TW200909459A - Polymer having unsaturated side chain, radiation-sensitive resin composition and spacer for liquid crystal display element - Google Patents

Abstract

The present invention provides a sensitive and radiation resin composition with high sensitivity which can acquire abundant spacer shape even if the light exposure is under 1, 000J/m<2>, and which can form a spacer with good rub resistance, sealing performance with a transparent substrate, heat-resistance, flexibility of a spacer, and stability of a composition for a liquid display element, and effective polymer as the component and the like of the composition. The polymer is obtained by a compound shown as the formula reaction with undersaturation carboxylic acid or undersaturation carboxylic acid anhydride and co-polymer with hydroxy unsaturated compound. The sensitive and radiation resin composition comprises the polymer, polymerism unsaturated compound and sensitive and radiation polymerization initiator.; In the formula, R<1> represents hydrogen atom or methyl, R<2> represents vinyl or propenyl, and n represents an integer of 1 to 5.

Description

200909459 IX. Description of the Invention [Technical Field] The present invention relates to a polymer which is highly suitable for forming a spacer of a liquid crystal display element, a radiation sensitive linear resin composition comprising the polymer, and a spacer and the formation method And liquid crystal display elements. [Prior Art] In the liquid crystal display device, in order to maintain the interval between the two substrates, that is, the liquid crystal cell pitch (C e 11 G ap) is constant, conventionally, a space between glass beads and plastic beads having a specific particle diameter is used. Pieces. 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 problem of the contrast reduction is therefore, in order to solve this problem, the method of forming spacers by lithography is 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 has increased in size (for example, 1,50 〇χ 1,800 mm, and even more, 1,870×2, 200 mm) from the viewpoints of large-area liquid crystal display elements and improvement in productivity. ) is progressing rapidly. In the conventional substrate size, since the substrate size is smaller than the mask size, it can be processed by the single exposure method of -4-200909459. However, it is almost impossible to produce light of the same size as the substrate in a large substrate. The cover is not easy to handle in a single exposure. Therefore, as a method of exposure that can correspond to a large substrate, a step exposure method is advocated. However, in the stepwise exposure mode, the exposure is performed in a fraction of the number of substrates, and the time for the alignment and the stepping movement is required for each exposure. Therefore, the processing amount 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 conventional separator, it is difficult to achieve a sufficient spacer shape and film thickness at an exposure amount of 1, 〇〇〇 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. That is, in the peeling of the alignment film, the spacer of the underlayer is preferably not subjected to swelling or dissolution to cause a change in film thickness, 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 height of the spacer. However, in the 〇DF (DeD Drop F i 11 ing: liquid crystal dropping method), the load formed by the weight of the substrate is initially bonded to the atmospheric pressure, and the initial 200909459 is attached to the conventional method. The combined load is small. Therefore, it is important that even if the spacer is pressed with a small load, uniform pressing can show 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 Japanese Laid-Open Patent Publication No. 2000-105456, Japanese Patent Publication No. 2000-1718, No. 2000-A No. 2000-298, No. The property of the separator or the protective film of high sensitivity and chemical resistance is improved. The copolymerizable resin is a photosensitive resin composition and has a (meth) acryloyloxy thiol isophthalic acid. A methacrylate (Meth) acryloyloxy Alkyl Isocyanate is a photopolymerizable functional group which reacts with a copolymerizable resin having a hydroxyl group 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 may be lowered. SUMMARY OF THE INVENTION 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 less than 1,0 0 0/m2, and has good wear-resistant brushability. The adhesion to the transparent substrate, the heat resistance, the flexibility of the spacer, and the storage stability of the composition can form a liquid crystal display -6-200909459. The radiation sensitive linear resin composition showing the spacer for the element is another object of the present invention. A polymer of a resin component which can be used as a resin composition. Another object of the present invention is to provide a liquid crystal display spacer and an image element formed of a resin composition. Another object of the present invention is to provide a method of forming the above. Other objects and advantages of the present invention can be attained by the following objects in accordance with the present invention and preferably by a radiation sensitive linear resin composition (hereinafter referred to as a fat composition) characterized by comprising a unit The single system composed of the following formula (1) contains at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [B] Polymeric unsaturated unsaturated radiation linear polymerization initiation R1 CH2-CC-Ο-(OR2 NH-(wherein R1 is a hydrogen atom or a methyl group, R2 is an integer of 1 to 5, and "*" is a bonding bond). The present invention and the above object of the present invention are superior to the linear radiation display of the above-mentioned sensitive radiation linearly having the sensitivity. The point, first, can be borrowed from the "sensitive radiation linear tree: [A] from the single a polymer of a polyradical group, in the group consisting of: a compound: and [C] -* (1) a C group or a propyl group, a η point, a second, which can be borrowed from the above-mentioned [A] polymer According to the present invention, the above objects and advantages of the present invention, and thirdly, by the aforementioned sensitive radiation The liquid crystal display element formed by the resin composition is obtained by a spacer. According to the present invention, the above objects and advantages of the present invention can be achieved by a method for forming a spacer for a liquid crystal display element. Is a step comprising at least the following steps in the order described below: (a) a step of forming a film of the aforementioned radiation-sensitive linear resin composition on a substrate; (b) a step of exposing at least a portion of the film (c) a step of developing the film after exposure: and (d) a step of heating the film after development. According to the present invention, the above objects and advantages of the present invention, fifth, The present invention has been described in detail with reference to a liquid crystal display device in which a liquid crystal display spacer is used. [Embodiment] The present invention will be described in detail below. Polymer The polymer of the present invention is composed of a polymerization unit of a monomer and has the above-described a group represented by the formula (1) (hereinafter referred to as "[A] polymer"), the single system containing at least 1 selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (These compounds are collectively referred to as "(a 1) unsaturated-8-200909459 carboxylic acid compound"). [A] The polymer can be represented, for example, by the following formula (2) The compound (hereinafter referred to as "unsaturated isocyanate compound")' is obtained by reacting a (al) unsaturated carboxylic acid compound with a copolymer containing one or more hydroxyl groups or an amino group-containing unsaturated compound in one molecule. The preferred [A] polymer is, for example, an unsaturated isocyanate compound represented by the following formula (2), and (al) unsaturated carboxylic acid compound and (a2) having one or more hydroxyl groups in one molecule. A polymer obtained by reacting a copolymer of an unsaturated compound (hereinafter referred to as "copolymer [α]") R1 CH2=C-C-Ο-C2H4-f〇R2 七N=C: Ο :〇(2) (In the formula (2), R1, R2 and η are respectively synonymous with R1, R2 and η of the formula (1)) 〇 constitutes a component of the copolymer [α], and (al) an unsaturated carboxylic acid compound, for example Acrylic acid, methacrylic acid, Crotonic acid, 2-propanol oxyacetate (2-Acryloyloxy) Ethyl Succinate), 2-methylpropenyl ethoxysuccinate, 2-Acryloyloxy Ethyl Hexahydroplithalate, 2-methylpropenyloxyhexahydroorthophenyl Monocarboxylic acid such as ethyl dicarboxylate; maleic acid, fumaric acid, citraconic acid (Citraconic)

