WO2007026629A1

WO2007026629A1 - Photosensitive resin composition, spacer, color filter, and liquid crystal display device

Info

Publication number: WO2007026629A1
Application number: PCT/JP2006/316829
Authority: WO
Inventors: Mana Miyamoto; Kazumi Wakao; Shujiro Sadanaga
Original assignee: Kyocera Chemical Corporation
Priority date: 2005-08-30
Filing date: 2006-08-28
Publication date: 2007-03-08
Also published as: KR20080044253A; JPWO2007026629A1; JP5313499B2

Abstract

This invention provides a photosensitive resin composition, which has high sensitivity and high resolution and can provide a spacer for a liquid crystal display device, which can evenly keep cell gap even at room temperature and high temperature and has excellent heat resistance, chemical resistance and strength, and a spacer for a liquid crystal display device. The photosensitive resin composition is a photosensitive resin composition for the formation of a spacer for a negative-working liquid crystal display device, which, in a cured product, the percentage change in storage modulus between -20ºC and 25ºC is 5 to 20%, the percentage change in storage modulus between 25ºC and 180ºC is 30 to 80%, the glass transition temperature is 160ºC or above, and the tan δ value at -50 to 250ºC is not more than 0.1. The spacer for a liquid crystal display device is small in a variation in total deformation level or in a variation in plastic deformation level as measured with a microhardness meter by a load-unloading test.

Description

Specification

Photosensitive resin composition, spacer, color filter and liquid crystal display

[0001] The present invention provides a negative photosensitive resin composition that provides a spacer for a liquid crystal display device having excellent heat resistance, chemical resistance, and strength. The negative photosensitive resin composition is formed using the photosensitive resin composition. The present invention relates to a spacer for a liquid crystal display device having properties, a power color filter for a liquid crystal display device including the spacer, and a liquid crystal display device using the color filter.

Background art

In order to obtain the intended electrical engineering characteristics, a liquid crystal panel needs to obtain a uniform distance between two substrates over the entire display. Therefore, use spacer beads such as glass beads and plastic beads with a predetermined particle size.

The distance between the glass substrates is kept constant.

Since these spacer beads are randomly distributed on the glass substrate, the spacer beads exist in the effective pixel area, and the spacer beads are reflected, scattered incident light, light leakage, etc. There was a problem. In recent years, with the increase in size of the substrate, liquid crystal injection has shifted to the drop injection method in addition to the force of the vacuum injection method. However, in the drop injection method, the spacer beads move as the liquid crystal is injected. There is also a problem that the uniform arrangement is not maintained.

On the other hand, a method of forming a spacer at a predetermined position on a color filter using a photosensitive resin has been used. This is because a photosensitive resin is applied on a color filter. It is applied to the substrate, irradiated with actinic rays such as ultraviolet rays through a predetermined mask, and then developed to form spacers in the form of dots or stripes. When the spacer is formed in this way, selectively on the black matrix of the color filter, and

In addition, a spacer can be formed without causing misalignment.

In this spacer, it is important that the spacer material does not generate any eluate after the panel is assembled to come into contact with the liquid crystal material. If there is a curing component such as a monomer, it must be fully cured. There was a point. Heat resistance is required so that the pattern shape does not collapse during this heat treatment. In the panel manufacturing process, pressure is applied at room temperature to spread the liquid crystal in the liquid crystal drop injection process, and the seal is sealed at high temperature by applying pressure at the substrate bonding process. When deformation or crushing occurs, the gap width becomes non-uniform. Such a non-uniform gap leads to an undesirable situation such as a reduction in display contrast. For this reason, for example, a technique using a negative photosensitive resin composition as a spacer material is disclosed (for example, see Patent Document 1).

However, even when such a photosensitive resin composition is used, the amount of deformation is inevitable at the seal sealing temperature, and it is difficult to maintain the cell gap uniformity of a large panel. I helped.

In addition, it is flexible and has a small amount of plastic deformation! A photosensitive resin composition for forming spacers capable of forming a spacer is disclosed (for example, see Patent Document 2). However, even when such a photosensitive resin composition is used, the spacer is deformed at the time of sealing the seal, and the gap width becomes non-uniform due to the variation in the deformation amount, resulting in a decrease in display contrast. There was a problem that occurred. In addition, if the amount of deformation is significantly different between the center and the edge within the substrate surface, the portion of the spacer having a uniform height is reduced, which causes a problem that the yield of the product is lowered.

Patent Document 1: Japanese Patent Laid-Open No. 2003-29405

Patent Document 2: JP 2005-292270 A

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention solves such problems in the prior art, has high sensitivity and high resolution, and can maintain a uniform cell gap even at room temperature and high temperature. A photosensitive resin composition that provides a spacer for a liquid crystal display device having excellent strength, and a spacer for a liquid crystal display device having the above-mentioned properties formed by using the photosensitive resin composition, the spacer. It is an object to provide a color filter for a liquid crystal display device having a spacer and a liquid crystal display device using the color filter.

Means for solving the problem [0006] As a result of intensive studies to achieve the above object, the present inventors have found that the object can be achieved by a photosensitive resin composition having a specific composition and properties. The present invention has been completed based on powerful knowledge.

That is, Invention 1 of the present invention is

(1) A negative photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent,

(a) the rate of change between the storage elastic modulus at 20 ° C and the storage elastic modulus at 25 ° C of the cured product from which the composition of the resin composition is also obtained is 5 to 20%;

(b) The rate of change of the storage elastic modulus at 25 ° C and the storage elastic modulus at 180 ° C of the cured product.

(c) The glass transition temperature of the cured product is 160 ° C or higher, and

(d) a photosensitive resin composition for forming a spacer of a liquid crystal display device, wherein the cured product has a value of tan δ at 50 to 250 ° C. of 0.1 or less,

(2) Negative photosensitive resin composition strength (i) Alkali-soluble resin having a polymerizable functional group having a weight average molecular weight of 10,000 to 20,000 and a glass transition temperature of 110 ° C or higher 1 The liquid crystal display device according to (1) above, comprising 00 parts by mass, (B) 50 to 250 parts by mass of a polymerizable polyfunctional compound, (C) 1 to 20 parts by mass of a photopolymerization initiator, and (D) a solvent. Photosensitive resin composition for forming a spacer,

[0007] (3) (A) Alkali-soluble rosin comprises (al) a carboxylic acid having an ethylenically unsaturated bond and a carboxylic acid anhydride having Z or an ethylenically unsaturated bond, and (a2) other ethylenic acid. In the above item (1), which is a resin obtained by reacting a part of a copolymer with an unsaturated compound having an ethylenically unsaturated bond with an epoxy compound having (a3) an ethylenically unsaturated bond A photosensitive resin composition for forming a liquid crystal display device spacer,

(4) The photosensitive resin composition for forming a liquid crystal display device spacer according to the above item (1), wherein the polymerizable polyfunctional compound (B) has 5 or more functional groups,

(5) The photosensitive resin composition for forming a liquid crystal display device spacer as described in the above item (1), wherein the polymerizable polyfunctional compound (B) has a glass transition temperature of 100 ° C or higher,

(6) (B) The polymerizable polyfunctional compound described in the above item (1), which has a urethane bond Photosensitive resin composition for forming a liquid crystal display device spacer,

(7) The liquid crystal display device according to (1) above, wherein the rate of change in indentation deformation at 25 ° C and indentation deformation at 180 ° C of the formed spacer is 100 to 120%. Photosensitive resin composition for spacer formation,

(8) A spacer for a liquid crystal display device formed by using the photosensitive resin composition according to the above item (1),

(9) A color filter comprising a spacer for a liquid crystal display device formed by using the photosensitive resin composition according to (1) above, and

(10) A liquid crystal display device comprising a spacer for a liquid crystal display device formed using the photosensitive resin composition according to the above (1),

Is to provide.

