TWI425011B - Side chain unsaturated polymer, sensitive radiation linear resin composition and spacer for liquid crystal display element - Google Patents

Description

Side chain unsaturated polymer, sensitive radiation linear resin composition and spacer for liquid crystal display element

The present invention relates to a polymer which is extremely suitable for formation of a spacer of a liquid crystal display element, a radiation sensitive linear resin composition comprising the polymer, and a spacer, the formation method and the liquid crystal display element.

In the liquid crystal display device, in order to maintain the interval between the two substrates, that is, the cell gap (Cell Gap) is constant, a spacer such as a glass bead or a plastic bead having a specific particle diameter is conventionally used. Since the spacers are randomly dispersed on a transparent substrate such as a glass substrate, if a spacer is present in the pixel formation region, a spacer phenomenon may be generated, or the incident light may be scattered to cause the liquid crystal display element. The contrast is reduced.

Therefore, in order to solve this problem, a method of forming a spacer by lithography has been gradually adopted. In this method, the sensitive radiation linear resin composition is applied onto a substrate and is exposed to a specific mask, for example, by exposure to ultraviolet light, to form a dot or strip-shaped spacer, since only the pixel is formed. Spacers are formed at specific locations outside the area, so the aforementioned problems are basically solved.

In addition, in recent years, the size of the mother glass substrate (for example, 1,500 × 1,800 mm, and more preferably 1,870 × 2,200 mm) has progressed rapidly from the viewpoints of large-area liquid crystal display elements and improvement in productivity. . In the conventional substrate size, since the substrate size is smaller than the size of the mask, it is possible to The single exposure method is used for processing, but in a large substrate, it is almost impossible to produce a photomask having the same size as the substrate, and it is not easy to perform processing in a single exposure manner.

Therefore, as an exposure method that can correspond to a large substrate, a step exposure method is advocated. However, in the stepwise exposure mode, since one substrate is subjected to exposure in several steps, the time for alignment and step movement is required for each exposure, and therefore, the amount of processing is more reduced than that of the single exposure mode.

Therefore, in the single exposure mode, an exposure amount of about 3,000 J/m ² can be tolerated, but in the step exposure mode, it is necessary to reduce the amount of exposure per time. However, in the sensitive radiation linear resin composition used in the formation of the separator, it is difficult to achieve a sufficient spacer shape and film thickness at an exposure amount of 1,000 J/m ² or less.

Further, as the substrate is increased in size, when a defect occurs in the step, the alignment film formed on the color filter must be peeled off and reused. Since the peeling of the alignment film is carried out using a stripping solution of an alkaline aqueous solution, the separator needs to have resistance to the stripping liquid. In other words, when the alignment film is peeled off, the spacer of the underlayer preferably does not undergo film thickness change due to swelling or dissolution, and the physical properties such as elastic properties must also exhibit properties equivalent to those before peeling.

Further, in the conventional bonding method, when the TFT array and the color filter are bonded, a load is applied, and the spacer is uniformly pressed by the load to maintain the uniformity of the height of the spacer. However, in the ODF (One Drop Filling) method, the load formed by the weight of the substrate is initially bonded to the atmospheric pressure, and the initial state is compared with the conventional method. The bonding load is small. Therefore, it is important that even if the spacer is pressed with a small load, uniform pressing can show the consistency of the height of the spacer. Therefore, the spacer must have softness. If the heights of the spacers do not match, the uniformity of the pitch of the liquid crystal cells cannot be maintained, and a gap is formed in the liquid crystal cell to cause display ripple.

In the Japanese Patent Publication No. 2000-105456, JP-A-2000-171804, and JP-A-2000-298339, it is disclosed that a high-sensitivity and chemical resistance is achieved by using a copolymerizable resin. The property of the separator or the protective film is improved, and the copolymerizable resin is a photosensitive resin composition having (meth)acryloyloxy Alkyl Isocyanate (Meth) A photopolymerizable functional group in which a compound reacts with a copolymerizable resin having a hydroxyl group is used as a constituent unit. In addition, it is used in the molecule for the purpose of improving the heat resistance of the separator or the protective film, the adhesion to the substrate, the chemical resistance, and particularly the resistance to the alignment film peeling solution or the alkaline aqueous solution. Epoxy based epoxy resin. However, when this epoxy resin is added, there is a concern that the storage stability of the photosensitive resin composition or the solubility of the developing solution is lowered.

Accordingly, it is an object of the present invention to provide a high-sensitivity, which can obtain a sufficient spacer shape even at an exposure amount of 1,000 J/m ² or less, and has good abrasion resistance and adhesion to a transparent substrate. The heat-resistant property, the flexibility of the spacer, and the storage stability of the composition can form a sensitive radiation linear resin composition of the spacer for a liquid crystal display element.

Another object of the present invention is to provide a polymer which can be used for the resin component of the radiation sensitive linear resin composition.

Another object of the present invention is to provide a liquid crystal display spacer formed of the above-mentioned sensitive radiation linear resin composition and a liquid crystal display element comprising the same.

Another object of the present invention is to provide a method of forming the above liquid crystal display spacer.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention can be attained by a sensitive radiation linear resin composition (hereinafter referred to as "sensitive radiation linear resin composition"), which is characterized in that: a polymer composed of a polymerization unit of a monomer and having a group represented by the following formula (1), the single system containing at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride 1 kind; [B] polymerizable unsaturated compound; and [C] sensitive radiation linear polymerization initiator (In the formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an exoethyl group or a propyl group, n is an integer of 1 to 5, and "*" is a bonding bond).

According to the present invention, the above objects and advantages of the present invention, second, can be borrowed It is achieved by the aforementioned [A] polymer.

According to the present invention, the above objects and advantages of the present invention, and thirdly, can be achieved by a spacer for a liquid crystal display element formed of the above-mentioned sensitive radiation linear resin composition.

According to the present invention, the above objects and advantages of the present invention can be attained by a method for forming a spacer for a liquid crystal display element, characterized in that it comprises at least the following steps in the order described below: a step of forming a film of the above-mentioned sensitive radiation linear resin composition on a substrate; (b) a step of exposing at least a portion of the film; and (c) a step of developing the film after exposure; (D) A step of heating the film after development.

According to the present invention, the above objects and advantages of the present invention can be attained by a liquid crystal display device comprising the spacer for a liquid crystal display element.

The invention is described in detail below.

polymer

The polymer of the present invention is composed of a polymerization unit of a monomer and has a group represented by the above formula (1) (hereinafter referred to as "[A] polymer"), and the single system contains an unsaturated carboxylic acid. And at least one selected from the group consisting of unsaturated carboxylic anhydrides (hereinafter, these compounds are collectively referred to as "(a1) unsaturated A carboxylic acid compound").

[A] The polymer can be, for example, a compound represented by the following formula (2) (hereinafter referred to as "unsaturated isocyanate compound"), and (a1) an unsaturated carboxylic acid compound and 1 molecule; A copolymer of more than one hydroxyl or amino group unsaturated compound is obtained by reacting. In the preferred [A] polymer of the present invention, for example, an unsaturated isocyanate compound represented by the following formula (2), and (a1) an unsaturated carboxylic acid compound and (a2) are contained in one molecule or more. a polymer obtained by reacting a copolymer of a hydroxyl group-unsaturated compound (hereinafter referred to as "copolymer [α]") (R in the formula ^{(2), R 1, R} 2 , and n, respectively of formula (1) of ^1, R ² and n are synonymous).

Among the components constituting the copolymer [α], (a1) an unsaturated carboxylic acid compound, for example, acrylic acid, methacrylic acid, Crotonic acid, and 2-Acryloyloxy Ethyl. Succinate), 2-methylpropenyl ethoxysuccinate, 2-Acryloyloxy Ethyl Hexahydrophthalate, 2-methylpropenyloxyhexahydrophthalate Monocarboxylic acid such as ethyl formate; maleic acid, fumaric acid, Citraconic acid, mesaconic acid, itaconic acid And the like; a dicarboxylic acid; an acid anhydride of the above dicarboxylic acid.

Among these (a1) unsaturated carboxylic acid compounds, acrylic acid and methacrylic acid are preferable in terms of copolymerization reactivity and ease of solubility and availability of the obtained [A] polymer to an alkaline developing solution. , maleic anhydride, and the like.

In the copolymer [α], the (a1) unsaturated carboxylic acid compound may be used singly or in combination of two or more.

The content of the repeating unit (polymerization unit) derived from the (a1) unsaturated carboxylic acid compound is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably 15%, based on the copolymer [α]. 30% by weight. When the content of the repeating unit (polymerization unit) derived from the (a1) unsaturated carboxylic acid compound is less than 5% by weight, the polymer obtained by the reaction with the unsaturated carboxylic acid compound (1) is alkaline. The solubility of the liquid tends to decrease. On the other hand, when it exceeds 50% by weight, the solubility of the polymer in the alkaline developing solution is excessively increased.