Acid), mesaconic acid, itaconic acid, 200909459, etc.; dicarboxylic acid; Among these (a 1) unsaturated carboxylic acid compounds, acrylic acid and methyl groups are preferred in terms of copolymerization reactivity and ease of solubility and availability of the obtained [A] polymer to an alkaline developing solution. Acrylic acid, maleic anhydride, and the like are used in the copolymer [α], and the (a 1) 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 (a 1) unsaturated carboxylic acid compound is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, based on the copolymer [α], and particularly preferably 15 to 30% by weight. If the content of the repeating unit (polymerization unit) derived from the (al) 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-hydroxy decyl acrylate, H-hydroxyindole-ester, Hydroxyalkyl acrylate similar to 1-hydroxylauryl acrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxy methacrylate Amyl ester, 6-hydroxyhexyl methacrylate, 7-hydroxyheptyl methacrylate, 8-hydroxyoctyl methacrylate, methyl propyl-10-200909459 9-hydroxy decyl enoate, methacrylic acid 10- Hydroxydecyl ester, n_undecyl methacrylate, hydroxyalkyl methacrylate like 12-hydroxylauryl methacrylate; 2-(6-hydroxyhexyloxy)ethyl acrylate, acrylic acid 3- (6-hydroxyhexyloxy)propyl ester, 4-(6-hydroxyhexyloxy)butyl acrylate, 5-(6-hydroxyhexyloxy)pentyl acrylate, 6-(6-hydroxyhexyl)acrylate Decyloxy)hexyl ester Acetyl (6-hydroxyhexyloxy)alkyl acrylate; 2-(6-hydroxyhexyloxy)ethyl methacrylate, 3-(6-hydroxyhexyloxy)propyl methacrylate, 4-(6-hydroxyhexyloxy)butyl methacrylate, 5-(6-hydroxyhexyloxy)pentyl methacrylate, 6-(6-hydroxyhexyloxy)hexyl methacrylate a commercially available product of a mixture of (6-hydroxyhexyloxy)alkyl methacrylate; a mixture of (6-hydroxyhexyloxy)alkyl methacrylate and 2-hydroxyethyl methacrylate, for example The trade names are PLACCEL FM1D, 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 Base) propyl ester, 4-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-butyl acrylate, 5-(3-hydroxy-2,2-dimethyl-propenyl acrylate Oxycarbonyloxy)-pentyl vinegar, 6-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-hexyl acrylate-like propionic acid (3-carbyl-2,2) -Dimethyl-propoxyfluorenyloxy)-honey base vinegar, etc. » 2-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-ethyl methacrylate, methyl 3-(3-Hydroxy-2,2-dimethyl-propoxycarbonyloxy-11 - 200909459 )-propyl acrylate, 4-(3-hydroxy-2,2-dimethyl-propyl methacrylate Oxycarbonyloxy)-butyl ester, 5-(3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-pentyl methacrylate, 6-(3-hydroxy-2, methacrylate (3-Hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl methacrylate such as 2-dimethyl-propoxycarbonyloxy)-hexyl ester. A commercially available product of a mixture of (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy)-alkyl (meth)acrylate and 2-hydroxyethyl methacrylate, for example, the trade name is HEMAC1 (manufactured by Daicel Chemical Industries Co., Ltd.). Further, 4-hydroxycyclohexyl acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxyethyl-cyclohexylethyl acrylate, 3-hydroxy-bicycloacrylate [2. 2·]]hept-5-en-2-yl ester' 3-hydroxymethyl-bicycloacrylate [2. 2. 1]hept-5-en-2-ylmethyl ester, 3-hydroxyethyl-bicyclo(2-acrylate) [2. 2·]]hept-5-en-2-ylethyl ester, acrylic acid 8-hydroxy-bicyclo[2. 2. 1]hept-5-en-2-yl ester, 2-hydroxy-octahydro-4,7-methanol-non-5-yl acrylate (eight £:"14 八幻〇12-1^£11'〇 ?{丫-〇ctahydro-4,7-Methano-Indene-5-Yl Ester), acrylic acid 2-methyl-octahydro-4,7-methanol-non-5-yl methyl ester, acrylic acid 2- Hydroxyethyl-octahydro-4,7-methanol-indole-5-ylethyl ester, Acrylic Acid 3-Hydroxy- Adamantane-l-Yl Ester, propylene a hydroxyalkyl acrylate having an alicyclic structure like 3-hydroxymethyl-adamantan-1-ylmethyl ester, 3-hydroxyethyl-adamantane-l-ylethyl acrylate; methacrylic acid 4- Hydroxy-cyclohexyl ester, 4-hydroxymethyl-cyclohexylmethyl methacrylate, 4-hydroxyethyl-cyclohexylethyl methacrylate, 3-hydroxy-bicyclo methacrylate [2. 2. 1]hept-5-en-2-yl ester, 3-hydroxymethyl methacrylate -12- 200909459 base-bicyclo[2. 2. 1] Gn-5-en-2-ylmethyl ester, 3-hydroxyethyl-bicyclomethylic [2. 2. 1]hept-5-ene·2-ylethyl ester, 8-hydroxy-bicyclo methacrylate [2. 2. 1]hept-5-en-2-yl ester, 2-hydroxy-octahydro-4,7-methanol-non-5-yl methacrylate, 2-hydroxymethyl-octahydro-4, methacrylate 7-Methanol·茚-5-ylmethyl ester, 2-hydroxyethyl methacrylate octahydro-4,7-methanol-fluoren-5-ylethyl methacrylate, 3-hydroxy-adamantane methacrylate Ester, hydroxyalkyl methacrylate with alicyclic structure like 3-hydroxymethyl-adamantane-1 -ylmethyl methacrylate and 3-hydroxyethyl-adamantan-1-ylethyl methacrylate Base ester; 1,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3 -dihydroxypropyl acrylate, 3,4-dihydroxybutyl acrylate, 3-[3-( Dihydroxyalkyl acrylate such as 2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropyl ester; 1,2-dihydroxyethyl methacrylate, methacrylic acid 2, 3. Dihydroxypropyl ester, 1,3-dihydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 3-[3-(2,3-dihydroxypropoxy) methacrylate Dihydroxyalkyl methacrylate such as 2-hydroxypropoxy]-2-hydroxypropyl 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-cyclohexylmethyl-13- 200909459 ester, 3, hydroxymethyl-adamantane-1 - Methyl ester, 3-hydroxymethyl-adamantan-1-ylmethyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 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 ratio of the repeating unit (polymerization unit) derived from (a2) the unsaturated compound containing one or more hydroxyl groups in one molecule is preferably from 1 to 50% by weight, more preferably 3, based on the copolymer [α]. ~40% by weight 'especially ideally 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 decrease, and in the copolymer [α ], (a) 1) and an unsaturated compound other than (a2) (hereinafter referred to as "(a3) other unsaturated compound") is a component of a 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, Acrylic 2·甲-14- 200909459 diglycidyl ester, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxy acrylate Acrylic epoxy (cyclo)alkyl ester of ester, 3,4-epoxycyclohexyl acrylate, etc.; glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-cyclomethacrylate Oxybutyl acrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate, etc. Cycloalkyl ester; 〇t-glycidyl methacrylate, α-n-propyl acrylate Other alkyl acrylate epoxies such as water glyceride, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester, α-ethyl acrylate 3,4-epoxycyclohexyl ester (cyclo)alkyl ester; o-ethylbenzyl glycidyl ether, m-ethylbenzyl glycidyl ether, p-glycidyl ether of p-ethylbenzyl glycidyl ether; 3-(methacryloxyl group 3-(Methacryloyloxymethyl)Oxetane, 3-(methyl propyloxymethyl)_3_ethyloxetane, 3-(methacryloxymethyl)- 2-methyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)_ 2 -pentafluoro Oxycyclobutane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methylpropenyloxymethyl)_2,2-difluorooxetane Institute, 