Invention 2 of the present invention is

(11) A spacer capable of obtaining a negative photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent. The variation of the total deformation in the load-unloading test measured with a micro hardness tester is (e) within the 0.25 standard deviation (σ) at 25 ° C within the substrate surface. The standard deviation (σ) at 180 ° C is within 0.30, and

(f) By two figures formed by connecting the points on the center side of the substrate and the points on the end side of the substrate, each of which bisects the line segment connecting the center of the substrate and the plurality of ends. Within 2 cm square in each of the three regions formed, the standard deviation (σ) at 25 ° C is within 0.20, and the standard deviation (σ) at 80 ° C is within 0.25,

Spacer for liquid crystal display device, characterized by

(12) A spacer that can also provide a negative photosensitive resin composition comprising (Α) an alkali-soluble resin, (Β) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent. The variation in the amount of plastic deformation in the load-unloading test measured with a microhardness meter is

(g) Within the substrate surface, the standard deviation (σ) at 25 ° C is within 0.20, the standard deviation (180) at 180 ° C is within 0.25, and

(h) The center of the substrate at the point where each line segment connecting the center of the substrate and the plurality of ends is divided into three equal parts The standard deviation (σ) at 25 ° C is 0. within 2 cm square in each of the three regions formed by the two figures formed by connecting the points on the side and the points on the edge side of the substrate. Within 15, the standard deviation (σ) at 180 ° C is within 0.20,

Spacer for liquid crystal display device, characterized by

(13) Negative photosensitive resin composition strength (i) Alkali-soluble resin having a polymerizable functional group having a weight average molecular weight of 10,000 to 20,000 and a glass transition temperature of 110 ° C or higher. 100 parts by weight of fat, (B) 50 to 250 parts by weight of polymerizable polyfunctional compound, (C) 1 to 20 parts by weight of a photopolymerization initiator, and (D) a cured product obtained from the resin composition. The glass transition temperature of the liquid crystal display device according to the above (11) or (12), wherein the glass transition temperature is 160 ° C or higher.

(14) (A) Alkali-soluble resin is (al) a carboxylic acid having an ethylenically unsaturated bond and a carboxylic acid anhydride having Z or an ethylenically unsaturated bond, and (a2) other ethylenically unsaturated Item (11) or (12), which is a resin obtained by reacting a part of a copolymer with an unsaturated compound having a bond with an epoxy compound having (a3) an ethylenically unsaturated bond. Spacers for liquid crystal display devices

(15) The spacer for a liquid crystal display device according to the above (11) or (12), wherein the polymerizable polyfunctional compound (B) has 5 or more functional groups,

(16) The spacer for a liquid crystal display device according to the above (11) or (12), wherein the polymerizable polyfunctional compound (B) has a glass transition temperature of 100 ° C. or higher.

(17) The spacer for a liquid crystal display device according to the above (11) or (12), wherein the polymerizable polyfunctional compound (B) has a urethane bond,

(18) A color filter characterized by having a spacer for a liquid crystal display device according to the above (11) or (12), and

(19) A liquid crystal display device comprising the spacer for a liquid crystal display device according to the above (11) or (12),

Is to provide.

The invention's effect

[0010] According to the present invention, it has high sensitivity and high resolution, and at room temperature and high temperature! It is possible to provide a photosensitive resin composition that can maintain a uniform yap and provide a spacer for a liquid crystal display device having excellent heat resistance, chemical resistance, and strength.

Further, a spacer for a liquid crystal display device having the above-mentioned properties formed by using this photosensitive resin composition, a color filter for a liquid crystal display device having the spacer, and this color filter were used. A liquid crystal display device can be provided.

Brief Description of Drawings

FIG. 1 is an explanatory diagram of measurement points in a loader-unloading test of a spacer.

FIG. 2 is an explanatory diagram of measurement points in a spacer load-unloading test.

FIG. 3 is a graph showing a hysteresis curve used in a loader-unloading test of a spacer.

FIG. 4 is a diagram showing a criterion for evaluating the cross-sectional shape of a pattern after curing in a photosensitive resin composition.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] <Invention 1>

The photosensitive resin composition for forming a spacer of a liquid crystal display device of the present invention (hereinafter sometimes simply referred to as photosensitive resin composition) includes (A) an alkali-soluble resin and (B) a polymerizable resin. A negative photosensitive resin composition containing a polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent. Preferably, (A) the weight average molecular weight is 10,000 to 20,000. And 100 parts by mass of an alkali-soluble resin having a polymerizable functional group having a glass transition temperature of 110 ° C. or higher, (B) 50 to 250 parts by mass of a polymerizable polyfunctional compound, and (C) a photopolymerization initiator 1 to A negative photosensitive resin composition containing 20 parts by mass and (D) a solvent.

Examples of the alkali-soluble resin of component (A) in the photosensitive resin composition of the present invention include, for example, (al) a carboxylic acid having an ethylenically unsaturated bond and a carboxylic acid having Z or an ethylenically unsaturated bond. A part of a copolymer of an anhydride and (a2) another unsaturated compound having an ethylenically unsaturated bond was reacted with (a3) an epoxy compound having an ethylenically unsaturated bond. Fats can be preferably used.

The copolymer of (al) a carboxylic acid having an ethylenically unsaturated bond and Z or a carboxylic acid anhydride having an ethylenically unsaturated bond, and (a2) another compound having an ethylenically unsaturated bond, (al) and (a2) are radical radicals in a solvent in the presence of a polymerization initiator. It can be manufactured by combining.

[0013] Examples of the component (al) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, and carboxylic anhydrides thereof. Things. These can be used alone or in combination of two or more.

On the other hand, as the component (a2), for example, methyl metatalylate, ethyl metatalylate, n-butyl metatalylate, sec butyl metatalylate, t-butyl metatalylate, etc. Alkyl esters of acrylic acid such as acrylate and isopropyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopenta-methacrylate, dicyclopenta-roxetyl methacrylate, isopololol methacrylate Methacrylic acid cyclic alkyl esters such as: cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopenta-butyl acrylate, dicyclopenta-luxhetyl acrylate, isopolo-butyl acrylate Steal; Metalarylic acid aryl ester such as phenol metatalylate and benzyl metatalylate; Acrylic acid aryl ester such as phenol atalylate and benzyl atallate; Jetyl maleate, Jetyl fumarate, Jetyl itaconate, etc. Dicarboxylic acid diesters; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; and styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, butyltoluene, p-methoxystyrene , Atari mouth Nitryl, Metatari mouth-tolyl, Butyl chloride, Sodium chloride vinylidene, Acrylamide, Methacrylamide, Vinyl acetate, 1,3 Butadiene, Isoprene, 2,3 Dimethyl-1,3 Butadiene and the like. These may be used alone or in combination of two or more.

[0014] Solvents used in the copolymerization of the component (al) and the component (a2) include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycolenomonomethinoleate. Glycol ethers such as tenole and ethylene glycol monoethylenoate ethere; ethylene glycol alkyl ether acetates such as methyl acetate sorb acetate and ethyl acetate sorb acetate; diethylene glycol monomethyl ester Diethylene glycols such as diterene glycol, diethylene glycol monoethyl ether, diethylene glycol dimethyl etherate, diethylene glycol nole chinenoate ethere, diethylene glycol noretino methinole ether; propylene glycol methyl ether, propylene glycol noretino rea Propylene glycol monoalkyl ethers such as tenole, propylene glycolenopropenoleatenole, propylene glycol butyl ether; propylene glycolenolemethinoatenoate acetate, propylene glycolenoretinoatenoate acetate, propylene glycol propyl ether acetate, propylene Propylene glycol alkyl ether acetate such as glycol butyl ether acetate Propylene glycol methylalenolequinol ethers such as propylene glycol methyl ether propionate, propylene glycol nole thiol ether ether propionate, propylene glycol propinole ether terpropionate, propylene glycol butinole ether propionate Acetates; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy mono 4-methyl 2 pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropion Ethyl acid, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy 2-methylethyl ethyl propionate, methyl hydroxyacetate, ethyl ethyl acetate, hydroxybutyl acetate, methyl lactate, lactate Propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, methoxy Ethyl acetate, Propyl methoxyacetate, Ptyl methoxyacetate, Methyl ethoxy acetate, Ethyl acetate, Propyl ethoxy acetate, Butyl ethoxy acetate, Methyl propoxyacetate, Ethyl propoxyacetate, Propyl acetate, Propyl butyl acetate, Methyl butoxyacetate, Butoxyacetic acid Ethyl, butyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyric 2-methoxypropionate 2-Methyl 2-ethoxypropionate, 2-ethyl ethoxypropionate, 2-propyl ethoxypropionate, 2-butyl ethoxypropionate, 2-butoxypropionate methyl, 2-butoxypropionate ethyl, 2-butoxypropionate Propyl, 2-butyl butoxypropionate Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, propyl 3-ethoxypropionate, 3-Butyl ethoxypropionate, Methyl 3-propoxypropionate, 3-Ethyl propoxypropionate, 3-Propylpropoxypropionate, 3-Butyl propoxypropionate, Methyl 3-butoxypropionate, 3-Ethylbutoxypropionate And esters such as propyl 3-butoxypropionate and butyl 3-butoxypropionate. These solvents can be used alone or as a mixture of two or more.