Further, (a2) an unsaturated compound containing one or more hydroxyl groups in one molecule, for example, 2-hydroxyethyl acrylate (2-Hydroxyethyl Acrylate), 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic acid 5-hydroxypentyl ester, 6-hydroxyhexyl acrylate, 7-hydroxyheptyl acrylate, 8-hydroxyoctyl acrylate, 9-hydroxydecyl acrylate, 10-hydroxydecyl acrylate, 11-hydroxyundecyl acrylate, acrylic acid 12-hydroxylauryl ester-like hydroxyalkyl acrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, A 6-hydroxyhexyl acrylate, 7-hydroxyheptyl methacrylate, 8-hydroxyoctyl methacrylate, methyl propyl 9-hydroxydecyl enoate, 10-hydroxydecyl methacrylate, 11-hydroxyundecyl methacrylate, hydroxyalkyl methacrylate like 12-hydroxylauryl methacrylate; 2-(2-acrylic acid) -Hydroxyhexyloxy)ethyl ester, 3-(6-hydroxyhexyloxy)propyl acrylate, 4-(6-hydroxyhexyloxy)butyl acrylate, 5-(6-hydroxyhexyloxy)acrylate Ethyl acetate, 6-(6-hydroxyhexyloxy) hexyl acrylate (6-hydroxyhexyloxy) alkyl acrylate; 2-(6-hydroxyhexyloxy) methacrylate Ester, 3-(6-hydroxyhexyloxy)propyl methacrylate, 4-(6-hydroxyhexyloxy)butyl methacrylate, 5-(6-hydroxyhexyloxy) methacrylate Amyl Ester (6-hydroxyhexyloxy)alkyl methacrylate like 6-(6-hydroxyhexyloxy)hexyl methacrylate; (6-hydroxyhexyloxy) methacrylate Commercially available products of a mixture of a base ester and 2-hydroxyethyl methacrylate are, for example, available under the trade names of PLACCELFM1D, FM2D (manufactured by Daicel Chemical Industries Co., Ltd.).

Further, 2-(3-hydroxy-2-2-dimethyl-propoxycarbonyloxy)-ethyl acrylate, 3-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) acrylate -propyl ester, 4-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-butyl acrylate, 5-(3-hydroxy-2,2-dimethyl-propyl acrylate Oxycarbonyloxy)-pentyl ester, acrylic acid 6-(3-hydroxy-2,2-dimethyl,propoxycarbonyloxy)-hexyl acrylate (3-hydroxy-2,2-dimethyl Base-propoxycarbonyloxy)-alkyl ester; etc.; 2-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl methacrylate, 3-(methacrylic acid) 3-hydroxy-2,2-dimethyl-propoxycarbonyloxy )-propyl ester, 4-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-butyl methacrylate, 5-(3-hydroxy-2,2-dimethyl methacrylate Methyl-propyloxycarbonyloxy)-pentyl ester, 6-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-hexyl methacrylate -2,2-Dimethyl-propoxycarbonyloxy)-alkyl ester and the like.

A commercially available product of a mixture of (3-hydroxy-2,2-dimethyl,propoxycarbonyloxy)-alkyl (meth)acrylate and 2-hydroxyethyl methacrylate, for example, under the trade name HEMAC1 (manufactured by Daicel Chemical Industries Co., Ltd.).

Further, 4-hydroxy-cyclohexyl acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxyethyl acrylate, cyclohexylethyl ester, 3-hydroxy-bicyclo[2.2.1]g-5 -al-2-yl ester, 3-hydroxymethyl-bicyclo[2.2.1]hept-5-en-2-ylmethyl acrylate, 3-hydroxyethyl-bicyclo(2.2.1]hept-5-acrylate Alkenyl-2-ylethyl ester, 8-hydroxy-bicyclo[2.2.1]hept-5-en-2-yl acrylate, 2-hydroxy-octahydro-4,7-methanol-non-5-yl acrylate (Acrylic Acid 2-Hydroxy-Octahydro-4, 7-Methano-Indene-5-Y1 Ester), 2-hydroxymethyl-octahydro-4,7-methanol acrylate, indole-5-yl methyl ester, acrylic acid 2- Hydroxyethyl-octahydro-4,7-methanol-indol-5-ylethyl ester, Acrylic Acid 3-Hydroxy-Adamantane-1-Y1 Ester, Acrylic acid 3 -Hydroxymethyl-adamantan-1-ylmethyl ester, 3-hydroxyethyl-adamantan-1-ylethyl acrylate, hydroxyalkyl acrylate having an alicyclic structure; 4-hydroxy-methacrylate Cyclohexyl ester, 4-hydroxymethyl-cyclohexylmethyl methacrylate, 4-hydroxyethyl-cyclohexylethyl methacrylate, 3-hydroxy-bicyclo[2.2.1]hept-5-ene methacrylate -2-yl ester, 3-hydroxy methacrylate A Base-bicyclo[2.2.1]hept-5-en-2-ylmethyl ester, 3-hydroxyethyl-bicyclo[2.2.1]hept-5-en-2-ylethyl methacrylate, methacrylic acid 8-Hydroxy-bicyclo[2.2.1]hept-5-en-2-yl ester, 2-hydroxy-octahydro-4,7-methanol-non-5-yl methacrylate, 2-hydroxy methacrylate Methyl-octahydro-4,7-methanol-indol-5-yl methyl ester, 2-hydroxyethyl-octahydro-4,7-methanol-indol-5-ylethyl methacrylate, methacrylic acid 3 -Hydroxy-adamantan-1-yl ester, 3-hydroxymethyl-adamantane-1-yl methacrylate, 3-hydroxyethyl-adamantan-1-ylethyl methacrylate Cyclic structure of hydroxyalkyl methacrylate; 1,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl acrylate, 3,4-dihydroxybutyl acrylate Dihydroxyalkyl acrylate such as ester, 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropyl acrylate; 1,2- methacrylic acid Hydroxyethyl ester, 2,3-dihydroxypropyl methacrylate, 1,3-dihydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 3-[3-(2 methacrylate) ,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxy Propyl methacrylate, etc. dihydroxy alkyl ester.

Among these unsaturated compounds having one or more hydroxyl groups in one molecule, 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate are preferable from the viewpoint of copolymerizability and reactivity with an isocyanate compound. 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-(6-hydroxyhexyloxy)ethyl acrylate, A 2-(6-hydroxyhexyloxy)ethyl acrylate, 2-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl acrylate, 2-(3) methacrylate -hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl ester, 4-hydroxymethyl-cyclohexyl acrylate Ester, 3-hydroxymethyl-adamantan-1-ylmethyl acrylate, 3-hydroxymethyl-adamantan-1-yl methacrylate, 2,3-dihydroxypropyl acrylate, methacrylic acid 2 , 3-dihydroxypropyl ester, and the like.

In the copolymer [α], (a2) an unsaturated compound containing one or more hydroxyl groups in one molecule may be used singly or in combination of two or more.

The content of the repeating unit (polymerization unit) derived from (a2) an unsaturated compound having one or more hydroxyl groups in one molecule is preferably from 1 to 50% by weight, more preferably from 3 to 5%, based on the copolymer [α]. 40% by weight, particularly preferably 5 to 30% by weight. When the content of the repeating unit derived from (a2) the unsaturated compound containing one or more hydroxyl groups in one molecule is less than 1% by weight, the introduction ratio of the unsaturated isocyanate compound to the polymer is lowered, and the sensitivity is lowered. On the other hand, when it exceeds 50% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound tends to be lowered.

Further, as the copolymer [α], an unsaturated compound other than (a1) and (a2) (hereinafter referred to as "(a3) other unsaturated compound") may be used as a component of the copolymer.