3_(methacryloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4·tetrafluoro Oxygen ring, 3_(methylpropyl oxyethyl)oxycyclobutane, 3-(methacryloxyethyl)-3-ethyloxetane, 2 - 3-(Methylpropoxycarbonylethyl)oxetane, 3-(methacryloxyethyl)_2-trifluoromethyloxetane, 3_(methylpropione Oxygen•15- 200909459 base ethyl)-2 -pentafluoroethyloxycyclobutane, 3-(methacryloxyethyl)-2-phenyloxycyclobutane, 2,2-difluoro- 3-(Methethyloxyethyl)oxycyclobutane, 3-(methacryloxyethyl)-2,2,4-trifluorooxocyclobutane, 3-(methylpropene oxime Ethyl acetoacetate having an oxocycloyl group such as oxyethyl)-2,2,4,4-tetrafluorooxocyclobutane; 3-(acryloxymethyl)oxygen Cyclobutane, 3-((acryloxymethyl)-3-ethyloxycyclobutane, 3-(acryloxymethyl)-2-methyloxycyclobutane, 3-(acryloxy) Methyl)-2·trifluoromethyloxycyclobutane, 3-(acryloxymethyl)-2-pentafluoroethyloxycyclobutane, 3-(acryloxymethyl)-2- Phenyloxycyclobutane, 3-(acryloxymethyl)-2,2-difluorooxocyclobutane, 3-(acryloxymethyl)-2,2,4-trifluorooxane Butane, 3-(acryloxymethyl)-2,2,4,4-tetrafluorooxocyclobutane, 3- (Allyloxyethyl)oxycyclobutane, 3·(acryloxyethyl)-3-ethyloxycyclobutane, 2-ethyl-3-(acryloxyethyl)oxy ring Butane, 3-(acryloxyethyl)-2-trifluoromethylcyclobutane, 3-(acryloxyethyl)-2-pentafluoroethyloxycyclobutane, 3-( Propylene methoxyethyl)-2-phenyloxycyclobutane, 2,2·difluoro-3-(acryloxyethyl)oxycyclobutane, 3-(acryloxyethyl)- Acrylate having an oxocyclobutyl group such as 2,2,4-trifluorooxocyclobutane or 3-(acryloxyethyl) 2,2,4,4-tetrafluorooxocyclobutane; Hexyl ester, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5_2. 1_〇2'6]decane-8-yl ester' 2-acrylic acid 2-(tricyclic [5. 2. 1. 02'6] decyl octadecyl ester of decane 8-octyloxy)ethyl ester, IsobornylAcrylate, etc.; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate , methyl-16- 200909459 acrylic tricyclic [5. 2. 1. 02'6] decane-8-yl ester, 2-(tricyclic) methacrylate [5. 2. 1. 02'6] methacrylate alicyclic ester of decane-8-yloxy)ethyl ester, isodecyl methacrylate or the like; aryl or aralkyl ester of acrylic acid such as phenyl acrylate or benzyl acrylate; An aromatic or arylalkyl methacrylate of phenyl methacrylate or benzyl methacrylate; unsaturated of diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Dialkyl dicarboxylate; propylene tetrahydrofuran-2-yl vinegar, tetrahydrofuran-2-yl acrylate, methyl tetrahydrofuran-2-yl acrylate, etc. Acrylate containing 6-membered ring of oxygen-containing heterocyclic ring; tetrahydrofuran-2-yl methacrylate, tetrahydrofuran-2-yl methacrylate, methyltetrahydrofuran-2-yl methacrylate, etc. Oxygen heterocyclic 5-membered ring or oxyalkyl ester of 6-membered ring containing oxygen ring; styrene-butadiene, α-methylstyrene (α-Methyl Styrene), m-toluene, m-methylstyrene, p-methoxystyrene, etc. a vinyl aromatic compound; maleimide, n-phenyl maleimide, n-cyclohexyl maleimide, etc. a conjugated diene compound such as 1,3-butadiene, isoprene or 2,3-dimethyl-1,3-butadiene; Acrylonitrile, A Acrylic nitrile, Acrylic Amide, methacrylamide, vinyl chloride, dichloroethylene, ethyl acetate, and the like. -17- 200909459 Among these (a3) other unsaturated compounds, from the viewpoint of copolymerizability and the solubility of the obtained [A] polymer to an alkaline developing solution, n-butyl methacrylate is preferred. Methyl glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-methyl-3(methyl) propylene methoxymethyl oxygen Cyclobutane, 3-ethyl-3(methyl) propylene methoxymethyloxycyclobutane, 3-(methacryloxymethyl)-3-ethyloxycyclobutane, methacrylic acid Benzyl ester, methacrylic acid tricyclo [5. 2. 1 . 02'6] decane-8-yl ester, 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 1 to 75% by weight, more preferably from 20 to 7 % by weight, particularly preferably from 30 to 65% by weight, based on the copolymer [α]. . If the content of the repeating unit derived from (a3) other unsaturated compound is less than 1% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (2) tends to decrease, and the other In the aspect, if it exceeds 7.5 wt%, the solubility of the polymer in the alkaline developing solution tends to decrease. The copolymer [α], for example, can be used to render an (al) unsaturated carboxylic acid compound, (a2) a trans-unsaturated compound and U3) other unsaturated compound in the presence of a radical polymerization initiator in a suitable solvent. The solvent to be used in the polymerization is produced by polymerization, and examples thereof include alcohols such as methanol 'ethanol' n-propanol and isopropanol; and ethers such as tetrahydrofuran and dioxane (Di〇Xane); 200909459 ethylene glycol alkyl ether, ethylene glycol methyl ether, ethylene glycol n-butyl ether, ethylene glycol alkyl ether, etc.; ethylene glycol methyl ether acetate, ethylene glycol Ethylene glycol alkyl ether acetate such as ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate; ethylene glycol methyl ether propionate, ethylene glycol ethyl ether Ethylene glycol alkyl ether propionate such as acid ester, ethylene glycol n-propyl ether propionate or ethylene glycol n-butyl ether propionate; diethylene glycol methyl ether, diethylene glycol ethyl ether, Diethylene glycol alkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; propylene glycol methyl a propylene glycol alkyl ether such as ether, propylene glycol ethyl ether, propylene glycol n-propyl 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 alkyl ether such as dipropylene glycol methyl ethyl ether; propylene glycol alkyl group such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate Ethyl 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, two An aromatic hydrocarbon such as toluene; a ketone such as butanone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4methyl-2-penta-19-200909459 ketone; 2-methoxypropionic acid Methyl ester, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxyl Ethyl propionate, 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, Ethyl 2-n-butoxypropionate, 2-n-butane N-propyl oxypropionate, 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, n-propyl 3-ethoxypropionate, 3-ethoxypropionic acid N-butyl ester, 3-n-propoxy propionate methyl vinegar, 3-n-propoxy propionate ethyl ester, 3-n-propoxy propionate n-propyl ester, 3-n-propoxy propionate n-butyl ester, Alkoxy groups such as methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate Alkyl propionate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methyl acetate Oxybutyl butyl ester, 3-methoxybutyl acetate, 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, methyl lactate, lactic acid Ester, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-hydroxypropionate, 3-hydroxypropane Ethyl acetate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, A N-propyl oxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethoxy-20-200909459 ethyl acetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, positive Methyl propoxyacetate, ethyl n-propoxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, positive Other esters such as n-propyl 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 aforementioned radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile (2,2'-Bisisobutyronitrile) and 2,2'-azobis-(2,4- Dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis-(4-cyanovaleric acid) , azo such as dimethyl-2,2'-azobis(methyl 2-propionate) or 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) Compound; Benzoyl Peroxide, Laurel Oxide, Tert-Butyl Peroxypivalate, 1,1-Bis(tert-butylperoxy)cyclohexane Etc. peroxide; hydrogen peroxide and the like. Further, when a peroxide is used as a radical polymerization initiator, this may be used as a redox type initiator as a redox initiator. These radical polymerization initiators may 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 [Α] a polymer after being separated from the solution. -21 - 200909459 The styrene-converted weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [α] is preferably 2,000 to 10,000,000. It is 5,000~5 0,000. When the weak M w is less than 2,0 0 0, the alkali imaging property and residual film ratio of the obtained film may be lowered, or the shape shape and heat resistance may be impaired, and if it exceeds 1 00,000, the resolution will be reduced, or the shape of the pattern will be detrimental. The [Α] 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-Isocyanopropoxy)ethyl acrylate, 2-[2- Acrylic acid derivative of (2-isocyanatopropoxy)propoxy]ethyl ester; 2-(2-isocyanatoethoxy)ethyl methacrylate, 2-[2-( 2-isocyanatoethoxy)ethoxy]ethyl ester, 2-{2-[2-(2-isocyanatoethoxy)ethoxy]ethoxy}ethyl methacrylate, Derivative of methacrylic acid such as 2-(2-isocyanatopropoxy)ethyl methacrylate or 2-[2-(2-isocyanatopropoxy)propoxy]ethyl methacrylate Things. 