[0016] As the polymerization initiator used in the copolymerization of the (al) component and the (a2) component, those generally known as radical polymerization initiators can be used. 2'—Azobisisobuty-tolyl, 2,2,1-azobis (2,4 dimethylvale-tolyl), 2,2, -azobis (4-methoxy-1,2,4 dimethylvale-tolyl), etc. Zo compounds; organic peroxides such as benzoyl peroxide, lauroyl belloxide, t-butylperoxypivalate, 1,1,1 bis (t-butylperoxy) cyclohexane; and hydrogen peroxide. When using a peroxide as a radical polymerization initiator, use a peroxide together with a reducing agent as a redox initiator.

The temperature at the time of copolymerization varies depending on the type of monomer used and is usually about 40 to 150 ° C, preferably 50 to 100 ° C.

Next, by reacting a part of the reactive functional group such as a carboxylic acid group of the copolymer thus obtained with an epoxy compound having (a3) an ethylenically unsaturated bond, (A3) ) Component alkali-soluble rosin is obtained.

[0017] Examples of the component (a3) include glycidyl acrylate, glycidyl methacrylate, a glycidyl ethyl acrylate, glycidyl a-n-propyl acrylate, an butyl glycidyl acrylate, acrylic acid-3, 4-epoxybutyl, Methacrylic acid—3,4-epoxybutyl, acrylic acid 6, 7—epoxyheptyl, methacrylic acid 6,7—epoxyheptyl, α-ethylacrylic acid 6,7—epoxyheptyl, ο-bulubenzylglycidyl ether, m— Examples include benzylbenzyl glycidyl ether and p-butylbenzyl glycidyl ether. Of these, as preferred, Examples include sidyl, methacrylic acid-6,7-epoxyheptyl, o-bulubenzyl glycidyl ether, m-bulubenzyl glycidyl ether, and p-bullbenzyl glycidyl ether. These may be used alone or in combination of two or more.

[0018] Although this reaction can be carried out without a catalyst, a catalyst can also be used to accelerate the reaction. Examples of the catalyst include triethylamine, benzyldimethylamine, pyridine, triethylammochloride, Examples include benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, chromium octoate, and zirconium octoate.

These may be used alone or in combination of two or more. The amount used is usually about 0.1 to 10% by mass, preferably 0, based on the mass of the reaction product. . 5-5% by mass. The reaction temperature is usually about 60 to 150 ° C, preferably 80 to 120 ° C, and the reaction time depends on the reaction temperature and cannot be determined in general, but usually about 5 to 60 hours is sufficient. is there.

[0019] The alkali-soluble coconut oil of component (A) thus obtained preferably has a weight average molecular weight Mw in the range of 10,000 to 20,000. If this Mw is 10,000 or more, the resulting film has good developability, residual film properties, pattern shape, heat resistance, etc., whereas if it is 20,000 or less, the sensitivity is lowered or the pattern shape is poor. And the storage stability of the photosensitive resin composition is also good. A more preferred Mw is 12,000-18,000.

The weight average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography method (GPC method).

It is preferable to select the use ratio of the components (al), (a2) and (a3) so that the alkali-soluble coagulant of the component (A) has a solid acid value of 50 to 200 mgKOHZg. If the solid content acid value is 50 mgKOHZg or more, good developability is obtained, and if it is 200 mgKOHZg or less, the residual film ratio and pattern shape are good. A more preferable solid content acid value is 80 to 150 mgKOH / g. [0020] As the polymerizable polyfunctional compound of component (B) in the photosensitive resin composition of the present invention, those having a functional group number of 5 or more can be preferably used. As such a polymerizable polyfunctional compound, a pentafunctional or higher functional compound can be preferably used. Examples of such polymerizable polyfunctional compounds include penta- or higher-functional (meth) acrylates, such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hex (meth) acrylate. Commercially available products include, for example, Alonics M-402 (manufactured by Toa Gosei Chemical Co., Ltd.), K AYARADDPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20 , DPCA-30, DPCA-60, DPCA-120 [manufactured by Nippon Kayaku Co., Ltd.], Beamset 700 [manufactured by Arakawa Chemical Co., Ltd.], SR299E, SR9041 (manufactured by Sartoma) It is done. These may be used alone or in combination of two or more.

[0021] As the polymerizable polyfunctional compound of component (B), those having a glass transition temperature (Tg) of 100 ° C or higher can be preferably used. Examples of such polymerizable polyfunctional compounds include 1,3 butylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meta). ) Atalylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, neopentyl glycol di (meth) acrylate, cresolol novolac type epoxy (meta ) Atalylate, phenol novolac type epoxy (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, trimethylol propantri (meth) acrylate, trimethylol propane PO-modified tri (meth) acrylate, dipentaerythritol Rupenta (meth) Atari rate, hexa to dipentaerythritol (meth) Atarire over preparative, ditrimethylolpropane tetra (meth) Atari rate, pentaerythritol tetra (meth) Atari rate, and polyester Atari rate. Examples of commercially available products include SR212, SR508, SR368, SR444, SR295, CD540 (manufactured by Thermar), light atelate NP-A (manufactured by Kyoeisha), Lipoxy SP-4060, SP-4010 [Showa Polymer Co., Ltd.], Aronix M-215, M-305, M-309, M-310, M-315, M-402, M-408, M-450 , M-7100, M-8030, M 8060, M-8100, M-8050 [Toa Gosei Chemical Co., Ltd.] The These may be used alone or in combination of two or more.

[0022] Furthermore, as the polymerizable polyfunctional compound of component (B), a polymerizable compound having a pentafunctional or higher functional urethane bond can be preferably used. Examples of such a polymerizable polyfunctional compound include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate. Commercially available products include CN-968, CN-975 (manufactured by Sartoma), NK Oligo U—15HA, UA—32, U—324A, U—6HA, UA—100H, U— 6LPA, U-6 Shin-Nakamura Chemical Co., Ltd.], Beam Set 575 [Arakawa Chemical Co., Ltd.], Aronix M-1960 [Toa Gosei Chemical Co., Ltd.], and the like. These can be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, the polymerizable polyfunctional compound of the component (B) is a ratio of 50 to 250 parts by mass with respect to 100 parts by mass of the alkali-soluble resin of the component (A). It is blended with. If the blending amount of the component (B) is 50 parts by mass or more, the crosslinking reaction proceeds sufficiently, and film loss due to development hardly occurs. On the other hand, if it is 250 parts by mass or less, good resolution is obtained. . The amount of component (B) is preferably 80 to 200 parts by mass.