Specific examples thereof include alkyl acrylates such as methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, secondary butyl acrylate, and tertiary butyl acrylate; methyl methacrylate, An alkyl methacrylate such as ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, butyl methacrylate or butyl methacrylate; Glycidyl Acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, acrylic acid 3 , epoxy epoxy (cyclo)alkyl esters such as 4-epoxycyclohexyl ester; glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-butyl butyl methacrylate, Ethylene methacrylate epoxy (cyclo)alkyl group such as 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate Ester; α-ethyl methacrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylate Other α-alkyl acrylate epoxy (cyclo)alkyl esters such as glyceride, α-ethyl acrylate 6,7-epoxyheptyl ester, α-ethyl acrylate 3,4-epoxycyclohexyl ester; Glycidyl ethers such as glycidyl glycidyl ether, m-ethylbenzyl glycidyl ether, p-ethylbenzyl glycidyl ether, etc.; 3-(methacryloxymethyl)oxycyclobutane (3- (Methacryloyloxymethyl)Oxetane), 3-(methacryloxymethyl)-3-ethyloxycyclobutane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-2-trifluoromethylcyclobutane, 3-(methacryloxymethyl)-2-pentafluoroethyloxycyclobutane, 3- (methacryloxymethyl)-2-phenyloxycyclobutane, 3-(methacryloxymethyl)-2,2-difluorooxocyclobutane, 3-(methacryl醯oxymethyl)-2,2,4-trifluorooxycyclobutane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluorooxocyclobutane, 3- (methacryloxyethyl)oxycyclobutane, 3-(methacryloxyethyl)-3-ethyloxycyclobutane, 2-ethyl-3-(methacryloxy) Ethyl ethyl) oxycyclobutane, 3-(methacryloxyethyl)-2- Fluoromethyloxycyclobutane, 3-(methacryloxyethyl)-2-pentafluoroethyloxycyclobutane, 3-(methacryloxyethyl)-2-phenyloxy Cyclobutane, 2,2-difluoro-3-(methacryloxyethyl)oxycyclobutane, 3-(methacryloxyethyl)-2,2,4-trifluoroox a methacrylate having an oxocycloyl group such as cyclobutane or 3-(methacryloxyethyl)-2,2,4,4-tetrafluorooxocyclobutane; (Allyloxymethyl)oxycyclobutane, 3-(acryloxymethyl)-3-ethyloxycyclobutane, 3-(acryloxymethyl)-2-methyloxane Butane, 3-(acryloxymethyl)-2-trifluoromethyloxycyclobutane, 3-(acryloxymethyl)-2-pentafluoroethyloxycyclobutane, 3-( Propylene methoxymethyl)-2-phenyloxycyclobutane, 3-(acryloxymethyl)-2,2-difluorooxocyclobutane, 3-(acryloxymethyl)- 2,2,4-trifluorooxocyclobutane, 3-(acryloxymethyl)-2,2,4,4-tetrafluorooxocyclobutane, 3-(acryloxyethyl)oxyl Cyclobutane, 3-(acryloxyethyl)-3-ethyloxycyclobutane, 2-ethyl-3-(acryloxyethyl)oxycyclobutane, 3-(propylene oxide) Base ethyl)-2 -trifluoromethyloxocyclobutane, 3-(acryloxyethyl)-2-pentafluoroethyloxycyclobutane, 3-(acryloxyethyl)-2-phenyloxetane Alkane, 2,2-difluoro-3-(acryloxyethyl)oxycyclobutane, 3-(acryloxyethyl)-2,2,4-trifluorooxocyclobutane, 3- (Acetyloxyethyl)-2,2,4,4-tetrafluorooxocyclobutane, etc., oxycyclobutyl acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, acrylic acid Ring [5.2.1.0 ^2,6 ]decane-8-yl ester, 2-(tricyclo[5.2.1.0 ^2'6 ]decane-8-yloxy)ethyl acrylate, isodecyl acrylate (Isobornyl Acrylate) Ethyl acrylate cyclic ester; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[cyclopropyl] methacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, methyl Acrylic acid alicyclic ester of 2-(tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxy)ethyl acrylate, isodecyl methacrylate, etc.; phenyl acrylate, benzyl acrylate, etc. Aromatic or arylalkyl acrylate; aromatic or aryl methacrylate of phenyl methacrylate, benzyl methacrylate, etc.; diethyl maleate, fumaric acid Dialkyl dicarboxylates such as diethyl ester and diethyl itaconate; tetrahydrofuran-2-yl acrylate, tetrahydrofuran-2-yl acrylate, methyltetrahydrofuran-2-yl acrylate An acrylate having an oxygen-containing heterocyclic 5-membered ring or an oxygen-containing heterocyclic 6-membered ring; tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl methacrylate, methyl methacrylate a methacrylate having an oxygen-containing heterocyclic 5-membered ring or an oxygen-containing heterocyclic 6-membered ring, such as tetrahydrofuran-2-yl ester; styrene, α-methylstyrene (α-Methyl Styrene), m-methylstyrene, a vinyl aromatic compound such as p-methylene styrene or p-methoxy styrene; maleimide, n-phenyl maleimide, n-cyclohexyl succinimide, etc. Unsaturated quinone imine; conjugated diene compound such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; acrylonitrile (Acrylonitrile), A Acrylonitrile, Acrylic Amide, methacrylamide, vinyl chloride, dichloroethylene, ethyl acetate, and the like.

Among these (a3) other unsaturated compounds, it is preferred that the copolymerization property and the solubility of the obtained [A] polymer to an alkaline developing solution are n-butyl methacrylate or methacrylic acid. Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-methyl-3(methyl)propenyloxymethyloxycyclobutane, 3-ethyl-3(methyl)propenyloxymethyloxycyclobutane, 3-(methacryloxymethyl)-3-ethyloxycyclobutane, benzyl methacrylate, A ^Tricyclo [5.1.02 ^2'6 ]decane-8-yl acrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and the like.

In the copolymer [α], (a3) other unsaturated compounds may be used singly or in combination of two or more.

The content of the repeating unit derived from (a3) other unsaturated compound is preferably from 10 to 75% by weight, more preferably from 20 to 70% by weight, particularly preferably from 30 to 65% by weight, based on the copolymer [α]. On the other hand, if the content of the repeating unit derived from the (a3) other unsaturated compound is less than 10% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (2) tends to decrease. If it exceeds 75% by weight, the solubility of the polymer in the alkaline developing solution tends to decrease.

The copolymer [α] can be, for example, an (a1) unsaturated carboxylic acid compound, (a2) a hydroxyl group-containing unsaturated compound, and (a3) other unsaturated compound in the presence of a radical polymerization initiator in a suitable solvent. It is produced by polymerization.

The solvent used in the above polymerization is, for example, an alcohol such as methanol, ethanol, n-propanol or isopropanol; an ether such as tetrahydrofuran or dioxane; Ethylene glycol alkyl ether such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ester Ethylene glycol alkyl ether acetate such as ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate; ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionic acid Ethylene glycol alkyl ether propionate such as ester, ethylene glycol n-propyl ether propionate, ethylene glycol n-butyl ether propionate; diethylene glycol methyl ether, diethylene glycol ethyl ether, two Diethylene glycol alkyl ether such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether or diethylene glycol methyl ethyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl a propylene glycol alkyl ether such as ether or propylene glycol n-butyl ether; dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, etc. Propylene glycol alkyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc. Alkyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate, etc. propylene glycol alkyl ether propionate; toluene , aromatic hydrocarbons such as xylene; butanone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4methyl-2-pentyl Ketones such as ketones; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, 2-B Methyl oxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, Ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, n-butyl 2-n-propoxypropionate, methyl 2-n-butoxypropionate, 2-n-butyl Ethyl oxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid N-propyl ester, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, 3 - n-butyl n-propoxy propionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-n-butoxy Alkoxy alkanoate such as n-butyl propyl propionate; methyl acetate, ethyl acetate , n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate , 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, 3-hydroxyl n-Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, B Methyl oxyacetate, ethoxy Ethyl acetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-propoxy Other esters such as n-butyl acetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, and n-butyl n-butoxyacetate.

Among these solvents, diethylene glycol alkyl ether, propylene glycol alkyl ether acetate, alkyl alkoxypropionate, and acetate are preferable.

These solvents may be used singly or in combination of two or more.

Further, the radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-bisbisisobutyronitrile (2,2'-Bisisobutyronitrile) and 2,2'-azobis-(2,4- Dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis-(4-cyanovaleric acid) , dimethyl-2,2'-azobis(2-propionic acid methyl ester), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) Nitrogen compound; Benzoyl Peroxide, Lauryl peroxide, tert-Butyl Peroxypivalate, 1,1-bis(tri-butylperoxy)cyclohexane Etc. peroxide; hydrogen peroxide and the like.

Further, when a peroxide is used as a radical polymerization initiator, this may be used in combination with a reducing agent as a redox type initiator.

These radical polymerization initiators can be used singly or in combination of two or more.

The copolymer [α] thus obtained can be used in the production of the [A] polymer in the form of a solution, or can be used in the production of the [A] polymer after being separated from the solution.

The styrene-converted weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [α] by gel permeation chromatography (GPC: Gel Permeation Chromatography) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the weak Mw is less than 2,000, the basic development property and residual film ratio of the obtained film may be lowered, or the shape and heat resistance may be impaired. On the other hand, if it exceeds 100,000, the resolution will be Reduce, or damage the shape of the pattern.

The [A] polymer of the present invention can be obtained by reacting an unsaturated isocyanate compound with a copolymer [α].

The unsaturated isocyanate compound is, for example, 2-(2-isocyanatoethoxy)ethyl acrylate, 2-[2-(2-isocyanatoethoxy)ethoxy]ethyl acrylate, acrylic acid 2 -{2-[2-(2-Isocyanoethoxy)ethoxy]ethoxy}ethyl ester, 2-(2-isocyanatopropoxy)ethyl acrylate, 2-[2-[ Acrylic acid derivative of 2-(2-isocyanatopropoxy)propoxy]ethyl ester; 2-(2-isocyanatoethoxy)ethyl methacrylate, 2-[methacrylic acid] 2-(2-isocyanatoethoxy)ethoxy]ethyl ester, 2-{2-[2-(2-isocyanatoethoxy)ethoxy]ethoxy}methacrylate Ethyl ester, 2-(2-isocyanatopropyloxy)ethyl methacrylate, 2-[2-(2-isocyanatopropoxy)propoxy]ethyl methacrylate Acrylic acid derivative.

Further, a commercially available product of 2-(2-isocyanatoethoxy)ethyl methacrylate is, for example, commercially available under the trade name MOI-EG (manufactured by Showa Denko Co., Ltd. (Japan)).

Among these unsaturated isocyanate compounds, from the viewpoint of reactivity with the copolymer [α], 2-(2-isocyanatoethoxy)acrylate is preferred. Ethyl ester, 2-(2-isocyanatoethoxy)ethyl methacrylate, and the like.

In the production of the [A] polymer, the unsaturated isocyanate compounds may be used singly or in combination of two or more.

In the present invention, the reaction between the copolymer [α] and the unsaturated isocyanate compound may be necessary, for example, to include a catalyst such as dibutyltin laurate (1V) or a polymerization inhibitor such as p-methoxyphenol. In the copolymer [α] solution, the unsaturated isocyanate compound is added dropwise while stirring at room temperature or under heating.

The amount of the unsaturated isocyanate compound used in the production of the [A] polymer is preferably 0.1 to 95 moles of the unsaturated compound having one or more hydroxyl groups in one molecule of the copolymer [α] (a2). The ear % is more preferably 1.0 to 80 mol %, and particularly preferably 5.0 to 75 mol %. If the amount of the unsaturated isocyanate compound used is less than 0.1 mol%, the effect on sensitivity, heat resistance, and elastic properties is small. On the other hand, if it exceeds 95 mol%, the residual reaction is unsaturated. The isocyanate compound tends to have a reduced storage stability of the resulting polymer solution or the radiation sensitive linear resin composition.