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)-22-200909459 ethyl acrylate or methacrylic acid 2 is preferred. -(2-Isocyanatoethoxy)ethyl ester or the like. In the production of the [A] polymer, the unsaturated isocyanate compound 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 dibutyl dilaurate (IV) 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 [Α] polymer is preferably 0. The unsaturated compound having one or more hydroxyl groups in one molecule of the copolymer [α] is preferably 0. 1 to 95% by mole, more preferably 1. 0 to 80% of the mole, especially ideally 5. 0 to 75 mol%. If the amount of unsaturated isocyanate compound is less than 0. 1% by mole, the effect on sensitivity, heat resistance improvement and elastic property improvement is small. On the other hand, if it exceeds 95% by mole, unreacted unsaturated isocyanate compound remains, and the obtained polymer solution is sensitive. The storage stability of the radiation linear resin composition tends to decrease. [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 easy to borrow even if it is not used 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 sensitive radiation linear resin composition of the present invention comprises [A] polymer -23-200909459, [B] a polymerizable unsaturated compound and [c] a radiation-sensitive linear polymerization initiator. In the present invention, the polymer component may also be a combination of [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 (al) 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 is preferably 50 to 100% by weight, more preferably 80 to 100, based on the total of the two polymers. weight%. If the proportion of the [A] polymer used is less than 50% by weight, sufficient effects for improvement in sensitivity, heat resistance and elastic properties cannot be obtained. _[B] Polymerizable unsaturated compound - [B] A polymerizable unsaturated compound is formed by generating 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 a 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 '-24- 200909459 diethylene glycol ethyl Ether acrylate, isodecyl acrylate, isodecyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2· propylene methoxyethyl) (2 -hydroxypropyl)phthalate, (2-methacryloxyethyl)(2-hydroxypropyl)phthalate, ω-carboxypolycaprolactone polyol monopropene Oleate (ω-Carboxy Polycaprolactone Monoacrylate) and 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 Nippon Chemical Co., Ltd.); VISCOAT 158, and 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 dimethyl propylene vinegar, Bisphenoxyethanol Fluorene Diacrylate, bisphenoxyethanol oxime dimethacrylate, and the like. Commercially available products are, for example, ARONIX M-210, M-240, M-6200 (above, East Asia Synthetic Co., Ltd.); KAYARAD HDDA, HX-220, and R-604 (above) Nippon Kayaku 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) System) and so on. Further, as the above-mentioned trifunctional or higher (meth) acrylate, for example, there are three (-25-200909459 methyl) ethane triacrylate, tris(hydroxymethyl)ethane trimethacrylate, and neopentyl alcohol triacrylate. Ester, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentapropyl acid ester, dipentaerythritol pentamethacrylic acid Ester, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, triacrylate, tris(2-propenyloxyethyl) phosphate, tris(2-methylpropenyloxy) Ethyl) phosphate; a 9-functional or higher (meth) acrylate, for example, a compound having a linear polyolefin group and an alicyclic structure and having two or more isocyanato groups and having 1 in the molecule A polyfunctional polyurethane acrylate-based compound obtained by reacting three or more compounds having four or five acryloxy groups and/or methacryloxy groups. A commercially available product of a trifunctional or higher (meth) acrylate, for example, a trade name of ARONIX M-3 09, the same M-400, the same M-405, the same M-450, the same M-7100, the same M-8030 , with M-8060, with TO-1450 (above is made by East Asia Synthetic Co., Ltd. (Japan)); KAYARAD ΤΜΡΤΑ, with DPHA, with DPCA-20, with DPCA-30, with DPCA-60, with DPCA-120, ( The above is manufactured by Nippon Kayaku Co., Ltd. (曰本); VISCOAT 295, the same as 00, the same as 3, 60, the same as GPT, the same as 3, the same 400 (the above is made by Osaka Organic Chemical Co., Ltd. (Japan)); Commercial product of a polyfunctional polyurethane acrylate compound, for example, New Frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (Japan Chemicals Co., Ltd. (Japan) System) and so on. These monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates are more preferably trifunctional or higher (meth)acrylic acid vinegar, especially tris(meth) ethane triacrylate, in -26-200909459, Neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate' or a commercial product containing a polyfunctional polyurethane acrylate compound More ideal. The above-mentioned monofunctional, bifunctional or trifunctional or higher (meth)acrylates 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 10 to 50 parts by weight, more preferably 40 to 25 parts by weight, of the [A] alkaline soluble polymer. Ideally 60 to 180 weight parts. 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] sensitive radiation linear polymerization initiator, formed by components capable of producing active substances, which can be obtained by visible light, ultraviolet light, far ultraviolet rays, charged particle lines The exposure of the radiation of X-rays or the like causes the [B] polymerizable unsaturated compound to start polymerization. The [C] sensitive light ray polymerization initiator is, for example, a 〇_Acyloxime-based compound, an acetophenone-based compound, a dimethoprim-based compound, a Benzoin-based compound, and a second An benzophenone-based compound, an α-diketone-based compound, a polynuclear benzoquinone-based compound, a xanthone-based compound, a phosphine-based compound, and a triazjne -27-200909459-based compound. 〇 - lanthanide compounds, for example, preferably 9 .  Oh. -carbazole (9.  Oh. -Carbazole) is a 0-indole type polymerization initiator. For example, there is 1-[9-ethyl-6_benzamide- 9. Hey. -oxazol-3-yl]-nonane-1,2-decane-2-indole-0-acetate, 1-[9-ethyl-6-benzamide- 9. Hey. -oxazol-3-yl]-pentane-1,2-pentane-2-indole-0-acetate; 1-[9-ethyl-6-benzamide- 9. Hey. -oxazol-3-yl]-octane-1-one oxime-0-acetate; ethyl ketone-1-[9-ethyl-6-(2-methylbenzoguanidine)-9Η-carbazole- 3-yl]-1-(〇-acetamidine); ethyl ketone-1-[9-ethyl-6-[2-methyl·4-(2,2-dimethyl-1,3-di) Oxolane) methoxybenzimid]-9. Hey. -oxazol-3-yl]-1-(0-acetamidine); 1-[9-ethyl-6-(1,3,5-trimethylbenzoguanidine)-9. H--oxazol-3-yl]-ethane-1-one oxime-indole-benzoate; 1-[9-butyl-6-(2-ethylbenzimid-3-yl) - ethane-1-ketooxime-indole-benzoate; 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzhydrazide)-9. H. _ oxazol-3-yl]-ethane-1-one oxime-0-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzhydrazide) -9. H. -oxazol-3-yl]-ethane-1-one oxime-indole-benzoate or the like. Among these 0-oxime compounds, particularly preferred is ethyl ketone-l-[9-ethyl-6-(2-methylbenzhydrazide)-9H-indazol-3-yl]-1-(0-B醯圬), ethyl ketone-l-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolan)methoxybenzyl hydrazide] Oxazol-3-yl]-1-(0-acetamidine). -28 - 200909459 It is widely known that O-indole compounds can be used alone or in combination of two or more, in the middle of the month, by using a 〇-醯圬 compound, even at 1,00 0J/m2 in 卞ύΛι seedlings, t/ θ The exposed star under the arm can also obtain a spacer with sufficient sensitivity and adhesion. The present ethyl ketone-based compound is, for example, a cardinone-based compound or an α-aminoketone-based compound. The α-hydroxyketone-based compound, for example, has 1-phenyl-2-hydroxy-2-methylpropanol, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-ketone, 4 (2-3⁄4 methoxy)phenyl-(2-hydroxy-2-propyl) ketone, hydroxycyclohexylphenyl hydrazine, etc. 