[0023] The photopolymerization initiator of the component (C) in the photosensitive resin composition of the present invention is efficient in i-line (365 nm) and g-line (436 nm) in ultraviolet rays as a photoreaction initiator. There is no particular limitation as long as it often generates reactive radicals. Examples of such compounds include OC-diketones such as benzyl and diacetyl, acyloines such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, thixanthone, 2- Benzophenones such as methyl thioxanthone, 2-isopropyl thioxanthone, 2,4 jetyl thioxanthone, thixanthone 4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (jetylamino) benzophenone, acetophenone , P Dimethylaminoacetophenone, 2, 2'-jetoxyacetophenone, 2-hydroxy 2-methylpropiophenone and other acetophenones, anthraquinone, 1, 4 quinones such as naphthoquinone, 2, 6 di (4 'ーDiazidobenzal) cyclohexanone, 2, 6 di (4, -diazidobenzal) -4-methylcyclohexanone, 2, 6- (4'-diazidobenzal) -4-ethylcyclohexanone, 2, 6- (4, -diazidobenzal) -4 butylcyclohexanone, 2, 6- (4 'di Azidobenzal) 4— (t-butyl) cyclohexanone and other azides, 1-phenol-1,2-butadione-2- (O benzoyl) oxime, 1-phenol-propanedione 2- (O-methoxy) (Carbonyl) oxime, 1-phenol 2-oxi (O ethoxycarbol) oxime, 1-phenol-propanedione 2- (O-benzoyl) oxime, 1,3-diphenylpropane trione 2— (O ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione 2— (O benzoyl) oxime and other oximes, N-phenylglycine, N— (p-ethyl) phenylglycine, N— (p-ethyl) phenol -Glycine derivatives such as glycine, halogenated compounds such as phenacyl chloride, tribromomethylphenol sulfone, tris (trichloromethyl) -s triazine, di-t-butyl Such as peracetic acid I 匕物 such peroxide. Examples of these commercial products include IRGA CURE-184, 369, 500, 651, 907, 1700, Darocur-1173, 1116, 2959, 1664, 4043 (Chinoku Specialty. Chemicals Co., Ltd.], KAYA CURE-DETX, MBP, DMBI, EPA, OA [Nippon Kayaku Co., Ltd.]. These may be used alone or in combination of two or more. In the photosensitive resin composition of the present invention, the photopolymerization initiator of the component (C) is an alkali-soluble resin of the component (A) from the viewpoint of balance between effect and economy. 1 to 20 parts by mass, preferably 3 to 15 parts by mass with respect to parts by mass.

Moreover, in the photosensitive resin composition of this invention, a sensitizer can be used together with the said photoinitiator as needed. Examples of this sensitizer include Michler's ketone, 4, 4'-bis (jetylaminobenzophenone), 2,5 bis (4'-jetylaminobenzal) cyclopentanone, 2, 6 bis (4'-jet). Tylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) 1-4-methylcyclohexanone, 2,6bis (4, -demethylaminobenzal) -4-methylcyclo Hexanone, 4, 4 'bis (jetylamino) chalcone, 4, 4, monobis (dimethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophene -Rubypherene) monobenzothiazole, 2- (p dimethylaminophenol- bis-len) benzothiazole, 1,3 bis (4'-dimethylaminobenzal) acetone, 3, 3 '— Cal Borubis (7-Jetylaminocoumarin), 3-acetylyl 7-dimethylaminocoumarin, 3 Ethoxycarbonyl 7-dimethylaminocoumarin, 3-benzyloxycarbonyl 7-dimethylaminocoumarin, 3-methoxycarbonyl7-jetylaminocoumarin, 3-ethylcarborulu 7-jetylaminocoumarin N-phenol N, monoethanolamine, N-phenolethanolamine, N-p-tolyldiethanolamine, N-phenolethanolamine, 4 morpholinobenzophenone, isoamyl dimethylaminobenzoate, 2-mercapto Examples thereof include benzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzozothiazole, 1-ferruo 5 mercapto-1H-tetrazole and the like.

[0025] These may be used singly or in combination of two or more. The blending amount is selected from the viewpoints of balance between effect and economics, and the like. The amount is preferably 0.1 to: L0 parts by mass, more preferably 0.3 to 8 parts by mass with respect to 100 parts by mass of the soluble resin. These sensitizers can be used in accordance with the wavelength to be used and further in accordance with the required sensitivity, thereby improving the resolution at each wavelength. In the photosensitive resin composition of the present invention, a polymerization inhibitor can be blended as desired in order to improve the storage stability of the resin. As the polymerization inhibitor, for example, hydroquinone derivatives such as hydroquinone, methylhydroquinone, and butylquinone can be used. These compounds may be used alone or in combination of two or more. The compounding amount is from the point of effect and economy, and the alkali-soluble resin of the component (A). It is preferably in the range of 0.1 to: L0 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass.

The photosensitive resin composition of the present invention comprises the component (A), the component (B), the component (C), a sensitizer used as necessary, a polymerization inhibitor, and other additive components as the component (D). It is usually used after being dissolved in a solvent.

[0026] The solvent of the component (D) is not particularly limited as long as each component is uniformly dissolved and does not react with the component. Examples of such a solvent include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycolate ethers such as ethylene glycol monomethino ethenore, ethylene glycol monomethino enoate, and methyl cetosolve. Ethylene glycol alkyl ether acetates such as acetate and ethyl acetate sorb acetate, diethylene glycol monomethyl ether, diethylene glycol Diethylene glycols such as ethylene glycol monoreino eno enoate, diethylene glucono regino methino ree enore, propylene glycol methyl ether, propylene glycol nereno enoate, propylene glycol enopropenoate enole, propylene glycol eno butyl ether, etc. Propylene glycol alkyls such as propylene glycol monoalkyl ethers, propylene glycol monoremethinoleateolate acetate, propyleneglycololeretinoatenoacetate, propyleneglycololepropenolateenoleacetate, propyleneglycololebutenoateacetate Aromatic hydrocarbons such as ether acetates, toluene xylene, methyl ethyl ketone, cyclohexanone , 4-hydroxy-4-methyl-2-pentanone and other ketones, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy 2-methyl methyl pionate, 2-hydroxy 2-methyl Examples thereof include esters such as ethyl ethyl propionate, methyl hydroxyacetate, ethyl ethyl acetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate and butyl lactate. These solvents may be used alone or as a mixture of two or more.

Furthermore, a high boiling point solvent can be used in combination with the solvent. Examples of high-boiling solvents that can be used in combination include N-methylformamide, N, N dimethylformamide, N-methylformamide, N-methylacetamide, N, N dimethylacetamide, N-methylbivinylidone, and dimethylsulfoxide. , Benzylethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, strong prillic acid, 1-octanol, 1-nonanol, pendyl alcohol, benzyl acetate, ethyl benzoate, jetyl maleate, γ-butyrolatone , Ethylene carbonate, propylene carbonate, ferrule sorb acetate and the like.

In the photosensitive resin composition of the present invention, the amount of the solvent is suitably set so that the viscosity is suitable for coating other components in the resin composition, for example, on a glass substrate. It only has to be selected.

In addition to these components, the photosensitive resin composition may contain various additives such as a leveling agent, a silane coupling agent, a filler, a colorant, and a viscosity modifier as necessary. it can. [0028] The photosensitive resin composition of the present invention thus obtained is a negative type and is used for forming a spacer for a liquid crystal display device. When manufacturing a liquid crystal cell, the sealing force is exerted by applying pressure at a temperature of about 120 to 180 ° C. In this case, it is not preferable that the spacer is plastically deformed so that the desired cell gap cannot be maintained. Further, it is preferable that the elastic deformation component has as little displacement as possible. From these facts, the present inventors have found that the physical properties of the spacer are defined by dynamic viscoelasticity.

In addition, there is a reliability test after manufacturing the liquid crystal cell, but if the thermal expansion coefficient of the spacer is large relative to the thermal expansion of the liquid crystal, the inside of the cell is evacuated from atmospheric pressure, and air is released from the sealing part. May cause foaming phenomenon. For this reason, spacers made of photosensitive resin must have corresponding characteristics within the range of 50 to 250 ° C.