[A] The polymer has a carboxylic acid group and/or a carboxylic acid anhydride group, is polymerizable unsaturatedly bonded, and has a moderate solubility to an alkaline developing solution, and is easily used without being used in combination with a special hardening agent. It is hardened by exposure and heating, and contains a sensitive radiation linear resin composition of [A] polymer, which does not cause development residue and film reduction during development, and can easily form spacers of a specific shape.

Sensitive radiation linear resin composition

The radiation sensitive linear resin composition of the present invention comprises [A] polymer [B] a polymerizable unsaturated compound and [C] a radiation-sensitive linear polymerization initiator.

In the present invention, the polymer component may be used in combination with [A] a polymer and other polymers (hereinafter, [A] polymer and other polymers are referred to as "[A] alkaline soluble polymer").

The other polymer is not particularly limited. For example, it is preferably at least one selected from the group consisting of the above (a1) unsaturated carboxylic acid and unsaturated carboxylic anhydride, and from the above (a2) to 1 molecule. A copolymer containing at least one selected from the group consisting of an unsaturated compound of one or more hydroxyl groups and (a3) other unsaturated compounds.

In the present invention, the ratio of the use of the [A] polymer when the [A] polymer and other polymers are used in combination is preferably 50 to 100% by weight, more preferably 80 to 100% by weight based on the total of the two polymers. %. If the use ratio of the [A] polymer is less than 50% by weight, sufficient effects for improvement in sensitivity, heat resistance and elastic properties cannot be obtained.

-[B]Polymerizable unsaturated compounds -

[B] A polymerizable unsaturated compound is formed by producing a polymerized unsaturated compound by exposure to radiation in the presence of a linear polymerization initiator of a radiation.

The [B] polymerizable unsaturated compound is not particularly limited, and is preferably monofunctional, bifunctional or trifunctional or higher (methyl) from the viewpoint of improving copolymerizability and improving the strength of the obtained separator. )Acrylate.

The aforementioned monofunctional (meth) acrylate, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol methyl ether acrylate, Diethylene glycol ethyl ether acrylate, isodecyl acrylate, isodecyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-propene oxime) (2-hydroxypropyl) phthalate, (2-methacryloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxypoly Omega-Carboxy Polycaprolactone Monoacrylate or the like. Commercially available products are, for example, ARONIX M-101, the same M-111, the same M-114, the same M-5300 (above is East Asia Synthetic Co., Ltd. (Japan)); KAYARAD TC-110S, the same TC-120S ( The above is manufactured by Nippon Kayaku Co., Ltd. (manufactured by Japan); VISCOAT 158, the same as 2311 (the above is manufactured by Osaka Organic Chemical Co., Ltd. (Japan)).

Further, the aforementioned bifunctional (meth) acrylate may, for example, be ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethyl ethane Diol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate 1,9-nonanediol dimethacrylate, Bisphenoxyethanol Fluorene Diacrylate, bisphenoxyethanol oxime dimethacrylate, and the like. Commercially available products are, for example, ARONIXM-210, M-240, M-6200 (above, East Asia Synthetic Co., Ltd.); KAYARAD HDDA, HX-220, and R-604 (above Japan) Chemical Co., Ltd. (made in Japan); VISCOAT 260, 312, 335HP (above is Osaka Organic Chemical Co., Ltd. (Japan)); Light-Acrylate 1,9-NDA (Kyoeisha Co., Ltd. (Japan) )Wait.

Further, the above-mentioned trifunctional or higher (meth) acrylate has, for example, three ( Hydroxymethyl)ethane triacrylate, tris(hydroxymethyl)ethane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, neopentyl Tetraol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, triacrylic acid Ester, tris(2-propenyloxyethyl)phosphate, tris(2-methylpropenyloxyethyl)phosphate; 9-functional or higher (meth)acrylate, for example, having a linear polyolefin a compound having two or more isocyanato groups and having one or more hydroxyl groups in the molecule, and having three or five propylene oxy groups and/or methyl groups in the molecule A polyfunctional polyurethane acrylate compound obtained by reacting a compound of a propylene oxy group.

A commercial product of a trifunctional or higher (meth) acrylate, for example, a trade name of ARONIX M-309, the same M-400, a same M-405, a same M-450, the same M-7100, the same M-8030, Same as M-8060, same as TO-1450 (above is made by East Asia Synthetic Co., Ltd. (Japan)); KAYARAD TMPTA, same DPHA, same DPCA-20, same DPCA-30, same DPCA-60, same DPCA-120, (above) It is manufactured by Nippon Kayaku Co., Ltd. (Japan); VISCOAT 295, the same 300, the same 360, the same GPT, the same 3PA, the same 400 (above is Osaka Organic Chemical Co., Ltd. (Japan)); in addition, it contains polyfunctional polyamino Commercially available products of the formic acid acrylate-based compound are, for example, New Frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.).

These monofunctional, bifunctional or trifunctional or higher (meth) acrylates More preferably, it is a trifunctional or higher (meth) acrylate, especially tris (hydroxymethyl) ethane triacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol Acrylate, dipentaerythritol hexaacrylate, or a commercially available product containing a polyfunctional polyurethane acrylate compound is more preferable.

The monofunctional, bifunctional or trifunctional or higher functional (meth) acrylate may be used singly or in combination of two or more.

In the sensitive radiation linear resin composition of the present invention, the amount of the [B] polymerizable unsaturated compound is preferably from 40 to 250 parts by weight, more preferably from 60 to 250 parts by weight, based on 100 parts by weight of the [A] alkali-soluble polymer. ~180 weights. When the amount of the [B] polymerizable unsaturated compound is less than 40 parts by weight, there is a fear that development remains during development. On the other hand, if it exceeds 250 parts by weight, the resulting separator is adhered. There is a tendency to decrease.

-[C]-sensitive radiation linear polymerization initiator

[C] a sensitive radiation linear polymerization initiator formed by a component capable of producing an active material which can be exposed by radiation of visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like [B The polymerizable unsaturated compound starts to polymerize.

The [C] radiation-sensitive linear polymerization initiator is, for example, an O-Acyloxime-based compound, an Acetophenone-based compound, a biimidazole-based compound, a Benzoin-based compound, and a diphenylene group. A ketone compound, an α-diketone compound, a polynuclear benzoquinone compound, a xanthone compound, a phosphine compound, or a triazine. A compound or the like.

The O-lanthanide compound is, for example, preferably an O-staining type polymerization initiator of the 9.H.-Carbazole system. For example, 1-[9-ethyl-6-benzoguanidine-9.H.-oxazol-3-yl]-nonane-1,2-decane-2-stain-O-acetate, 1- [9-ethyl-6-benzamide-9.H.-oxazol-3-yl]-pentane-1,2-pentane-2-soil-O-acetate; 1-[9-B -6-benzhydryl-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetate; ethyl ketone-1-[9-ethyl-6-(2- Methyl benzamidine)-9H-carbazol-3-yl]-1-(O-ethylidene); ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2) , 2, dimethyl-1,3-dioxolan) methoxybenzimid]-9.H.-carbazol-3-yl]-1-(O-ethylidene); 1-[ 9-ethyl-6-(1,3,5-trimethylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one-stain-O-benzoate; -[9-butyl-6-(2-ethylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate; 1-[9 -ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzhydrazide)-9.H.-carbazol-3-yl]-ethane-1-one stain-O- Benzoic acid ester, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylammonium)-9.H.-oxazol-3-yl]-ethane-1- Ketooxime-O-benzoate and the like.

Among these O-staining compounds, particularly preferred is ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydrazin)-9H-indazol-3-yl]-1-(O-B醯圬), ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolan)methoxybenzyl hydrazine] -9.H.-carbazol-3-yl]-1-(O-ethyl smear). These O-quinone compounds can be used singly or in combination of two or more. In the present invention, by using an O-staining compound, a spacer having sufficient sensitivity and adhesion can be obtained even at an exposure amount of 1,000 J/m ² or less.

Examples of the acetophenone-based compound include an α-hydroxyketone compound and an α-amine ketone compound.

The aforementioned α-hydroxyketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane 1-ketone, 4-(2-hydroxymethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, etc., and the above α-amine ketone compound, For example, 2-methyl-1-(4-methylsepenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine) Phenyl)-butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butane -1-ketone and the like. Examples of the compound other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and the like.

Among these acetophenone-based compounds, 2-methyl-1-(4-methylsexyl)-2-morpholinylpropan-1-one and 2-dimethylamino-2-one are particularly preferred. 4-Methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.

In the present invention, sensitivity, spacer shape or compressive strength can be further improved by using an acetophenone-based compound in combination.

Further, the above bisimidazole compound is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2' -biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-bisimidazole, 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2,4, 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2 '-Diimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, and the like.

Among these bisimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2' is preferred. - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, etc., especially 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-bisimidazole.

In the present invention, sensitivity, resolution or adhesion can be further improved by using a bisimidazole compound in combination.

Further, when a bisimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamine group (hereinafter referred to as "amine based sensitizer") may be added in order to increase the sensitivity.

The amine-based sensitizers are, for example, n-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, P-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like.

Among these amine-based sensitizers, 4,4'-bis(diethylamino)benzophenone is particularly preferred.

These amine-based sensitizers can be used singly or in combination of two or more.