'In addition' the aforementioned α-amine ketone compound, for example, 2_A Base·^(4-methylsepenyl)_2_morpholinopropane-indolone, 2-benzyl-2-dimethylamino-y-(4-morpholinylphenyl)-butane a ketone, 2/dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1.one or the like. Examples of the compound other than these include 2,2-dimethoxyacetophenone and 2,2-diethoxyacetophenone 2,2-dimethoxy-2-phenylacetophenone. Among these acetophenone-based compounds, 2-methylmethylsepenyl-2-morpholinylpropan-1-one and 2-dimethylamino-2-(4-methyl-benzyl are particularly preferred. Keto)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. In the present invention, the sensitivity, the shape of the spacer or the compressive strength can be further improved by using an acetophenone-based compound. Further, the above biimidazole-based compound is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyldiimidazole, 2'2' · Bis(2-bromophenyl)-4,4,5,5,-tetrakis(4-ethoxycarbonylphenyl)-1,2'·bisimidazole, 2,2,-bis(2-chloro Phenyl)-4,4,5,5,-tetraphenyl-1,2,-bisimidine, -29- 200909459 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,-four Phenyl-1,2,-bisimidazole, 2,2 bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidine, 2,2 ,-bis(2,4-bromophenyl)_4,4',5,5'-tetraphenyl-bis-mid-s, 2,2'-bis(2,4,6-dibromophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidine, etc. Among these biimidazole compounds, 'preferably 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'-Bismidene, 2,2,-bis(2,4,6-trichlorophenyl)·4,4',5,5'-tetraphenyl-1,2'-biimi Etc., especially, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bimidoxime. In the present invention, by hydrazine The use of a bisimidazole compound can improve the sensitivity, resolution or adhesion. In addition, in the case of using a bisimidazole compound, in order to increase the sensitivity, an aliphatic or aromatic group having a divalent amine group can be added. a compound (hereinafter referred to as "amine-based sensitizer"). The amine-based sensitizer is, for example, n-methyldiethanolamine or 4,4,-bis(dimethylamino)benzophenone, 4 , 4,-bis(diethylamino)benzophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, etc. Among these amine-based sensitizers, In particular, 4,4'-bis(diethylamino)-benzazole is preferably used. The above-mentioned amine-based sensitizer may be used alone or in combination of two or more. In the case of the amine-based sensitizer, a thiol-based compound may be added as a hydrogen-donating compound. The bis-imidazole-based compound -30-200909459 is sensitized by the amine-based sensitizer and is cleaved. The imidazole radicals are produced, but most of them do not exhibit a higher polymerization initiation energy in this state, so that the shape of the obtained spacer is formed into a less desirable anti-cone shape. However, the bisimidazole compound and the amine group are formed. When a sensitizer is present, by adding a thiol compound, a hydrogen radical can be supplied to the imidazole radical from the thiol compound, and as a result, the imidazole radical can be converted into a neutral imidazole, and the polymerization is started. The composition of the higher sulfur radicals is initially formed, whereby the shape of the spacer is formed into a desired smooth shape. The aforementioned thiol-based compound, for example, has 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio-5-methoxybenzothiazole An aromatic compound such as 2-hydrothio-5-methoxybenzimidazole; 3-hydrothiopropylpropionic acid, methyl 3-hydrothiopropionate, ethyl 3-hydrothiopropionate, An aliphatic monothiol such as octyl 3-hydrothiopropionate; 3,6-dioxa-1,8-octanedithiol, neopentyltetrakis(hydrothioacetate), neopentyl An aliphatic thiol having two or more functional groups such as an alcohol tetrakis(3-hydrothiopropionic acid) ester. Among these thiol-based compounds, 2-hydroxythiobenzothiazole oxime is particularly preferred. When the bis-imidazole compound and the amine-based sensitizer are used, the amount of the amine-based sensitizer added is bis-imidazole. The weight of the compound is 100 parts by weight, more preferably 0 _ 1 to 150 parts by weight, more preferably 1 to 1 2 5 parts by weight. If the amount of the amine-based sensitizer added is less than 1 Μ 1 Μ, the effect of improving the sensitivity, resolution, or adhesion tends to be lowered. On the other hand, if it exceeds 150 parts by weight, the result is The shape of the spacer has a tendency to be damaged. Further, when the diimidazole-based compound and the amine-based sensitizer are used, the amount of the sulfur-31 - 200909459 alcohol-based compound is 'preferably the weight of the bisimidazole-based compound 1 〇 ,.  1 〇 weight, more preferably 1 to 7 5 weight. 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 the weight is more than 1 〇〇, the resulting spacer is obtained. The shape has a tendency to be damaged. The above-mentioned radiation-sensitive linear polymerization initiator 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 preferably 1 to 50 parts by weight, more preferably 1 to 50 parts by weight of the [Α] alkaline soluble polymer. Ideally 3 to 40 parts by weight. - Additive - In the sensitive radiation linear resin composition of the present invention, a surfactant, a secondary auxiliary agent, a preservation stabilizer may be added in addition to the aforementioned components, as long as the desired effect of the present invention is not impaired. Additives such as heat resistance enhancers. 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 group, a main chain and a side chain. The specific example is 1,1,2,2·tetrafluorooctyl group. (1,1,2,2-tetrafluoro-n-propyl)ether, l,l,2,2·tetrafluoro-n-octyl (n-hexyl)ether, octyl glycol di(l,;l,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-T-32- 200909459 Fluorated n-dodecane, sodium perfluoro-n-dodecylsulfonate, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, Sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl trimethylglycine, fluoroalkyl polyoxyethylene ether , perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxylate, fluoroalkyl ester, and the like. Further, as a commercial product of a fluorine-based surfactant, for example, the product name is BM-1 000, the same -1 00 (the above is manufactured by BM CHEMIE); Megaface F142D, the same F172, the same F173, the same F183, the same F178 , F191, F471, and F476 (the above is manufactured by Dainippon Ink and Chemicals Co., Ltd. (Japan); Fluorad FC 170C, FC-171, and FC-430' with FC-431 (above Sumitomo 3M Co., Ltd.) (Japan) system; Surfflon S-112, same S-113, same S-131, same S-141, same S-145, same S-382, same SC-101, same SC-102, same SC-103 , the same SC-104, the same SC105, the same SC-106 (the above is manufactured by Asahi Glass Co., Ltd. (Japan)); FT〇P EF301 'with EF303, the same EF352 (above is the new Akita Chemical Co., Ltd. (Japan)); Ftergent FT-1 00 ' with FT-110, with FT-140A, with FT-150, with FT-25 0, with FT-251, with FTX-251, with FTX-218, with FT-300, with FT-310 In the same way as FT-400S (the above is manufactured by Neos (Japan)). The above-mentioned anthrone-based surfactant is commercially available, for example, as Toray Silicone DC 3 PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH-193. Same as SZ-6032, SF-8428, and DC-57' with DC-190 (above is Toray Dow Corning Silicone Co., Ltd. (-33-200909459 Japan); TSF-4440, same -4300, same -4445, Same as -4446, -45060, and -4452 (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 a commercial product is, for example, KP3 4 1 (manufactured by Shin-Etsu Chemical Co., Ltd. (Japan); Polyflow No. 57. Tongyu ο. 95 (manufactured by Kyoeisha Chemical Co., Ltd. (Japan)). 