That is, the spacer according to the present invention is defined by the storage elastic modulus, loss tangent, and glass transition temperature based on the dynamic viscoelasticity of the cured product that also provides the photosensitive resin composition strength. Storage elastic modulus at 0 ° C and storage elastic modulus at 25 ° C is 5-20%, preferably 10-18%, storage elastic modulus at 25 ° C and storage elastic modulus at 180 ° C are 30 to 80%, preferably 50 to 80%, the glass transition temperature (Tg) of the cured product is 160 ° C or higher, and the loss tangent (tan δ) value of −50 to 250 ° C is 0.1 or lower. It is characterized by being. The upper limit of the glass transition temperature (Tg) of the cured product is not particularly limited, but is usually about 165 ° C. The lower limit of the loss tangent (tan S) value of 50 to 250 ° C is not particularly limited, but is usually about 0.08.

[0030] The storage modulus, glass transition temperature (Tg), and loss tangent (tan δ) of dynamic viscoelasticity employ the following measuring apparatus and measuring method.

Sample for measurement: An appropriate amount that gives a film thickness of 400 / zm after curing the photosensitive resin composition of the present invention is placed in an aluminum cup, and heated at 120 ° C. for 1 hour to drive off the solvent. Then expose to 500 mjZcm ² and cure at 220 ° C for 1 hour. Remove the cured product from the aluminum cup and

Cut out to 4mm and 40mm in length and cut into strips.

Measuring device: Dynamic viscoelastic device DMS6100 (manufactured by Seiko Instruments Inc.) Measuring method: A sample for measurement is set in the device, tensile mode, sine wave, frequency 1Ηζ, amplitude 10 μm, initial load 100 mN, rising Temperature range 50 to 250 ° C at 5 ° C Zmin Measure and obtain storage modulus (Ε ', GPa), glass transition temperature (Tg, ° C), and loss tangent (tan δ). In addition, the rate of change of the storage elastic modulus is obtained from the following formula.

Change rate of storage elastic modulus (-20 ° C → 25 ° C) (%) = {["Storage elastic modulus at 20 ° C"-"Storage elastic modulus at 25 ° C"] Z "-20 ° C storage Elastic modulus "} X 100

Change rate of storage elastic modulus (25 ° C → 180 ° C) (%) = {["Storage elastic modulus at 25 ° C"-"Storage elastic modulus at 180 ° C"] Z "Storage elastic modulus at 25 ° C } X 100

[0031] The spacer of the present invention is defined by the indentation deformation amount of the spacer in which the photosensitive resin composition force is also formed. The change rate of the indentation deformation at ° C is preferably 100 to 120%. The following measuring device and measuring method are used for the rate of change of indentation deformation.

Measurement sample: After the photosensitive榭脂composition was coated on a glass substrate, and the pre-beta 3 minutes 90 ° C, followed 500NijZcm ² was exposed, 0.10 mass ^_0/0 tetramethylammonium - Umuhidoro Kishido (TMAH ) Develop with aqueous solution to make a spacer with a height of 5 μm and a width of 10 μm.

Measuring device: Shimadzu Dynamic Ultra Micro Hardness Tester DUH-W201 (manufactured by Shimadzu Corporation) Measuring method: Set the sample for measurement on the device and use a flat indenter with a diameter of 50 m. 1. Spacer at a constant speed of 324 mN Zsec. Apply the load, measure the displacement of the spacer when the maximum load reaches 30mN, and calculate the rate of change using the following formula.

Rate of change (%) = ["displacement at 180 ° C" Z "displacement at 25 ° C"] X 100 In the liquid crystal display device of the present invention, the spacer is defined by viscoelasticity as described above. Thus, a desired cell gap with less deformation in the cell sealing step can be maintained, and the low-temperature bubble phenomenon can be suppressed.

[0032] The spacer according to the present invention is formed of the photosensitive resin composition according to the present invention having such characteristics, and the color filter according to the present invention having the spacer is A colored layer and a protective layer for protecting the colored layer are provided on the substrate, an alignment film is provided on the protective layer to align the liquid crystal, and a columnar spacer is provided on the alignment film. The configuration is the same as that of a known color filter provided with a. On the protective film, a transparent electrode for driving a liquid crystal may be formed if necessary.

Next, a method for manufacturing the spacer according to the present invention will be described. In the photosensitive resin composition of the present invention, the component (A) component-soluble polyfunctional group having a polymerizable polyfunctional group and the component (B) polymerizable polyfunctional compound are polymerized by radicals generated by light irradiation. In contrast, when it becomes insoluble in the developer, contrast can be generated and a no-turn can be formed. When considering application to a glass substrate, first, a film is formed on the substrate intended for the photosensitive resin composition using a spin coater, and then the film is heated at about 90 to 130 ° C. Then, it passes through a mask on which a pattern is drawn on the obtained film and is irradiated with active ultraviolet rays having a wavelength of 365 nm and 436 nm.

[0033] Next, this coating is applied to, for example, an inorganic aqueous alkaline solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, etc., primary amine such as n-propylamine, jetylamine, Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldimethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary amines such as tetramethylammonium hydroxide and tetraethylamine hydroxide Development is performed using an alkaline aqueous solution in which grade amin is dissolved, and only unexposed portions are dissolved and removed, followed by rinsing with pure water. As the developing method, methods such as spraying, paddle, dipping, and ultrasonic can be used.

By this operation, a desired negative pattern can be obtained on the target substrate. Furthermore, by heat-treating this film, the alkali-soluble resin having a polymerizable functional group and the polymerizable polyfunctional compound are further cross-linked, and the film has excellent film properties such as adhesion, heat resistance and chemical resistance. The part can be formed at a desired position.

[0034] The shape of the spacer is not particularly limited, but is preferably a square, rectangle, polygon, circle, or ellipse when viewed from directly above the substrate surface. In the case of an ellipse, the long axis direction is preferably horizontal or perpendicular to the rubbing direction. In addition, when looking at the lateral force with respect to the substrate surface, a square, a rectangle, or a trapezoid is preferable. In addition, the lower part of the trapezoid may be rounded even if the upper corner of the trapezoid is rounded. The trapezoidal shape is particularly effective when an alignment film is applied and rubbed on the spacer, and when the alignment film is uniformly applied or rubbed.

Examples of the substrate include white plate glass, blue plate glass, and silka coated blue plate glass. Transparent glass substrate, polycarbonate, polyester, acrylic resin, butyl resin resin, aromatic polyamide resin, polyamideimide, polyimide resin sheet, film or plate, aluminum plate, copper plate, nickel plate And metal substrates such as stainless steel plates, other ceramic substrates, and semiconductor substrates having photoelectric conversion elements.

[0035] If necessary, these substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering method, gas phase reaction method, and vacuum deposition method.

Substrate sizes include 320 mm x 400 mm first generation boards, 370 mm x 4470 mm second generation boards, 550 mm x 650 mm third generation boards, and 680 mm x 880 mm to 730 mm x 920 mm fourth generation boards.

The liquid crystal display device of the present invention is characterized by having a color filter provided with the spacer, and the color filter is connected to the mating member via the spacer on the color filter. It is made to face and adhere to the liquid crystal driving substrate. The liquid crystal can be injected by dropping the liquid crystal on one substrate and then sticking the other substrate together to spread the liquid crystal.Injection liquid crystal provided in the seal part is injected and the injection port is sealed. There is a way to stop. Any of the color filters provided with the spacer of the present invention can be manufactured by a known method, but the dropping injection method is more effective.

[Invention 2]

The spacer for a liquid crystal display device of the present invention comprises a negative photosensitive resin containing (A) an alkali-soluble resin, (B) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent. The negative photosensitive photosensitive resin composition obtained from the oil composition is not particularly limited. The liquid crystal display device spacer of the present invention described in the above-mentioned Invention 1 The forming photosensitive resin composition can be preferably used.