Further, when a bisimidazole compound and an amine based sensitizer are used in combination, a thiol compound may be added as a hydrogen supply compound. Bisimidazole compound It is sensitized by the above-mentioned amine-based sensitizer to be cleaved, and an imidazole radical is generated, but most of them do not exhibit a high polymerization initiation energy in this state, so that the shape of the obtained spacer is formed as Less ideal anti-cone shape. However, when a diimidazole-based compound and an amine-based sensitizer coexist, by adding a thiol-based compound, a hydrogen radical can be supplied from the thiol-based compound to the imidazole radical, and as a result, the imidazole radical can be converted into Neutral imidazole, and produces a component having a sulfur radical having a higher polymerization initiation energy, whereby the shape of the spacer is formed into a desired smooth shape.

The aforementioned thiol-based compound, for example, 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio-5-methoxybenzothiazole An aromatic compound such as 2-hydrothio-5-methoxybenzimidazole; 3-hydrothiopropionic acid, methyl 3-hydrothiopropionate, ethyl 3-hydrothiopropionate, An aliphatic monothiol such as octyl 3-hydrothiopropionate; 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetrakis(hydrothioacetate), neopentyl An aliphatic thiol having two or more functional groups such as an alcohol tetrakis(3-hydrothiopropionic acid) ester.

Among these thiol compounds, 2-hydrothiobenzothiazole is particularly preferred.

Further, when the bisimidazole compound and the amine based sensitizer are used in combination, the amount of the amine based sensitizer added is preferably from 0.1 to 150 parts by weight, more preferably from 1 to 150 parts by weight, based on 100 parts by weight of the bisimidazole compound. 125 weight parts. When the amount of the amine-based sensitizer added is less than 0.1 part by weight, the effect of improving the sensitivity, the resolution, or the adhesion tends to be lowered. On the other hand, if it exceeds 150 parts by weight, the shape of the obtained spacer is obtained. There is a tendency to damage.

Further, when a bisimidazole compound and an amine based sensitizer are used in combination, sulfur is used. The amount of the alcohol-based compound to be added is preferably from 0.1 to 100 parts by weight, more preferably from 1 to 75 parts by weight, per 100 parts by weight of the bisimidazole compound. When the amount of the thiol-based compound added is less than 0.1 part by weight, the effect of improving the shape of the separator is lowered, and the film is likely to be degraded. On the other hand, if it exceeds 100 parts by weight, the shape of the obtained spacer is affected. The tendency to lose.

The above-mentioned radiation radiation linear polymerization initiators may be used singly or in combination of two or more.

In the sensitive radiation linear resin composition of the present invention, the ratio of use of the [C] radiation-sensitive linear polymerization initiator is more preferably 100 parts by weight of the [A] alkaline soluble polymer, more preferably 1 to 50 parts by weight. It is 3~40 weights.

-additive-

In the sensitive radiation linear resin composition of the present invention, in addition to the above-mentioned components, a surfactant, a secondary auxiliary agent, a storage stabilizer, and heat resistance may be added as necessary within a range not impairing the desired effects of the present invention. Additives such as lifting agents.

The surfactant is a component having an effect of improving coatability, and is preferably a fluorine-based surfactant and an anthrone-based surfactant.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkenyl group in at least one of a terminal, a main chain and a side chain. The specific example is 1,1,2,2-tetrafluorooctyl. (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2, tetrafluoro-n-octyl (n-hexyl)ether, octyl glycol di(1,1,2,2- Tetrafluoro-n-butyl)ether, hexanediol (1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octylpropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl Ether, propylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl)ether, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2, 2,8,8,9,9,10,10-ten Fluorated n-dodecane, sodium perfluoro-n-dodecylsulfonate, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, diglycerin Alkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl trimethylglycine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxylate, fluorine Alkyl esters and the like.

Further, as a commercial product of a fluorine-based surfactant, for example, the product name is BM-1000, the same -1100 (above is BM CHEMIE); Megaface F142D, the same F172, the same F173, the same F183, the same F178, the same F191 F471, the same as F476 (the above is manufactured by Dainippon Ink Chemical Co., Ltd. (Japan)); Fluorad FC 170C, FC-171, FC-430, and FC-431 (above Sumitomo 3M Co., Ltd. (Japan) System); Surfflon S-112, with S-113, with S-131, with S-141, with S-145, with S-382, with SC-101, with SC-102, with SC-103, with SC -104, the same SC105, the same SC-106 (above is Asahi Glass Co., Ltd. (Japan)); F-TopEF301, the same EF303, the same EF352 (the above is the new Akita Chemical Co., Ltd. (Japan)); Ftergent FT-100, Same as FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, and FT-400S ( The above is manufactured by Neos (Japan) Co., Ltd., and the like.

The above-mentioned anthrone-based surfactant is commercially available, for example, as Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ. -6032, with SF-8428, with DC-57, with DC-190 (above is Toray Dow Corning Silicone Co., Ltd. ( Japan)); TSF-4440, -4,300, -4,445, -4,446, -4,460, and -4,452 (the above is manufactured by GE Toshiba Silicone Co., Ltd. (Japan)).

Further, examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether; a polyoxyethylene aromatic ether such as polyoxyethylene n-phenylene ether; a nonionic interface such as polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate The active agent or the commercial product is, for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd. (Japan); Polyflow No. 57, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants can be used singly or in combination of two or more.

The amount of the surfactant to be added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the [A] alkali-soluble polymer. When the compounding amount of the surfactant exceeds 5 parts by weight, the film tends to be rough at the time of coating.

The above-mentioned secondary auxiliary agent is a component having an effect of further improving the adhesion between the separator and the substrate, and is preferably a functional decane coupling agent.

The functional decane coupling agent may, for example, be a compound having a reactive functional group such as a carboxyl group, a methacryl group, a vinyl group, an isocyanate group or an epoxy group, and specifically, for example, a trimethoxynonylbenzene group Formate, γ-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, γ-isocyanatopropyltriethoxydecane, γ -glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)B Trimethoxy decane and the like.

These adjunct agents may be used singly or in combination of two or more.

The amount of the auxiliary agent to be added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the [A] alkali-soluble polymer. When the amount of the auxiliary agent is more than 20 parts by weight, the development of the developer tends to be likely to occur.

The storage stabilizer is, for example, sulfur, benzoquinone, hydroquinone, polyoxy compound, amine, nitronitroso compound, etc., specifically, for example, 4-methoxyphenol, N-nitroso- N-phenylhydroxylamine aluminum and the like.

These storage stabilizers can be used singly or in combination of two or more.

The amount of the stabilizer to be added is preferably 3% by weight or less, more preferably 0.001 to 0.5 parts by weight, based on 100 parts by weight of the [A] alkali-soluble polymer. If the amount of the stabilizer to be added exceeds 3 parts by weight, there is a fear that the sensitivity is lowered to impair the shape of the pattern.

Examples of the heat resistance improving agent include N-(Alkoxymethyl)Glycoluril compounds, N-(alkoxymethyl)melamine compounds, and the like.

The aforementioned N-(alkoxymethyl) glycoluril compound, for example, N, N, N', N'-tetrakis(methoxymethyl) glycoluril, N, N, N', N'-tetra (B Oxymethyl)glycoluril, N,N,N',N'-tetrakis(n-propoxymethyl)glycoluril, N,N,N',N'-tetrakis(isopropoxymethyl)gan Urea, N, N, N', N'-tetrakis (n-butoxymethyl) glycoluril, N, N, N', N'-tetrakis (tertiary butoxymethyl) glycoluril and the like.

Among these N-(alkoxymethyl)glycoluric compounds, N,N,N',N'-tetrakis(methoxymethyl)glycolil is preferred.

Further, the aforementioned N-(alkoxymethyl)melamine compound is, for example, N,N,N',N',N",N"-hexa(methoxymethyl)melamine, N,N,N', N',N",N"-hexa(ethoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-propoxymethyl)melamine, N,N, N', N', N", N"-hexa(isopropoxymethyl) melamine, N, N, N', N', N", N"-hexa(n-butoxymethyl) melamine, N, N, N', N', N", N"-hexa(tris-butoxymethyl) melamine and the like.

Among these N-(alkoxymethyl)melamine compounds, N,N,N',N',N",N"-hexa(methoxymethyl)melamine is particularly preferred, and commercial products thereof are commercially available, for example. The name is Nikalac N-2702, the same as MW-30M (the above is manufactured by Sanwa Chemical Co., Ltd.).

The heat-resistant enhancer may be used singly or in combination of two or more.

The amount of the heat-resistant improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the [A] alkaline-soluble polymer. When the blending amount of the heat-resistant enhancer exceeds 30 parts by weight, the storage stability of the radiation-sensitive linear resin composition tends to be lowered.

The sensitive radiation linear resin composition of the present invention is preferably used as a composition solution obtained by dissolving in a suitable solvent. The solvent is a one which can uniformly dissolve the components constituting the linear radiation-sensitive resin composition, and does not react with each component and has a moderate volatility, and the solubility of each component and the reactivity of each component and coating From the viewpoint of easiness of film formation, it is preferred to be an alcohol, a monoalkyl glycol ether acetate, a monoalkyl diethylene glycol ether acetate, a diethylene glycol alkyl ether, a monoalkyl propylene glycol ether. acetic acid

Ester, dipropylene glycol alkyl ether, alkyl alkoxypropionate, acetate, etc., especially preferably benzyl alcohol, 2-phenylethanol, 3-phenyl-propanol, mono-n-butyl glycol ether acetate , monoethyl diethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, monomethyl propylene glycol ether acetate, single B Propylene glycol ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 2-methoxyethyl acetate, and the like.

