alignment Protrusions of the Present Invention and Method for Producing Liquid Crystal Panel The photosensitive composition of the present invention is not particularly limited as long as it satisfies the above relational expression. For example, as described in [A] and [3] above, the content of the alkali-soluble resin / the content of the ethylenically unsaturated compound and the weight-average molecular weight of the alkali-soluble resin are specific, and the side chain ethylenic addition polymerizability This is specifically achieved by using a group having a group.

Next, a method for forming liquid crystal split alignment protrusions using the photosensitive composition for liquid crystal split alignment protrusions according to the first aspect of the present invention and a method for manufacturing a liquid crystal panel according to the second aspect of the present invention will be described.
[1] Method for Forming Liquid Crystal Divided Alignment Protrusion First, a black matrix obtained by the method described in JP-A-2003-33011 and the like, a red, blue, and green color filter are provided, and a 150 nm thick film is further formed thereon. Application device such as spinner, wire bar, flow coater, die coater, roll coater, spray etc. on the above-mentioned photosensitive composition for liquid crystal split alignment protrusions of the present invention on a transparent substrate usually 0.1 to 2 mm thick with ITO deposited Apply using. The coating film thickness of the composition is usually 0.5 to 5 μm. After the coating film made of the composition is dried, a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. Usually, an image obtained after development is required to have a fine line reproducibility of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with a clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferable.

In the present invention, the developed image has a cross-sectional shape close to a rectangular shape. In order to obtain an arched shape necessary for the shape of the liquid crystal split alignment protrusion, it is usually 150 ° C. or higher, preferably 180 ° C.
Above, more preferably 200 ° C. or more, usually 400 ° C. or less, preferably 300 ° C. or less, more preferably 280 ° C. or less, and usually 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 A liquid crystal having a width of 0.5-20 μ and a height of 0.2 to 5 μm by transforming the rectangular cross-sectional shape into an arcuate shape by performing a heat treatment for 60 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less. Split alignment protrusions are formed. The range of deformation during heating is adjusted appropriately for the photosensitive composition and heating conditions, and the contact angle (W1) formed from the side surface of the fine line image (rectangular image cross-sectional shape) before heating and the substrate plane is the above heat treatment. When the contact angle (W2) formed from the side surface of the subsequent thin line image and the substrate plane is compared, W1 / W2 is 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, usually 10 or less. , Preferably 8 or less. The higher the heating temperature or the longer the heating time, the higher the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate. In addition, as described in [A] and [3] above, the content of the alkali-soluble resin / the content of the ethylenically unsaturated compound and the weight-average molecular weight of the alkali-soluble resin are specific, and the side chain ethylenic addition polymerizability Those having a group are particularly excellent in the deformation effect during heating, the rectangularity after development and the shape of the heating arch.

A hot plate, an IR oven, a convection oven, or the like can be used for drying the coating film made of the composition of the present invention. Preferred drying conditions are a temperature of 40 to 150 ° C. and a drying time of 10 seconds to 60 minutes.
Examples of the light source used in the exposure process of the dried coating film include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, and the like, an argon ion laser, and a YAG laser. And laser light sources such as excimer laser and nitrogen laser. When only light of a specific wavelength is used, an optical filter can be used.

The development process is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured portion. However, as described above, from the viewpoint of environmental pollution, harm to the human body, fire risk, etc., the organic solvent Instead, it is preferred to use an alkaline developer.
Examples of such an alkaline developer include inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, triethanol. An aqueous solution containing an organic alkali compound such as amine, tetraalkylammonium hydroxide, and tetramethylammonium hydroxide can be used.

If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.
For example, the surfactant used in the developer includes an anionic surfactant having a sodium naphthalene sulfonate group, a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants.
Although there is no restriction | limiting in particular about the method of development processing, Usually, it is 10-50 degreeC, Preferably it is carried out by methods, such as immersion development, spray development, brush development, ultrasonic development, at 15-45 degreeC.

[2] Liquid crystal display device (panel)
Next, a manufacturing method of the liquid crystal display device (panel) according to the present invention will be described. In the liquid crystal display device according to the present invention, an alignment film is usually formed on a color filter, a spacer and the above-mentioned liquid crystal split alignment protrusions are formed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell. Then, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate differs depending on the use of the liquid crystal display device, but is usually 2
It is selected in the range of not less than μm and not more than 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
[1] Example 1-3, Comparative Example 1
Each test solution was applied to a glass substrate (Asahi Glass Co., Ltd. color filter glass plate “AN100”) made of 150 nm thick ITO by sputtering, dried on a hot plate at 80 ° C. for 3 minutes, and dried. A coating film having a thickness of 1.7 μm was obtained. Thereafter, image exposure was performed from the coating film side through various fine exposure conditions of 25, 50, 100, and 200 mJ / cm ⁻² using 3 kW high-pressure mercury through a fine line pattern mask having a width of 15 μm. Subsequently, after performing a shower development with a water pressure of 0.25 megapascals at 23 ° C. using a developer composed of an aqueous solution containing 1% by weight of potassium carbonate and 4% by weight of a nonionic surfactant. The development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was twice the time (break time) for dissolving and removing the photosensitive layer. The glass substrate thus imaged was heated at 230 ° C. for 30 minutes to form a fine line pattern deformed into an arch shape. The obtained cross-sectional shape of the thin wire before and after heating was measured with a Violet laser electron microscope “VK9500” manufactured by Keyence, and the contact angle between the substrate plane and the side surface of the thin wire image was obtained. Evaluation was made by the method.