In the liquid crystal panel manufacturing process, in the liquid crystal dropping and injection process, pressure is applied at room temperature to spread the liquid crystal, and in the substrate bonding process, the seal is sealed at a high temperature. Therefore, it is necessary to have appropriate characteristics at normal temperature (25 ° C) and sealing temperature (180 ° C). That is, the spacer according to the present invention has a variation in the total deformation amount in the load-unloading test measured by a microhardness meter of the spacer formed from the photosensitive resin composition. Within the plane, the standard deviation (σ) at 25 ° C is within 0.25, preferably within 0.20, and the standard deviation (σ) at 180 ° C is within 0.30, preferably within 025. And (f) two points formed by connecting the points on the center side of the substrate and the points on the end side of the substrate of the points obtained by dividing the line segment connecting the center of the substrate and the plurality of ends into three equal parts. Within 2 cm square in each of the three areas formed by the figure, the standard deviation (σ) at 25 ° C is within 0.20, preferably within 0.15, and the standard deviation (σ) at 180 ° C is It is characterized by being within 0.25, preferably within 0.20.

Further, the spacer of the present invention has a variation in the amount of plastic deformation in the load-unloading test measured with a microhardness meter of the spacer formed of the photosensitive resin composition. The standard deviation (σ) at 25 ° C within the substrate surface is within 0.20, preferably within 0.15, and the standard deviation (σ) at 180 ° C is within 0.25, preferably within 0.20. (H) A point formed by connecting the center line of the substrate and the points on the edge side of the substrate at the point where each of the line segments connecting the center of the substrate and the plurality of edges is equally divided. Within 2 cm square in each of the three areas formed by the two figures, the standard deviation (σ) at 25 ° C is within 0.15, preferably within 0.10, standard at 180 ° C The deviation (σ) is within 0.20, preferably within 0.15.

The load-unloading test with the microhardness meter according to the present invention employs the following apparatus and measuring method.

Measurement sample: After the photosensitive榭脂composition was coated on a glass substrate, and the pre-beta 3 minutes 90 ° C, followed 500NijZcm ² was exposed, 0.10 mass ^_0/0 tetramethylammonium - Umuhidoro Kishido (TMAH ) After developing with aqueous solution, post-beta at 250 ° C for 30 minutes to produce a spacer with a height of 5 μm and a width of 10 μm.

Measuring device: Shimadzu Dynamic Ultra Hardness Tester DUH—W201 (manufactured by Shimadzu Corporation) Measuring point: (a) 5 points selected at random on the entire 370mm X 470mm substrate (see Figure 1)

(b) A point obtained by dividing the line connecting the center and end of a 370mm x 470mm board into three equal parts. Randomly selected 5 points within 2 cm square in each of the three areas (Center, Middle, Edge) formed by the connecting rectangle (see Figure 2)

Measurement method: Place the sample for measurement on the device and apply a load to the spacer at a constant speed of 324 mN Zsec with a 50 m diameter flat indenter, and when the maximum load reaches 30 mN Measure the total deformation amount and plastic deformation amount, and determine the variation. For the total deformation amount and plastic deformation amount of the spacer, obtain the hysteresis curve force of the load and deformation amount for the spacer as shown in Fig. 3, for example.

[0038] Further, the photosensitive resin composition forming the spacer preferably has a cured product having a glass transition temperature (Tg) of 160 ° C or higher. This glass transition temperature is measured by dynamic viscoelasticity measurement, and the following measuring apparatus and measuring method are employed.

Sample for measurement: An appropriate amount that gives a film thickness of 400 / zm after curing the photosensitive resin composition of the present invention is placed in an aluminum cup, and heated at 120 ° C. for 1 hour to drive off the solvent. Then expose to 500 mjZcm ² and cure at 220 ° C for 1 hour. Remove the cured product from the aluminum cup, cut it into 4mm width and 40mm length, and cut it into strips.

Measuring device: Dynamic viscoelastic device DMS6100 (manufactured by Seiko Instruments Inc.) Measuring method: A sample for measurement is set in the device, tensile mode, sine wave, frequency 1Ηζ, amplitude 10 μm, initial load 100 mN, rising Measured in the temperature range of 25-250 ° C at a temperature rate of 5 ° CZmin, and the peak position of loss tangent (tan δ) is defined as the glass transition temperature (Tg, ° C).

In the liquid crystal display device of the present invention, the height of the spacer in the liquid crystal injection and cell sealing process is determined by defining the spacer by a load-unloading test using a micro hardness tester as described above. Therefore, the desired cell gap can be maintained with less variation, and an improvement in manufacturing yield is expected.

The spacer according to the present invention has such characteristics, and the color filter according to the present invention having the spacer has a colored layer and a protective layer for protecting the colored layer on the substrate. In addition, an alignment film is provided on the protective layer for aligning the liquid crystal, and a columnar spacer is provided on the alignment film. . On the protective film, a transparent electrode for driving a liquid crystal may be formed as necessary. The manufacturing method of the spacer of the present invention, the shape of the spacer, the substrate, etc. The explanation is omitted because it is the same as Matter 1.

Example

[0040] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples! /.

Production Example 1 Manufacture of alkali-soluble rosin I

A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2,1azobis (2,4-dimethylbare-tolyl) and 200 parts by mass of diethylene glycol dimethyl ether. Subsequently, 33 parts by mass of acrylic acid and 27 parts by mass of acrylic acid n-butyl ester were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a copolymer. After the obtained copolymer solution is returned to room temperature, 40 parts by mass of glycidyl methacrylate and 2 parts by mass of pyridine are charged, heated to 100 ° C and stirred, and the acid value of the reaction solution is 0.5 mgKOHZg or less. The reaction was continued until When the weight average molecular weight of the obtained polymer was measured using GPC [HLC-8020 (manufactured by Tosohichi Co., Ltd.)], it was 18,000 in terms of polystyrene. Further, when the solid content acid value was measured, it was 102.8 mgKO HZg.

[0041] Production Example 2 Production of alkali-soluble rosin II

A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2,1azobis (2,4-dimethylvale-tolyl) and 200 parts by mass of diethylene glycol dimethyl ether. Subsequently, 43 parts by mass of acrylic acid and 24 parts by mass of acrylic acid n-butyl ester were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a copolymer. After the obtained copolymer solution is returned to room temperature, 33 parts by mass of glycidyl methacrylate and 1.6 parts by mass of triphenylphosphine are charged, heated to 100 ° C and stirred, and the acid value of the reaction solution is increased. The reaction was continued until 0.5 mg KOHZg or less. When the weight average molecular weight of the obtained polymer was measured using GPC [HLC-8020 (manufactured by Tosohichi Co., Ltd.)], it was 24,000 in terms of polystyrene. Moreover, it was 196.lmgKOHZg when the solid content acid value was measured.

[0042] <Invention 1>

Example 1 Into a reaction flask equipped with a nitrogen introduction tube, 100 parts by mass of the alkali-soluble resin I obtained in Production Example 1 and 300 parts by mass of diethylene glycol dimethyl ether [Maruzen Petrochemical Co., Ltd.] were added and stirred at 60 ° C for 3 hours. And dissolved. Next, the reaction solution was cooled to room temperature, 120 parts by mass of polymerizable polyfunctional compound A and 10 parts by mass of photopolymerization initiator I were added, and stirred at room temperature to dissolve. This solution was filtered through a filter having a pore size of 0.5 m to prepare a photosensitive resin composition.

Example 2 6 and Comparative Example 1 6

The same operation as in Example 1 was carried out to prepare photosensitive resin compositions having the compositions shown in Table 1 [Table 1]

[0044] [Note]

1) Alkali soluble fat

I: Obtained in Production Example 1

II: Obtained in Production Example 2

2) Polymerizable polyfunctional compound

A: KAYARAD DPHA [Nippon Kayaku Co., Ltd., trade name]

B: Lipoxy SP-4060 [Showa Polymer Co., Ltd., trade name]

C: CN- 975 [Product name, manufactured by Sartoma Company]

D: KAYARAD TMPTA [Nippon Kayaku Co., Ltd., trade name]

E: KAYARAD UX-4101 [Nippon Kayaku Co., Ltd., trade name]

3) Photopolymerization initiator

I: IRGACURE 907 [Product name, manufactured by Chinoku 'Specialty' Chemicals] II: IRGACURE 369 [Product name, manufactured by Chinoku 'Specialty' Chemicals] [0045] <Evaluation of various properties>

The characteristics shown below were evaluated for each photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 6. The results are shown in Tables 2 and 3.