These solvents may be used singly or in combination of two or more.

In the present invention, a high boiling point solvent can be used together with the above solvent.

The above high boiling point solvent is, for example, N-methylformamide, N,N-dimethylformamide, N-methylbenzamide, N-methylacetamide, N,N-dimethyl Acetamide, N-methylrrolidone, dimethyl sulfoxide, benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl Alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, monophenyl glycol ether acetate, and the like.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Further, the composition solution prepared as described above may be used after filtration using a microporous filter paper having a pore size of 0.5 μm.

The sensitive radiation linear resin composition of the present invention is particularly suitable for use in the formation of a spacer for a liquid crystal display element.

Method of forming spacer

Next, a method of forming the spacer of the present invention using the radiation sensitive linear resin composition of the present invention will be described.

The formation of the spacer of the present invention comprises at least the following steps of the following sequence: (a) a step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate; (b) the coating a step of exposing at least a portion of the film; (c) a step of developing the film after exposure; and a step of heating the film after development.

The steps are described in order below.

- (a) steps -

Forming a transparent conductive film on one surface of the transparent substrate, and coating the radiation-sensitive linear resin composition on the transparent conductive film, preferably coating the composition solution, and then heating (pre-baking) the coated surface to form a film .

The transparent substrate used for forming the spacer is, for example, a glass substrate, a resin substrate, or the like, specifically, a glass substrate such as soda lime glass or alkali-free glass; and polyethylene terephthalate or polybutene pair. A resin substrate formed of a plastic such as phthalate, polyether sulfonate, polycarbonate, or polyamine.

A transparent conductive film provided on one side of a transparent substrate, for example, a NESA film formed of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), formed of indium oxide-tin oxide (Iu ₂ O ₃ -SnO ₂ ) ITO film and the like.

The method of coating the composition solution forms a film of the film of the radiation sensitive linear resin composition of the present invention, for example, (1) coating method, and (2) dry film method.

Examples of the coating method of the composition solution include a spin coating method, a roll coating method, a spin coating method (spin coating method), a slit coating method, a bar coating method, and an inkjet coating method. A suitable method, in particular, a spin coating method or a slit coating method is preferred.

Further, in forming the film of the radiation sensitive linear resin composition of the present invention, when the (2) dry film method is employed, the dry film is preferably formed on the substrate film, preferably on the flexible substrate film. A linear layer of a sensitive radiation formed of the sensitive radiation linear resin composition of the present invention (hereinafter referred to as "photosensitive dry film") is laminated.

The photosensitive dry film is formed by coating the base film with the radiation sensitive linear resin composition of the present invention, preferably after coating the composition solution, followed by drying, thereby laminating the radiation sensitive linear layer. As the base film of the photosensitive dry film, for example, a film of a synthetic resin such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the matrix film is suitably in the range of 15 to 125 μm. The thickness of the photosensitive layer obtained is preferably about 1 to 30 μm.

Further, when the photosensitive dry film is not used, the cover film may be laminated on the photosensitive layer and stored. The cover film must have an appropriate release property which does not peel off when not in use and which is easily peeled off during use. The cover film which satisfies this condition is, for example, a film obtained by coating or sintering an anthrone-based release agent onto a surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, or a polyvinyl chloride film. The thickness of the cover film is preferably about 25 μm.

In addition, the conditions of prebaking are due to the type of each component and the ratio of blending, etc. It varies, for example, at 70 to 120 ° C for about 1 to 15 minutes.

- (B) steps -

At least a portion of the formed film is then exposed. At this time, when a part of the film is exposed, it is generally exposed through a mask having a specific pattern.

For the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used. Preferably, the radiation having a wavelength in the range of 190 to 450 nm is particularly preferably a radiation containing ultraviolet rays of 365 nm.

With respect to the amount of exposure, the intensity of the wavelength of the exposed radiation at 365 nm is measured by an illuminometer (OAI model 356, manufactured by OAIOptical Associates Inc.), preferably 100 to 10,000 J/m ² , more preferably 500. ~1,500Jm ² .

- (c) steps -

Next, the exposed film is developed, whereby unnecessary portions are removed to form a specific pattern.

The developing solution used for development is preferably an alkaline developing solution, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, or ammonia; ethylamine; An aliphatic primary amine such as n-butylamine; an aliphatic secondary amine such as diethylamine or di-n-butylamine; or an aliphatic 3 such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine Grade amine; Pyrrole, Piperidine, n-methyl acridine, n-methyl piperidine (N-Methyl Pyrrolidine), an alicyclic tertiary amine such as 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-decene; An aromatic tertiary amine such as pyridine, collidine, lutidine or quinoline; an alkanolamine such as ethanol dimethylamine, methyldiethanolamine or triethanolamine; hydrogen An aqueous solution of a basic compound such as a tetra-ammonium salt such as tetramethylammonium or tetraethylammonium hydroxide is oxidized.

Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the basic compound.

For the development method, any one of an impregnation method, a dipping method, a spray method, and the like can be used, and the development time is, for example, 10 to 180 seconds.

After development, for example, after washing with water for about 30 to 90 seconds, it is air-dried, for example, with compressed air or compressed nitrogen, thereby forming a specific pattern.

- (D) steps -

Then, for example, by means of a heating device such as a heating plate or a heating furnace, at a specific temperature, for example, 100 to 230 ° C, for a specific time, for example, 5 to 30 minutes in a heating plate, and 30 to 180 minutes in a heating furnace. The pattern is heated (post-baking), whereby a specific pattern can be obtained.

The conventional sensitive radiation linear resin composition used for the formation of the spacer is not subjected to heat treatment at a temperature of 180 to 200 ° C or higher, and the resulting spacer does not exhibit sufficient performance, but the sensitive radiation of the present invention In the linear resin composition, the heating temperature can be set lower than in the related art, and as a result, yellowing or deformation of the resin substrate can be prevented, and the compressive strength, the polishing strength at the time of liquid crystal alignment, and the transparent substrate can be formed. Intimacy And other spacers with better performance.

Liquid crystal display element

The liquid crystal display element of the present invention is provided with the spacer of the present invention formed as described above.

The structure of the liquid crystal display device of the present invention is not particularly limited. For example, as shown in Fig. 1, for example, a color filter layer and a spacer are formed on a transparent substrate, and an alignment film of two layers in which a liquid crystal layer is interposed is provided. The structure of the opposite transparent electrode, the opposite transparent substrate, and the like. Further, as shown in Fig. 1, a protective film may be formed on the polarizing plate or the color filter layer as necessary.

Further, as shown in FIG. 2, a color filter layer and a spacer may be formed on the transparent substrate, and the alignment film and the liquid crystal layer may be opposed to the thin film transistor (TFT: Thin Film Transistor) array. This constitutes a TN-TFT type liquid crystal display element. At this time, a protective film may be formed on the polarizing plate or the color filter layer as necessary.

Example

The embodiments are described in more detail below to illustrate embodiments of the invention. Here, the part and % are based on the weight.

Synthesis Example 1

5 parts of 2,2'-azobisisobutyronitrile and 250 parts of 3-methoxybutyl acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by the addition of 18 parts of methacrylic acid and tricyclomethacrylate [ 5.2.1.0 ^2,6 ] 25 parts of decane-8-yl ester, 5 parts of styrene, 30 parts of 2-hydroxyethyl acrylate, and 22 parts of benzyl methacrylate, and slowly carry out the environment after replacing with nitrogen. The temperature of the solution was raised to 80 ° C while stirring, and the temperature was maintained for 5 hours to carry out polymerization, whereby a copolymer [α-1] solution having a solid concentration of 28.8% was obtained.

The Mw of the obtained copolymer [α-1] solution was measured by GPC (gel permeation chromatography) GPC-101 (trade name, manufactured by Showa Denko Co., Ltd., Japan), and it was 13,000.

Synthesis Example 2

15 parts of 2-(2-isocyanatoethoxy)ethyl methacrylate (trade name: Karenz MOI-EG, manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4-methoxyphenol were added to the above copolymerization. After 100 parts of the [α-1] solution, the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours to carry out a reaction. The reaction between the isocyanato group derived from 2-(2-isocyanatoethoxy)ethyl methacrylate and the hydroxyl group of the copolymer [α-1] can be carried out by IR (infrared absorption) spectroscopy Confirm it. In the respective IR spectra of the solution of the polymer solution [α-1], the reaction after 1 hour of the reaction, and the solution after the reaction at 40 ° C for 1 hour and then at 60 ° C for 2 hours, it was confirmed that 2-(2-acrylic acid) was obtained. The peak of the 2-isocyanate ethoxy)ethyl group near 2,270 cm ^{-1 was} reduced. A [A] polymer solution having a solid concentration of 31.8% was obtained. This [A] polymer was set as the polymer (A-1).

Synthesis Example 3

15 parts of 2-(2-isocyanatoethoxy)ethyl acrylate and 4-methoxybenzene The phenol 0.1 was added to 100 parts of the copolymer [α-1] solution, and the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours to carry out a reaction. The reaction between the isocyanato group derived from 2-(2-isocyanatoethoxy)ethyl acrylate and the hydroxyl group of the copolymer [α-1] is carried out in the same manner as in Synthesis Example 2, and can be carried out by IR ( Infrared absorption) spectra are confirmed. A [A] polymer solution having a solid concentration of 31.5% was obtained. This [A] polymer was set as the polymer (A-2).