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 the weight of the [Α] alkali-soluble polymer. When the amount of the surfactant to be added 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 spacer 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)ethyl-34-200909459-based trimethoxydecane, 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 1 part by weight or less, based on the weight of the [A] alkaline soluble polymer. If the amount of the auxiliary agent is more than 20 parts by weight, the development tends to be likely to remain. The above-mentioned preservation 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 stored is preferably 1 part by weight or less, more preferably 0 part by weight to the [A] alkaline soluble polymer 1 〇 0 weight portion. 001~0. 5 weights. 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)glycoluride (N_(Alkoxymethyl)Glycoluril) compound, N-(alkoxymethyl)melamine compound and the like. The aforementioned N-(alkoxymethyl) glycoluril compound, for example, ruthenium, osmium, iridium, osmium, tetrakis(methoxymethyl)glycoluril, ruthenium, osmium, iridium, Ν'-tetrakis Methyl)glycolil, &gt;}, 1^,1^',&gt;}'-tetrakis (n-propoxymethyl) glycoluril, ^1, &gt;4,:^',:^-four (Isopropoxymethyl) glycoluril, hydrazine, hydrazine, hydrazine, Ν'-tetrakis (n-butoxymethyl) glycoluril, hydrazine, hydrazine, hydrazine, Ν'-tetrakis Methyl) glycoluril and the like. Among these Ν-(alkoxymethyl)glycoluric compounds, ruthenium, osmium, iridium, Ν'-tetrakis(methoxymethyl)glycolide are preferred. -35- 200909459 Further 'the aforementioned N-(alkoxymethyl) melamine compound, 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,m",N"-hexa(n-butoxymethyl)melamine, N, N, N', N', N", N"-hexa(tris-butoxymethyl) melamine, and the like. Among these N-(alkoxymethyl)melamine compounds, particularly preferred are 1^, &gt;13', !^', :^', &gt;1"-hexa(methoxymethyl)melamine, the city thereof For example, the product name is Nikalac N-2702, the same MW-30M (the above is manufactured by Sanwa Chemical Co., Ltd.), etc. The heat resistance enhancer can be used alone or in combination of two or more. The amount of the agent to be added is preferably less than 30 parts by weight, more preferably 20 parts by weight or less, of the [A] basic soluble polymer 1 〇〇 weight portion. If the heat-resistant enhancer is more than 30% by weight Further, the storage stability of the sensitive radiation 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. By using a component 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, the solubility of each component and the reactivity of each component and the formation of a coating film are formed. Easiness In view of point, 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-36-200909459 ester. , dipropylene glycol alkyl ether, alkyl alkoxypropionate, acetate, etc., particularly 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, monoethyl Propylene glycol ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl ether acetate, 2-methoxyethyl acetate, etc. The solvent may be used singly or in combination of two or more. In the present invention, A high boiling point solvent is used together with the above solvent. The above high boiling point solvent is, for example, N-methylformamide, ν, Ν-dimethylformamide, Ν-methylbenzamide, Ν-methyl ethane. Indoleamine, hydrazine, hydrazine-dimethylacetamide, hydrazine-methylpyrrolidone, dimethyl sulfoxide, benzyl ether, di-n-hexyl ether, acetone acetone, isophorone, ,octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid Acrylate, monophenyl glycol ether acetate, etc. These high-boiling solvents may be used singly or in combination of two or more. Further, the above-mentioned composition of the composition may be a pore size of 0. Use 5 μπι microporous filter paper for filtration and use. 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. -37- 200909459 The formation of the spacer of the present invention is a step comprising at least the following steps in the order described below: (a) a step of forming a film of the radiation-sensitive linear resin composition of the present invention on a 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. 'The following steps are explained in order. - (a) step - forming a transparent conductive film on one side of the transparent substrate, and coating the radiation-sensitive linear resin composition on the transparent conductive film, preferably after coating the composition solution 'after heating (pre-baking) the coated surface Thereby, a film is formed. The transparent substrate used for the formation of the spacer is, for example, a glass substrate, a resin substrate, or the like, specifically, a glass 1 substrate such as soda lime glass or alkali-free glass; and polyethylene terephthalate or polybutene. A resin substrate formed of a plastic such as terephthalate, polyether sulfonate, polycarbonate, or polyamine. The transparent conductive film provided on one side of the transparent substrate is, for example, a NESA film formed of tin oxide (Sn〇2) (registered trademark of PPG, USA), and an IT0 film formed of indium oxide and tin oxide (In203-Sn02). Wait. The coating method of the composition solution forms a film of the radiation sensitive linear resin composition of the present invention, for example, (1) coating method, and (2) dry film method. -38-200909459 The coating method of the composition solution is, for example, a spin coating method, a spin coating method (spin coating method), a slit coating method, an inkjet coating method, or the like, and the like. Rotary coating is preferred. Further, in forming the sensitive radiation linear resin group of the present invention, when the (2) dry film method is employed, the dry film is more preferably formed on the flexible film film than the substrate film, and the radiation sensitive linear resin composition The formed radiation line (hereinafter referred to as "photosensitive dry film"). The photosensitive dry film is formed by coating a radiation-sensitive linear resin composition on a substrate film, preferably by drying the coating composition by a layer of a sensitive radiation layer. As the photosensitive base film, for example, polyethylene terephthalate, ethylene, polypropylene, polycarbonate, polyvinyl chloride or the like can be used. The thickness of the base film is preferably from 15 to 125 μm, preferably from 1 to 3 μm. Further, when the photosensitive dry film is not used, it can be deposited by laminating a cover film. The cover film must be peeled off when it is used, and it is easy to peel off during use, and the cover film which satisfies this condition is suitable, for example, the oxime ketone is released from the PET film, the polypropylene film, the polyethylene film, the film, etc. The surface of the synthetic resin film is formed. The cover film is ideally about 25 μm. In addition, the pre-baking conditions are preferably based on the type of each component, the adjustment method, the roll coating method, the bar coating method, and the film formation of the slit product, and the laminate is formed by the present invention. The range of the solution after the dry film I (PET) and the film of the poly resin. The photosensitivity is such that film properties are not achieved. The thin thickness of the coating or burning of the polyvinyl chloride is different from that of -39 to 200909459, for example, at 70 to 120 ° C for about 1 to 15 minutes. - (B) Step - Next, at least a portion of the formed film is 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 1 90 to 450 nm is particularly preferably a radiation containing ultraviolet rays of 3 6 5 nm. Regarding the amount of exposure, by illuminance meter (OAI model 356, OAI Optical Associates Inc. The measurement of the intensity of the wavelength of the exposed radiation at 365 nm is preferably 1 〇〇 〇〇〇 J / m 2 , more preferably 500 1, 1, 5.00 J / m 2 ° - (C) - The exposed film is then imaged 'by taking unnecessary portions 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 the like; 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; Pyrro丨e, Piperidine, n-methyl acridine, n-methylpiperidine-40- 200909459