(1) Coating properties

Each photosensitive resin composition was coated on a glass substrate using a spin coater and heated on a beta plate at 120 ° C. for 3 minutes to prepare a 6 μm coating film. This coating film is set in a hot air circulating dryer, heated to 250 ° C at a speed of 100 ° C force 0.5 ° CZmin, held at 250 ° C for 30 minutes, and then at 5 ° CZmin. The film was cooled to room temperature at a speed to obtain a coating film having a thickness of 5 m. The surface condition of this coating film was visually observed and the film thickness uniformity was evaluated using a surface roughness meter (vertical magnification: 500 times) according to the following criteria.

, Visual (surface condition)

Y: Smooth

X: There is a non-smooth and uneven grid pattern or wavy pattern

• Surface roughness meter (film thickness uniformity)

Obtain the variation rate (%) from the following formula. Variation rate (%) = {[(Maximum film thickness)-(Minimum film thickness)] / (Average film thickness)} X 100

○: Variation rate is 10% or less

X: Variation rate exceeds 10%

(2) Adhesion with glass substrate and ITO film

Each photosensitive resin composition was coated on a glass substrate using a spin coater and a substrate on which a 250 nm ITO film was formed, and heated on a beta plate at 120 ° C for 3 minutes to 6 m. A coating film was prepared. Set this coating film in a hot-air circulating dryer, raise the temperature to 250 ° C at a speed of 0.5 ° C Zmin at 100 ° C force, hold it at 250 ° C for 30 minutes, and then speed it at 5 ° CZmin. Was cooled to room temperature to obtain a coating film having a thickness of 5 m. The surface of the obtained coating film was cut into 100 mm lmm openings based on JIS K5600, peeled off after applying a cellophane tape, and the adhesion of the coating film was evaluated according to the following criteria.

○: No peeling

X: With peeling

(3) Resolution after curing and cross-sectional shape of pattern

Each photosensitive resin composition was coated on a glass substrate using a spin coater and heated on a beta plate at 120 ° C. for 3 minutes to prepare a 6 m coating film. This coating film was exposed using a test pattern. The exposure was performed with exposures of 100, 200, 300, and 500 miZcm ² using filters that transmit only i-line (365 nm), respectively. Subsequently, paddle development was performed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), rinsed with pure water, and finally spin-dried. The obtained negative pattern is set in a hot air circulating dryer, heated to 100 ° C at a rate of 0.5 ° CZmin to 250 ° C, held at 250 ° C for 30 minutes, then 5 ° Cooled to room temperature at a CZmin rate. The obtained pattern was observed with an optical microscope, and the resolution and cross-sectional shape were evaluated according to the following criteria.

'Resolution

◎: Spacer formation of less than 10 m

○: Spacer formation of less than 10-12 μm

Δ: Spacer formation of 12-14 m

Χ: Spacer formation of 14 μm or more Cross-sectional shape

○, △, X: Evaluation according to Figure 4

(4) Chemical resistance

The resolution test Nio after curing of the (3), Te, a pattern of sample formed by 300MjZcm ² irradiation, N- methyl-2-pyrrolidone (drug A), y Buchirorataton (drug B), peeling Liquid 104 (manufactured by Tokyo Ohka Co., Ltd.) (Chemical C) is each immersed for 30 minutes at room temperature, and the appearance of the pattern such as swelling and peeling of the pattern is observed, and the tape peeling test is performed on the pattern after immersion!ヽ Each appearance and adhesion were evaluated according to the following criteria

'Appearance

○: No change in appearance such as swelling or peeling

X: Appearance changes such as swelling and peeling

'Adhesiveness

○: No peeling

X: With peeling

(5) Thermophysical properties of cured products

An appropriate amount of each photosensitive resin composition with a thickness of 400 μm after curing was placed in an aluminum cup and heated to remove the solvent at 120 ° C. for 1 hour. Thereafter, it was exposed to 500 mjZcm ² and cured at 220 ° C. for 1 hour. The cured product was removed from the aluminum cup, cut into a width of 4 mm and a length of 40 mm, and formed into a strip shape. The measurement apparatus and measurement conditions were as shown below.

Measuring device: Dynamic viscoelastic device DMS6100 (manufactured by Seiko Instruments Inc.) Measuring method: A sample for measurement is set in the device, tensile mode, sine wave, frequency 1Ηζ, amplitude 10 μm, initial load 100 mN, rising Measurements were made at a temperature rate of 5 ° CZmin in the temperature range of 50 to 250 ° C, and the storage elastic modulus (Ε ', GPa), glass transition temperature (Tg, ° C), and loss tangent (tan δ) were determined. Moreover, the change rate of the storage elastic modulus was calculated | required from the following formula.

Rate of change in storage modulus [― 20 ° C → 25 ° C] (%) = {[“Storage modulus at 20 ° C” − “Storage modulus at 25 ° C”] Z “-20 ° C Storage modulus "} X 100

Change rate of storage modulus [25 ° C → 180 ° C] (%) = {["Storage modulus at 25 ° C"-"180 ° C Storage modulus ”] Z“ storage modulus at 25 ° C ”} X 100

(6) Spacer push-in displacement

Each photosensitive resin composition was coated on a glass substrate, pre-betated at 90 ° C for 3 minutes, then exposed to 500 mjZcm ² , developed with 0.10 wt% TMAH aqueous solution, and height 5 / ζ πι A spacer with a width of 10 m was produced. The measurement apparatus and measurement conditions were as shown below. Measuring equipment: Shimadzu Dynamic Ultra-Hardness Tester DUH— W201 [manufactured by Shimadzu Corporation] Measuring method: A measuring sample is set in the equipment and a flat indenter with a diameter of 50 m is used. When the maximum load was 30 mN, the displacement of the spacer was measured, and the rate of change was calculated using the following formula.

Rate of change (%) = ["Displacement at 180 ° C" Z "Displacement at 25 ° C"] X 100

[0048] [Table 2]

Table 2

[0049] [Table 3] Table 3

Examples 7-12 and Comparative Examples 7-14

The same operation as in Example 1 was performed to prepare photosensitive resin compositions having the compositions shown in Table 4. [Table 4]

[note]

1) Alkali soluble fat

I: Obtained in Production Example 1

II: Obtained in Production Example 2

2) Polymerizable polyfunctional compound

A: KAYARAD DPHA [manufactured by Nippon Kayaku Co., Ltd., quotient: Lipoxy SP-4060 [manufactured by Showa Polymer Co., Ltd., quotient C: CN-975 [trade name, manufactured by Sartoma Co., Ltd.] D: KAYARAD TMPTA [Nippon Kayaku Co., Ltd., trade name]

E: KAYARAD R—130 [Nippon Kayaku Co., Ltd., trade name]

3) Photopolymerization initiator

I: IRGACURE 907 [Product name, manufactured by Chinoku 'Specialty' Chemicals] [0053] <Evaluation of various properties>

The characteristics shown below were evaluated for each photosensitive resin composition prepared in Examples 7 to 12 and Comparative Examples 7 to 14. The results are shown in Tables 5-9. In Tables 6 to 9, MAX is the maximum value, MIN is the minimum value, Ave. is the average value, and S. D. is the standard deviation.

(1) Coating properties

Evaluation was performed by the method described above.

(2) Adhesion with glass substrate and ITO film

Evaluation was performed by the method described above.

(3) Resolution after curing and cross-sectional shape of pattern

Evaluation was performed by the method described above.

(4) Chemical resistance

Evaluation was performed by the method described above.

(5) Thermophysical properties of cured products

Measuring device: Dynamic viscoelastic device DMS6100 (manufactured by Seiko Instruments Inc.) Measuring method: A sample for measurement is set in the device, tensile mode, sine wave, frequency 1Ηζ, amplitude 10 μm, initial load 100 mN, rising The temperature was measured at a temperature rate of 5 ° CZmin in the temperature range of 25 to 250 ° C, and the peak position of loss tangent (tan δ) was defined as the glass transition temperature (Tg, ° C).