Synthesis Example 4

19 parts of 2-[2-(2-isocyanatoethoxy)ethoxy]ethyl methacrylate and 0.1 part of 4-methoxyphenol were added to 100 parts of the copolymer [α-1] solution. The mixture was stirred at 40 ° C for 1 hour and then at 60 ° C for 2 hours to carry out a reaction. The reaction between the isocyanato group derived from 2-[2-(2-isocyanatoethoxy)ethoxy]ethyl methacrylate and the hydroxyl group of the copolymer [α-1], and the synthesis The same as in Example 2, it can be confirmed by IR (infrared absorption) spectrum. A [A] polymer solution having a solid concentration of 32.5% was obtained. This [A] polymer was set as the polymer (A-3).

Synthesis Example 5

12 parts of 3-methacryloxyphenyl isocyanate (trade name: Karenz MOI-PH, manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4-methoxyphenol were added to the above copolymer [α-1] solution. Thereafter, the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours to carry out a reaction. The reaction between the isocyanato group derived from 3-methacryloxyphenyl isocyanate and the hydroxyl group of the copolymer [α-1] is carried out in the same manner as in Synthesis Example 2, and can be carried out by IR (infrared absorption) spectrum. Confirm it. A [A] polymer solution having a solid concentration of 31.0% was obtained. This [A] polymer was set as the polymer (A-4).

Synthesis Example 6

12 parts of methacryloxyethyl isocyanate (product name: Karenz MOI, manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4-methoxyphenol were added to the copolymer [α-1] solution, and then 40 The reaction was carried out by stirring at ° C for 1 hour and then at 60 ° C for 2 hours. The reaction between the isocyanato group derived from methacryloxyethyl isocyanate and the hydroxyl group of the copolymer [α-1] was carried out in the same manner as in Synthesis Example 2, and was confirmed by IR (infrared absorption) spectrum. A [A] polymer solution having a solid concentration of 31.2% was obtained. This [A] polymer was set as the polymer (A-5).

Synthesis Example 7

Add 2 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methyl ethyl ether to a flask equipped with a cooling tube and a stirrer, followed by methylation 18 parts of acrylic acid, 25 parts of tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, 5 parts of styrene, 5 parts of butadiene, 10 parts of glycidyl methacrylate, methacrylic acid 25 parts of 2-hydroxyethyl ester and 12 parts of tetrahydrofuran-2-yl methacrylate, and after replacing the environment with nitrogen gas, the temperature of the solution was raised to 70 ° C while stirring slowly, and the temperature was maintained for 5 hours. Polymerization, whereby a copolymer [α-2] solution having a solid concentration of 28.3% was obtained.

For the obtained copolymer [α-2] solution, GPC (gel permeation chromatography) was used. GPC-101 (product name, manufactured by Showa Denko Co., Ltd., Japan) was measured for Mw and found to be 9,000.

Synthesis Example 8

15 parts of 2-(2-isocyanatoethoxy)ethyl methacrylate and 0.1 part of 4-methoxyphenol were added to 100 parts of the copolymer [α-2] solution, and stirred at 40 ° C for 1 hour. The reaction was further carried out by stirring at 60 ° C for 2 hours, whereby a [A] polymer solution having a solid concentration of 31.2% was obtained. This [A] polymer was set as the polymer (A-6).

Synthesis Example 9

5 parts of 2,2'-azobisisobutyronitrile and 250 parts of 3-methoxybutyl acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by the addition of 18 parts of methacrylic acid and tricyclomethacrylate [ ^5.2.1.0 2'6] decane-8-yl ester 25, styrene-5, 5-butadiene, methacrylic acid, 2- (6-hydroxyhexyl acyl) ethyl acrylate (trade name PLACCEL FM1D ( 25 parts of Daicel Chemical Industries Co., Ltd. (made in Japan) and 22 parts of tetrahydrofuran-2-yl methacrylate. After replacing the environment with nitrogen gas, the temperature of the solution was raised to 80 ° C while slowly stirring. The polymerization was carried out at a temperature of 5 hours, whereby a copolymer [?-3] solution having a solid concentration of 29.0% was obtained.

The Mw of the obtained copolymer [α-3] solution was measured by GPC (gel permeation chromatography) GPC-101 (trade name, manufactured by Showa Denko Co., Ltd., Japan), and it was 18,000.

Synthesis Example 10

15 parts of 2-(2-isocyanatoethoxy)ethyl methacrylate and 0.1 part of 4-methoxyphenol were added to the copolymer [α-3] solution, and then stirred at 40 ° C for 1 hour, and then The reaction was carried out by stirring at 60 ° C for 2 hours, whereby a [A] polymer solution having a solid concentration of 31.0% was obtained. This [A] polymer was set as the polymer (A-7).

Synthesis Example 11

12 parts of methacryloxyethyl isocyanate and 0.1 part of 4-methoxyphenol were added to the copolymer [α-3] solution, and the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours to carry out a reaction. Thereby, a [A] polymer solution having a solid concentration of 31.0% can be obtained. This [A] polymer was set as the polymer (A-8).

Synthesis Example 12

2 parts of 2,2'-azobisisobutyl phthalate and 200 parts of 3-methoxybutyl acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by the addition of 18 parts of methacrylic acid and tricyclomethacrylate [ 5.2.1.0 ^2'6 ] 25 parts of decane-8-yl ester, 5 parts of styrene, 30 parts of 2-hydroxyethyl methacrylate and 22 parts of benzyl methacrylate, and slowly replaced the environment with nitrogen. The temperature of the solution was raised to 80 ° C while stirring, and the temperature was maintained for 6 hours to carry out polymerization, whereby a copolymer [α-4] solution having a solid concentration of 33.5% was obtained.

GPC (gel permeation chromatography) GPC-101 (trade name, manufactured by Showa Denko Co., Ltd.) was used for the obtained copolymer [α-4] solution. The measurement was carried out by Mw, and the result was 30,000.

Synthesis Example 13

15 parts of 2-(2-isocyanatoethoxy)ethyl methacrylate (trade name: Karenz MOI-EG, manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4-methoxyphenol were added to the above copolymerization. After the solution of [α-4], the mixture was stirred at 40 ° C for 1 hour and then at 60 ° C for 2 hours to carry out a reaction. A [A] polymer solution having a solid concentration of 36.0% was obtained. This [A] polymer was set as the polymer (A-9).

Synthesis Example 14

12 parts of 3-methacryloxyphenyl isocyanate (trade name: Karenz MOI-PH, manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4-methoxyphenol were added to the copolymer [α-4] solution. Thereafter, the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours to carry out a reaction. A [A] polymer solution having a solid concentration of 35.0% was obtained. This [A] polymer was set as the polymer (A-10).

Synthesis Example 15

12 parts of methacryloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko Co., Ltd.) and 0.1 part of 4-methoxyphenol were added to the copolymer [α-4] solution, and then 40 The reaction was carried out by stirring at ° C for 1 hour and then at 60 ° C for 2 hours. A [A] polymer solution having a solid concentration of 35.0% was obtained. This [A] polymer was set as the polymer (A-11).

Examples 1 to 14 and Comparative Examples 1 to 7 Modulation of composition solution

The component [A] was obtained by using 100 parts of the [A] polymer solution obtained in Synthesis Example 2 as the polymer (A-1) and the component [B], using dipentaerythritol hexaacrylate (trade name KAYARAD). DPHA (manufactured by Nippon Kayaku Co., Ltd.), part 100, [C], using ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-carbazole -3-yl]-1-(O-ethyl smear) (trade name: Irgacure OXE02, manufactured by Chiba Specialty Chemicals Co., Ltd. (Japan)), 5,2,2'-bis(2-chlorophenyl)-4, 5',5,5'-tetraphenyl-1,2'-bisimidazole 5, 4,4'-bis(diethylamino)benzophenone 5, and 2-hydrothiobenzophenone In the case of 2.5 parts of thiazole, 5 parts of γ-glycidoxypropyltrimethoxy decane were used as an auxiliary agent, and 0.5 part of FTX-218 (product name, manufactured by Neos (Japan)) was used as a surfactant, and it was preserved. In the stabilizer, 0.5 parts of 4-methoxyphenol was used and mixed, and the solid content was 30%, and it was dissolved in monoethyl propylene glycol ether acetate, and then filtered using a microporous filter paper having a pore diameter of 0.5 μm. The composition solution (S-1) was prepared. The first watch shows the composition of (S-1).

In the first table, the components other than the polymer are as follows.

[B] ingredient

B-1: dipentaerythritol hexaacrylate (trade name KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.))

B-2: City containing polyfunctional polyurethane acrylate compounds Sales item (product name KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.))