Pyrrolidine), an alicyclic tertiary amine such as 1,8-diazabicyclo[5·4.0]-7-^--ene, 1,5-diazabicyclo[4.3 ·0]-5-nonene ; an aromatic tertiary amine such as pyridine, trimethylpyridine (Collidine), lutidine (Quitidine), quinoline or the like; an alkane such as ethanol dimethylamine, methyldiethanolamine or triethanolamine An alcohol solution; an aqueous solution of a basic compound such as a tetra-ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. 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, 1 〇 to 1880 seconds. After development, for example, after washing with water for about 30 to 90 seconds, it is air-dried by, for example, compressed air or compressed nitrogen, thereby forming a specific pattern. - (d) step - followed by heating means such as a heating plate, a heating furnace, etc., at a specific temperature, for example, 100 to 23 0 t:, for a specific time, for example, 5 to 30 minutes in a heating plate, in a heating furnace The obtained pattern was heated (post-baking) at 30 to 180 minutes, whereby a specific pattern was obtained. When the conventional radiation sensitive linear resin composition used for the formation of the separator is not subjected to heat treatment at a temperature of 1800 to 200 ° C or higher, the obtained separator does not exhibit sufficient performance, but the present invention In the sensitive radiation linear resin composition, the heating temperature can be set lower than the conventional one, and as a result, the resin substrate can be formed into a compressive strength, a polishing strength at the time of liquid crystal alignment, and a transparent layer without causing yellowing or deformation of the resin substrate. The adhesion between the substrates -41 - 200909459 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 element 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 having two layers of a liquid crystal layer interposed therebetween 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) array. This constitutes a TN-TFT type liquid crystal display element. At this time, a protective film can be formed on the polarizing plate or the color filter layer as necessary. EXAMPLES Hereinafter, examples of the present invention will be described in more detail by way of examples. 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 methacrylic acid methacrylic acid. 25 parts of tricyclo [5.2.1.02'6]nonane-8-yl ester, 5 parts of styrene-42-200909459 olefin, 30 parts of 2-hydroxyethyl acrylate and 22 parts of benzyl methacrylate After nitrogen gas, the temperature of the solution was raised to 80 ° C while slowly stirring, and the temperature was maintained for 5 hours to carry out polymerization, whereby a copolymer [α-1] solution having a solid content concentration of 28.8% was obtained. The Mw of the obtained copolymer [α-l] solution was measured by GPC (gel permeation chromatography) GPC-101 (trade name, manufactured by Showa Denko Co., Ltd.), and the result was 1 3, 0. 0 0. 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. After 100 parts of the copolymer [α-1] solution, the mixture was stirred at 40 ° C for 1 hour and 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 reaction at 40 ° C for 1 hour and then at 60 ° C for 2 hours, it was confirmed from the acrylic acid 2 -(2-Isocyanatoethoxy)ethyl 2,2 7 0 (:1^1 near peak 値 reduction pattern. Obtain a solid concentration of 31.8% [A] polymer solution. [A] The polymer was set to be a polymer (Α-1). Synthesis Example 3 15 parts of 2-(2-isocyanatoethoxy)ethyl acrylate and 4 parts of methoxybenzene-43-200909459 After adding to 100 parts of the copolymer [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 the reaction. From 2-(2-isocyanatoethoxy) acrylate The reaction between the isocyanato group of the ethyl ester and the hydroxyl group of the copolymer [α-1] was carried out in the same manner as in Synthesis Example 2, and it was confirmed by IR (infrared absorption) spectrum to obtain a solid concentration of 31.5%. [Α] polymer solution. This [Α] polymer was set as a polymer (Α-2). Synthesis Example 4 2-[2-(2-Isocyanoethoxy)ethoxylate methacrylate ] ethyl ester 19 and 4 methoxyphenol 0. The reaction was carried out after stirring 1 〇〇 of the copolymer [α·ι] solution and stirring at 40 ° C for 1 hour and then at 60 ° C for 2 hours. From 2-(2-(2-) methacrylate The reaction between the isocyanato group of isocyanatoethoxy)ethoxy]ethyl ester 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). The spectrum was confirmed to obtain a [A] polymer solution having a solid concentration of 3 2 · 5 %. This [a ] polymer was set as the polymer (A-3). Synthesis Example 5 3-Methyl propyl hydrazine 12 parts of oxyphenyl isocyanate (trade name: Karenz MOI-PH, manufactured by Showa Denko Co., Ltd.) and 4 parts of 4-methoxyphenol oxime were added to the copolymer [α · 1 ] solution, and then 4 〇. The reaction was carried out by stirring 〇c for 1 hour and stirring at 60 ° C for 2 hours. The reaction between the isocyanato group of 3-methacryloxyphenyl isocyanate and the hydroxyl group of the copolymer [α_]] was carried out. In the same manner as in Synthesis Example 2, it can be confirmed by IR (infrared absorption) spectrum -44 - 200909459. A [a] polymer solution having a solid concentration of 31% 〇% is obtained. A] The polymer was set to be a polymer (A·4). Synthesis Example 6 12 parts of methacryloxyethyl isocyanate (trade name: Karenz MOI, Showa Denko Co., Ltd., Japan) and 4-methoxyphenol 0.1 part was added to the above copolymer [α -1 ] solution, and the reaction was carried out at 40 ° (: stirring for 1 hour and stirring at 60 t for 2 hours). The reaction between the isocyanato group derived from methacryloxyethyl isocyanate and the hydroxyl group of the copolymer [?-1] was carried out in the same manner as in Synthesis Example 2, and was confirmed by IR (infrared absorption) spectrum. A [Α] polymer solution having a solid concentration of 3 ··2 % was obtained. This [A] polymer was set as the polymer (A-5). Synthesis Example 7 2 parts of 2,2,-azobis-(2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer. Adding 18 parts of methacrylic acid, methyl propylene succinic acid tricyclic [5.2.1 · 〇 2, 6] brothel-8-yl ester 25, styrene 5, butyl 2, methyl propylene 10 parts of acid glycidyl ester, 25 parts of methacrylic acid, 25 parts of acetonitrile and 12 parts of tetrachlorofuran-2-yl methacrylate, and the solution was slowly stirred while the environment was replaced with nitrogen. The temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization, whereby a copolymer [α_ 2] solution having a solid fraction of 28.3% was obtained. Mw of the obtained copolymer [α-2] solution was measured by GPC (gel permeation chromatography-45-200909459 method) GPC-101 (product name, manufactured by Showa Denko Co., Ltd.), and the result was 9,000. . Synthesis Example 8 15 parts of 2-(2-isocyanatoethoxy)ethyl methacrylate and 0.1 part of 4-methoxyphenol were added to 1 part of the copolymer [α_2] solution, and then 4 〇 The reaction was carried out by stirring at ° C for 1 hour and then at 60 ° C for 2 hours, whereby a [A] polymer solution having a solid concentration of 31.2% was obtained. This [A] polymer was designated as a 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, methacrylic acid. 25 parts of tricyclo[5·2·1·02'6]decane-8-yl ester, 5 parts of styrene, 5 parts of butadiene, 2-(6-hydroxyhexyloxy)ethyl methacrylate (product name: PLACEL F Μ 1 D (Daice 1 C hemica 1 I ndustries Co., Ltd.)) 25 parts and 22 parts of tetrahydrofuran-2-yl methacrylate, and slowly replaced the environment with nitrogen gas. 