[0054] (6) Spacer load-unloading test with micro hardness tester

After the photosensitive榭脂composition was coated on a glass substrate, and pre-beta 3 minutes 90 ° C, 500nijZcm ² exposed after its, 0.10 mass ^_0/0 tetramethylammonium - Umuhidorokishido (TMAH) After developing with an aqueous solution, postbeta was performed at 250 ° C. for 30 minutes to produce a spacer having a height of 5 μm and a width of 10 μm. The obtained spacer was subjected to a load-unloading test with the following measuring device and measurement conditions.

(b) Random selection within 2 cm square in each of three areas (Center, Middle, Edge) formed by quadrilaterals connecting points obtained by dividing the line connecting the center and edge of a 370mm X 470mm board into three equal parts 5 locations (see Figure 2)

Measurement method: Place the sample for measurement on the device and apply a load to the spacer at a constant speed of 324 mN Zsec with a 50 m diameter flat indenter, and when the maximum load reaches 30 mN The total deformation amount and the plastic deformation amount were measured, and the variation was obtained. The total deformation amount and plastic deformation amount of the spacer were obtained from the hysteresis curve of load and deformation amount for the spacer shown in Fig. 3.

[Table 5]

Table 5

Durability

Film properties Adhesion Properties after curing Thermophysical properties

(Appearance / welding)

ITO film Resolution Tg

Shape Chemical A Chemical B Chemical c

/ Uniformity / Glass (.c)

7 o / o o / o o o o / o o / o o / o 165

8 ○ / ○ o / o o ○ o / o o / o o / o 164 Actual 9 ○ / ○ o / o o ○ o / o ○ z o o / o 168

Example 10 o / o o / o o ○ o / o o / o o / o 160

11 o / o o / o o ○ o / o o / o o / o 162

12 o / o o / o o ○ O / O o / o o / o 176

7 o / o o / o ◎ X o / o o / o o / o 146

8 X / X o / o X Δ O / x O / x O / x 174

9 o / o o / o Δ ○ o / o o / o o / o 160 ratio 10 o / o o / o Δ ○ O / x O / x O / x 159 comparison

Example 11 ○ / 0 o / o ◎ X o / o o / o o / o 152

12 o / o X / X ◎ X O / x O / x O / x 149

13 o / o o / o 〇〇 o / o o / o o / o 173

14 X / XX / XXXO / x O / x O / x 179 Table ¹

s 〔sffi005 Table 7

§S

Table 8

[¾ [005

Industrial applicability

The photosensitive resin composition of the invention 1 has a negative pattern forming ability, a high contrast, a high sensitivity, and a negative forward taper pattern with good dimensional controllability. The finally obtained cured product has good heat resistance, chemical resistance and adhesion to the substrate, and can be used as a spacer for a liquid crystal display device having excellent strength. In addition, the spacer for a liquid crystal display device according to the second aspect of the present invention does not cause a display defect with a small cell gap variation when used in a liquid crystal display device, thereby realizing a high-quality liquid crystal display device. Can do.

Claims

The scope of the claims

[1] A negative photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent,

(d) A photosensitive resin composition for forming a spacer for a liquid crystal display device, wherein the cured product has a value of tan δ at −50 to 250 ° C. of 0.1 or less.

[2] Negative photosensitive resin composition strength (i) Alkali-soluble resin having a polymerizable functional group having a weight average molecular weight of 10,000 to 20,000 and a glass transition temperature of 110 ° C or higher. The liquid crystal display device spacer according to claim 1, comprising: (B) a polymerizable polyfunctional compound (50) to 250 parts by mass; (C) a photopolymerization initiator 1 to 20 parts by mass; and (D) a solvent. Forming photosensitive resin composition.

[3] (A) Alkali-soluble rosin comprises (al) a carboxylic acid having an ethylenically unsaturated bond and

Z or a part of a copolymer of a carboxylic acid anhydride having an ethylenically unsaturated bond and (a2) another unsaturated compound having an ethylenically unsaturated bond, (a3) an ethylenically unsaturated bond 2. The photosensitive resin composition for forming a spacer of a liquid crystal display device according to claim 1, which is a resin obtained by reacting with an epoxy resin compound.

[4] The photosensitive resin composition for forming a spacer for a liquid crystal display device according to [1], wherein the (B) polymerizable polyfunctional compound has 5 or more functional groups.

[5] The photosensitive resin composition for forming a spacer for a liquid crystal display device according to claim 1, wherein the polymerizable polyfunctional compound (B) has a glass transition temperature of 100 ° C or higher.

[6] The photosensitive resin composition for forming a liquid crystal display device spacer according to claim 1, wherein the polymerizable polyfunctional compound (B) has a urethane bond.

[7] The spacer of the liquid crystal display device according to claim 1, wherein a change rate of the indentation deformation amount at 25 ° C and the indentation deformation amount at 180 ° C of the formed spacer is 100 to 120%. Forming photosensitive resin composition.

[8] ¹ ~~ "Sa ¹ ~~ to photosensitive榭脂composition comprising formed by using a liquid crystal display device for scan of claim 1 -

[9] A color filter comprising a spacer for a liquid crystal display device formed by using the photosensitive resin composition according to claim 1.

[10] A liquid crystal display device comprising a spacer for a liquid crystal display device formed using the photosensitive resin composition according to claim 1.

[11] A negative photosensitive resin composition containing (A) an alkali-soluble resin, (B) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent. The variation of the total deformation in the load-unloading test measured with a microhardness meter is (e) within the 0.25 standard deviation (σ) at 25 ° C within the substrate surface, The standard deviation (σ) at 180 ° C is within 0.30, and

A spacer for a liquid crystal display device.

[12] A negative photosensitive resin composition containing (Α) an alkali-soluble resin, (Β) a polymerizable polyfunctional compound, (C) a photopolymerization initiator, and (D) a solvent. The variation in the amount of plastic deformation in the load-unloading test measured with a microhardness meter

(h) By two figures formed by connecting the points on the center side of the substrate and the points on the end side of the substrate at the points obtained by dividing each line segment connecting the center of the substrate and the plurality of ends into three equal parts. Within 2cm square in each of the three areas formed, the standard deviation (σ) at 25 ° C is within 0.15

The standard deviation (σ) at 180 ° C is within 0.20,

A spacer for a liquid crystal display device.

[13] Negative photosensitive resin composition power (ii) Weight average molecular weight is 10,000-20,000, 100 parts by mass of an alkali-soluble resin having a polymerizable functional group having a glass transition temperature of 110 ° C. or higher, (B) 50 to 250 parts by mass of a polymerizable polyfunctional compound, (C) a photopolymerization initiator 1 to 20 13. The spacer for a liquid crystal display device according to claim 11 or 12, wherein the glass transition temperature of the cured product obtained from the resin composition containing 160 parts by mass and (D) a solvent is 160 ° C or higher.

[14] (A) Alkali-soluble resin is (al) a carboxylic acid having an ethylenically unsaturated bond and a carboxylic acid anhydride having Z or an ethylenically unsaturated bond, and (a2) other ethylenically unsaturated bonds The liquid crystal according to claim 11 or 12, which is a resin obtained by reacting a part of a copolymer with an unsaturated compound having an epoxy compound having (a3) an ethylenically unsaturated bond. Spacer for display device.

[15] The spacer for liquid crystal display device according to [11] or [12], wherein (B) the polymerizable polyfunctional compound has 5 or more functional groups.

[16] The spacer for a liquid crystal display device according to [11] or [12], wherein the polymerizable polyfunctional compound (B) has a glass transition temperature of 100 ° C. or higher.

[17] The spacer for a liquid crystal display device according to [11] or [12], wherein the polymerizable polyfunctional compound (B) has a urethane bond.

[18] A color finolet having the spacer for a liquid crystal display device according to [11] or [12].

[19] A liquid crystal display device comprising the spacer for a liquid crystal display device according to [11] or [12].