B-3: Pentaerythritol tetraacrylate (trade name: ARONIX M-450, manufactured by Toagosei Co., Ltd. (Japan))

B-4: ω-carboxypolycaprolactone polyol monoacrylate (trade name: ARONIX M-5300, manufactured by Toagosei Co., Ltd. (Japan))

B-5: 1,9-nonanediol diacrylate (trade name: Light-Acrylate 1, 9-NDA, Kyoeisha Co., Ltd. (Japan))

[C] component

C-1: Ethyl-1-(9-ethyl-6-(2-methylbenzhydrazin)-9H-indazol-3-yl]-1-(O-ethylidene) (trade name Irgacure) OXE02, manufactured by Chiba Specialty Chemicals Co., Ltd. (Japan)

C-2: ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolan)methoxybenzyl hydrazide] -9.H.-carbazol-3-yl]-1-(O-ethyl smear) (manufactured by ADEKA, N-1919)

C-3: 2-methyl-1-(4-methylsepenyl)-2-morpholinylpropan-1-one (trade name: Irgacure 907, manufactured by Chiba Specialty Chemicals Co., Ltd. (Japan))

C-4: 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (trade name Irgacure) 379, Chiba Specialty Chemicals Co., Ltd. (made in Japan)

C-5: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole

C-6: 4,4'-bis(diethylamino)benzophenone

C-7: 2-Hydroxythiobenzothiazole

[D] component

D-1: Polyfunctional phenolic epoxy resin (trade name, manufactured by Japan Epoxy Resin Co., Ltd., Japan, Epicoat 152)

In Examples 2 to 14 and Comparative Examples 1 to 7, in the same manner as in Example 1, a composition solution was prepared in the composition shown in Table 1. In Example 14 and Comparative Examples 6 to 7, the composition solution was prepared so that the solid content concentration became 50%.

Spacer formation

In Examples 1 to 13 and Comparative Examples 1 to 5, a separator was formed by coating on a substrate using a spin coater. The details are shown below.

The composition solution was applied onto an alkali-free glass substrate using a spin coater, and then prebaked on a hot plate at 100 ° C for 3 minutes to form a film having a film thickness of 3.5 μm.

Then, on the obtained film, exposure was carried out through a mask of a residual pattern of 10 μm square. Thereafter, development was carried out by a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C for 60 seconds, followed by washing with pure water for 1 minute, and further heating in a heating furnace at 230 ° C for 30 minutes, thereby forming a spacer.

Further, in Example 14 and Comparative Examples 6 to 7, a spacer was formed by a dry film method. The details are shown below.

In Example 14, except that the coating film of the liquid composition (S-14) of the radiation sensitive linear resin composition was produced by the dry film method, The patterned films were formed in the same manner as in Examples 1 to 13 and evaluated. Each component is shown in the first table. Further, the peeling of the substrate film is performed before the exposure step. The evaluation results are shown in Table 2.

The production and transfer of the dry film were carried out in the following manner.

The liquid composition (S-14) of the radiation-sensitive linear resin composition was coated on a polyethylene terephthalate (PET) film having a thickness of 38 μm using a spreader, and the coating film was heated at 100 ° C for 5 minutes. A sensitive radiation linear dry film (J-1) having a thickness of 4 μm was produced. Then, on the surface of the glass substrate, the radiation-sensitive linear transfer dry film is laminated in such a manner that the sensitive radiation linear transfer layer abuts, and the sensitive radiation linear dry film (J-1) is transferred by thermocompression bonding to glass substrate.

In Comparative Example 6, except that the liquid composition (s-6) of the radiation sensitive linear resin composition was used in Example 14 to replace the liquid composition (S-14) of the radiation sensitive linear resin composition, After forming a radiation-sensitive linear dry film (J-2) in the same manner as in Example 14, a patterned film was formed and evaluated. Each component is shown in the first table. The evaluation results are shown in Table 2.

In Comparative Example 7, except that the liquid composition (s-7) of the sensitive radiation linear resin composition was used, the same pattern as Comparative Example 6 was used to prepare a radiation-sensitive linear dry film (J-3), and a pattern was formed. The film was evaluated and evaluated. Each component is shown in the first table. The evaluation results are shown in Table 2.

Then carry out various evaluations according to the following methods. The evaluation results are shown in Table 2.

(1) Assessment of sensitivity

In the same manner as the formation of the spacer, when the spacer is formed, the exposure amount after the post-baking residual film ratio (film thickness after post-baking × 100 / film thickness after exposure) is set to 90% or more as the sensitivity. When the exposure amount is 1,000 J/m ² or less, the sensitivity is good.

(2) Assessment of elastic recovery rate

For the obtained separator, a small compression tester (product name: DUH-201, manufactured by Shimadzu Corporation) was used, and the load speed and the slow load speed were both set to 2.6 mM by a flat head of 50 μm in diameter. In the second, the load is applied up to 50 mN, and after the load is held for 5 seconds, the load is released, and the load-deformation amount curve at the time of load and the load-deformation amount curve at the time of the load are produced. At this time, as shown in Fig. 3, the amount of deformation of the load of 50 mN at the time of load is set to L1, and the amount of deformation when the load is released is set to L2, and the elastic recovery rate is calculated by the following equation.

Elastic recovery rate (%) = L2 × 100 / L1

The elastic recovery rate (%) and the deformation amount L1 (μm) are shown in Table 2.

When the deformation amount L1 is 0.2 μm or more, the flexibility can be said to be good.

(3) Evaluation of wear resistance

On the substrate on which the separator was formed, AL3046 (trade name, manufactured by JSR Co., Ltd.) was applied as a liquid crystal alignment agent on a substrate for coating a liquid crystal alignment film, and then dried at 180 ° C for 1 hour to form a liquid crystal alignment agent. A coating film of a liquid crystal alignment agent having a film thickness of 0.05 μm.

Thereafter, on the coating film, a rubbing treatment was carried out under the conditions of a roll rotation number of 500 rpm and a stage moving speed of 1 cm/sec by a brush having a roll of a cloth made of polyamide. It is also evaluated whether or not the peeling of the pattern occurs at this time.

(4) Evaluation of adhesion

Other than the formation of the above-mentioned spacer except for the use of the mask, after the formation of the cured film, in the adhesion test of JIS K-5400 (1980) 8.5, the evaluation was carried out by the checkerboard method of 8.5.2. The number of chessboard objects remaining in the 100 chessboards at this time is shown in the second table.

(5) Evaluation of heat resistance

The film was formed by heating in a heating furnace at 240 ° C for 60 minutes, and the film thickness before and after the additional heating was measured, and the residual film ratio was measured, except that the mask was not used. (The film thickness after additional heating × 100 / film thickness before additional heating) was evaluated.

(6) Evaluation of preservation stability

The sensitive radiation linear resin composition was placed in a constant temperature layer at 40 ° C for one week, and the rate of change of viscosity at this time was measured. When the increase rate of viscosity is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor.

Effect of the invention:

The polymer of the present invention has a reactive unsaturated group in the side chain of the polymer, and is particularly suitable for the constituent component of the linear radiation-sensitive resin composition used in the formation of the spacer for a liquid crystal display element. It is also a constituent material of a radiation sensitive linear resin composition used for forming a protective film for a liquid crystal display element, a linear radiation sensitive resin composition for forming a colored layer, a radiation curable coating material, and a radiation curable adhesive. it works.

The present invention linear radiation-sensitive resin composition system having high sensitivity and high resolution, even at 1,000 J / m ² or ^less, an exposure amount is also sufficient pattern shape, and therefore can be used to form a good linear radiation-sensitive resin The spacer for a liquid crystal display element having good storage stability and excellent barrier softness, abrasion resistance, adhesion to a transparent substrate, and heat resistance.

The liquid crystal display element of the present invention has a spacer which is excellent in various properties such as sensitivity, elastic recovery ratio, flexibility, abrasion resistance, adhesion to a transparent substrate, and heat resistance, and thus can be used for a long time. Shows high reliability.

Fig. 1 is a schematic view for explaining an example of the structure of a liquid crystal display element.

Fig. 2 is a schematic view for explaining another example of the configuration of the liquid crystal display element.

Fig. 3 is a diagram showing an example of a load-deformation amount curve at the time of load and at the time of slow load in the evaluation of the elastic recovery rate.

Claims (8)

A radiation sensitive linear resin composition comprising: [A] a polymer composed of a polymerization unit of a monomer and having a group represented by the following formula (1), the single system containing unsaturated At least one selected from the group consisting of a carboxylic acid and an unsaturated carboxylic anhydride; [B] a polymerizable unsaturated compound; and [C] a radiation-sensitive linear polymerization initiator (In the formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an exoethyl group or a propyl group, n is an integer of 1 to 5, and "*" is a bonding bond). The sensitive radiation linear resin composition of claim 1, wherein the [A] polymer is a compound represented by the following formula (2), and (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid. a polymer obtained by reacting at least one selected from the group consisting of acid anhydrides and (a2) a copolymer obtained by reacting an unsaturated compound having one or more hydroxyl groups in one molecule (In the formula (2), R ¹ , R ² and n are each synonymous with R ¹ , R ² and n of the formula (1). The sensitive radiation linear resin composition of claim 1 or 2 is used for forming a spacer for a liquid crystal display element. A spacer for a liquid crystal display element, which is characterized in that it is formed of a sensitive radiation linear resin composition of the third application of the patent application. A method for forming a spacer for a liquid crystal display device, characterized in that it comprises at least the following steps in the order described below: (a) forming a film of the radiation-sensitive linear resin composition of claim 3 a step on the substrate; (b) a step of exposing at least a portion of the film; (c) a step of developing the film after exposure; and a step of heating the film after development . A liquid crystal display element comprising: a spacer for a liquid crystal display element of claim 4; A polymer comprising a polymerization unit of a monomer and having a group represented by the following formula (1), the single system comprising a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride At least one of the selected ones (In the formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an exoethyl group or a propyl group, n is an integer of 1 to 5, and "*" is a bonding bond). The polymer according to claim 7, wherein the compound represented by the following formula (2) and (a1) are selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. a polymer obtained by reacting at least one type of copolymer with (a2) an unsaturated compound containing one or more hydroxyl groups in one molecule (In the formula (2), R ¹ , R ² and n are each synonymous with R ¹ , R ² and n of the formula (1).