[Examples 4 and 5]
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 140 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an alkali-soluble resin P-2. When the weight average molecular weight Mw of the binder resin thus obtained was measured by GPC, it was about 5000.
Photosensitive materials were produced and evaluated in the same manner except that the test solution in Example 1 was changed to that in Table 1 (Example 4).
<Evaluation of rate of change of contact angle by heating>
Measure the cross-sectional shape of the thin line before and after heating with VK9500, determine the contact angle, and form the contact angle (W1) formed from the side surface and substrate plane of the pre-heating thin line image and the side surface and substrate plane of the heated thin line image The contact angle (W2) was determined, and the change in contact angle due to heating was evaluated from the value of the rate of change in contact angle (W1 / W2) as follows.

A: W1 / W2 is 2 or more
B: W1 / W2 is 1.5 or more and less than 2
C: W1 / W2 is 1.2 or more and less than 1.5
D: W1 / W2 is less than 1.2

<Image formation>
Images obtained by the above exposure and development processes were evaluated as follows.
A: An image having a film thickness of 70% or more with respect to the coating film thickness was formed.
B: An image having a film thickness of less than 70% with respect to the coating film thickness was formed.
C: The photosensitive layer was completely dissolved and no image was formed. D: The non-image area was not dissolved at all and no image was formed.

[3] Comparative example 2
As an alkali-soluble resin, a novolak resin (weight average molecular weight 7,000) composed of a polycondensate of mixed phenols having a mixing ratio of phenol: m-cresol: p-cresol of 20:50:30 in molar ratio with formaldehyde 80 parts by weight, naphthoquinone-1,2
-A positive photosensitive composition solution comprising 20 parts by weight of an ester compound (esterification rate 30 mol%, weight average molecular weight 2000) of diazide-5-sulfonyl chloride and pyrogallol / acetone resin, and 1000 parts by weight of PGMA. When a coated sample was prepared in the same manner as in Example 1 and the same evaluation was attempted, the evaluation of image formation was D. Also, the coated sample was 230 ° C 3
Redness was observed after 0 minutes of heat treatment. On the other hand, no red discoloration was observed in the samples obtained using the negative resists of Examples 1-3 and Comparative Example 1.

M-1: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate (DPHA)
M-2: bifunctional phosphate ester “PM-21” manufactured by Shin-Nakamura Scientific Co., Ltd.
S-1: “CGI 242 (CGI242)” manufactured by Ciba Special Chemicals Co., Ltd.
S-2: “Irgacure 369” manufactured by Ciba Special Chemicals Co., Ltd.
S-3: 2-mercaptobenzothiazole S-4: “Irgacure 907” manufactured by Ciba Special Chemicals Co., Ltd.
S-5: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer P-1: compound represented by the following formula (n represents an integer) Weight average molecular weight 2000, solid content acid value 100

・ F-1 Sumitomo 3M Fluorosurfactant "FC130"
-PGMA isopropylene glycol monomethyl ether acetate According to Table 1 above, Examples 1 to 5 using the photosensitive composition of the present invention have a high deformation rate of contact angle, and arch-shaped protrusions are well formed. As a result, it was found that the liquid crystal split alignment protrusions can be formed with good image formation.

  The present invention provides a photosensitive composition for liquid crystal split alignment protrusions that is capable of forming liquid crystal split alignment protrusions that are not colored, have excellent transmittance, and have a stable shape such as height and angle of contact with a substrate. In addition, since a high-quality liquid crystal display device can be provided, the industrial applicability in the field of the photosensitive composition for liquid crystal split alignment protrusions and the liquid crystal display device is extremely high.

It is explanatory drawing which showed the pattern formation characteristic before the heating of the photosensitive composition for liquid crystal division | segmentation alignment protrusions, and after a heating.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Cross section of thin line image before heat treatment 3 Cross section of thin line image after heat treatment 4 Contact angle formed from side surface and substrate plane of thin line image before heat treatment (W1)
5 Contact angle (W2) formed from the side of the thin line image after heat treatment and the substrate plane

Claims (3)

In the photosensitive composition for liquid crystal split alignment protrusions comprising an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin as a main component, the weight ratio of alkali-soluble resin / ethylenically unsaturated compound is 1.5 or more, In addition, the photosensitive layer coated with the photosensitive composition with a film thickness of 1.7 μm was irradiated with ultraviolet light with a wavelength of 365 nm at 50 mJ / cm ² through a mask having a fine line pattern with a line width of 15 μm. The contact angle formed from the side surface of the fine line image obtained by shower development at ℃ and water pressure of 0.25 MPa and the substrate plane is (W1), and the fine line image is further subjected to heat treatment at 230 ° C. for 30 minutes. The photosensitive composition for liquid crystal division | segmentation alignment protrusions characterized by satisfy | filling the following formula | equation, when the contact angle formed from the side surface of an alignment protrusion-like thin line image and a substrate plane is (W2).
W1 / W2 ≧ 1.2 The photosensitive composition for liquid crystal split alignment protrusions according to claim 1, wherein the alkali-soluble resin has a side chain ethylenic addition polymerizable group. A liquid crystal display device provided with the liquid crystal division | segmentation alignment protrusion formed using the photosensitive composition for liquid crystal division | segmentation alignment protrusion of Claim 1 or 2 .

Images