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 - 3 ] solution having a solid content concentration of 29.0 % was obtained. The Mw of the obtained copolymer [α-3] solution was measured by GPC (gel permeation chromatography) GPC · 1 0 1 (trade name, manufactured by Showa Denko Co., Ltd., Japan), and the result was 1 8 , 0 0 0. -46-200909459 Synthesis Example 15After adding 15 parts of 2-(2-isocyanatoethoxy)ethyl methacrylate and 0.1 part of 4-methoxyphenol to the copolymer [α-3] solution, The reaction was carried out at 4 (TC stirring for 1 hour and further stirring at 60 t for 2 hours, whereby a [A] polymer solution having a solid concentration of 31.0% was obtained. This [A] polymer was set as a polymer ( A-7) Synthesis Example 1 1 12 parts of methacryloxyethyl isocyanate and 4-methoxyphenol oxime. 1 part was added to the copolymer [α-3 ] solution, and it stirred at 40 ° C. The reaction was carried out by stirring at 60 ° C for 2 hours, whereby a [A] polymer solution having a solid concentration of 3 1.0% was obtained. This [A] polymer was designated as a polymer (A-8). Synthesis Example 1 2 3 parts of 2,2'-azobisisobutyronitrile 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. 25 parts of tricyclo [5.2.1.02'6]nonane-8-yl methacrylate, 5 parts of styrene, 30 parts of 2-hydroxyethyl methacrylate and 22 parts of benzyl methacrylate, replacing the environment with Slowly after 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 content concentration of 33 · 5% was obtained. Α-4] solution, using GPC (gel permeation chromatography) GPC-1 01 (trade name, manufactured by Showa Denko Co., Ltd.) to -47- 200909459

Mw was measured and found to be 3 〇, 〇〇〇° Synthesis Example 1 3 2-(2-isocyanatoethoxy)ethyl methacrylate (trade name: Karenz MOI-EG, Showa Denko Co., Ltd., Japan) 15 parts and 15 parts of 4-methoxyphenol were added to the copolymer [α_4] solution, and the mixture was stirred at 4 ° C for 1 hour and 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 a polymer (A - 9 ). Synthesis Example 1 4 3-Methyl propylene oxime; phenyl isocyanate (trade name Karen z MOI-PH, Showa Denko Co., Ltd. (Japan) 2) and 2 parts of 4-methoxyphenol were added to the copolymer [α_4] solution, and the mixture was stirred at 4 ° C for 1 hour, and further stirred at 60 t: 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 1 5 A part of the above copolymer [α _] was added to a part of the copolymer of methyl propylene oxyethyl isocyanate (trade name: Karenz MOI 'Showa Denko Co., Ltd. (made in Japan) 12 parts and 4-methoxybenzoquinone). 4] After the solution, the mixture was stirred at 40 ° C for 1 hour, and further stirred at 60 ° C for 2 hours to carry out the reaction. A [A] polymer solution having a solid concentration of 3 5 · 0 % was obtained. This [A] polymer was set as the polymer (A-] 1). -48-200909459 Examples 1 to 14 and Comparative Examples 1 to 7 The preparation of the composition solution [A] was carried out by using 100 parts of the [A] polymer solution obtained in Synthesis Example 2 as a polymer (A_1), [ In the component B), dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA (manufactured by Sakamoto Chemical Co., Ltd.)), part 00, [C], and ethyl ketone ethyl-6- (2-methylbenzhydrazide)·9Η-carbazol-3-yl]-b (〇-acetamidine) (trade name: Irgacure OXE02, manufactured by Chiba Specialty Chemicals Co., Ltd. (Japan)) 5, 2, 2 '-Bis(2-chlorophenyl)·4,4',5,5'-tetraphenyl-1,2'-bisimidazole 5, 4,4'-bis(diethylamino)diphenyl 5 parts of ketone and 2.5 parts of 2-hydrothiobenzothiazole, followed by 5 parts of γ-glycidoxypropyltrimethoxy decane, and FTX-21 8 (product name) 0.5 parts of Neos (manufactured by Japan Co., Ltd.) and 0.5 parts of 4-methoxyphene were used as a storage stabilizer, and were mixed and dissolved in monoethyl propylene glycol ether acetate so that the solid content concentration became 30%. After that, use the aperture 〇 · 5 μηι of microporous filter paper or the like is filtered to prepare a composition solution (S-1). The first expression shows the composition of (S -1). In the first table, the components other than the polymer are as follows: [Β] component Β·1 : dipentaerythritol hexaacrylate (trade name KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) B-2: City containing a polyfunctional polyurethane acrylate-based product -49-200909459 (Product name: KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)) B-3: New Epoch Alcohol tetraacrylate (trade name: ARONIX M-450, manufactured by Toagosei Co., Ltd.) B-4 : ω-carboxypolycaprolactone polyol monoacrylate (trade name: ARONIX Μ-5300, East Asia Synthetic Co., Ltd. Japan) B-5 : 1,9-nonanediol diacrylate (trade name Light-

Acrylate 1,9-NDA, manufactured by Kyoeisha Co., Ltd. (Japan)) [C] component C-1: ethyl ketone-l- [9-ethyl-6-(2-methylbenzhydrazide)-9H- Carbazole-3-yl]-1-(0-acetamidine) (trade name: Irgacure OXE02, manufactured by Chiba Specialty Chemicals Co., Ltd. (Japan)) C-2: Ethylketone-l-[9-ethyl-6- [2-Methyl-4(2,2-dimethyl-1,3-dioxolan)methoxybenzyl hydrazide]-9.Η·-carbazole-3-yl]-1-( 0-acetamidine) (manufactured by Adeka Co., Ltd., N-1 91 9) C-3 : 2-methyl-1-(4-methylsecenyl)-2-morpholinylpropan-1-one (Product) Name Irgacure 907, manufactured by Chiba Specialty Chemicals Co., Ltd. (Japan) C-4: 2-dimethylamino 2-(4-methylbenzyl)-indole (4-morpholin-4-yl) Phenyl)-butylene-l-copper (trade name Irgacure 379 'Chiba Specialty Chemicals Co., Ltd. (made by Japan)) C-5: 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-bisimidazole-50- 200909459 C-6 : 4,4'-bis(diethylamino)benzophenone C-7: 2-thiothiobenzene Thiazole [D] component D-1 : polyfunctional novolac type epoxy resin (trade name, japan Epoxy Resi n manufactured by Nippon Co., Ltd., Epicoat 152) Examples 2 to 14 and Comparative Examples 1 to 7 ′ As in the example, the composition solution was prepared in the composition shown in Table 1. Example 1 4 and Comparative Examples 6 to 7 A composition solution was prepared so that the solid content concentration became 50%. The spacer was formed in Example 3 and Comparative Examples 1 to 5, and was coated on a substrate by a spin coater to form a spacer. The details are shown below. The solution of the above composition was applied onto an alkali-free glass substrate using a spin coater, and then prebaked on a hot plate at 1 °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 μηα square. Thereafter, the image was developed by a potassium hydroxide 〇.〇5 wt% aqueous solution at 25 ° C for 60 seconds, then washed with pure water for 1 minute, and then heated in a heating oven at 23 ° C for 30 minutes. Thereby a spacer is formed. Further, in Example 14 and Comparative Examples 6 to 7, the 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-1 4) of the radiation sensitive linear resin composition was produced by the dry film method, the others were the same as those of the examples -51 - 200909459 Examples 1 to 1 3 A patterned film was formed and evaluated. The ingredients are shown in Table 1. 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. A liquid composition (S-14) of a 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. Minutes, a sensitive radiation linear dry film (J-1) having a thickness of 4 μΐη was produced. Then, on the surface of the glass substrate, the radiation-sensitive linear transfer dry film is superimposed 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 the comparative example, the liquid composition (S-6) of the radiation sensitive linear resin composition was replaced with the liquid composition (s-6) of the sensitive radiation linear resin composition in Example 14. Further, in the same manner as in Example 14 except that the radiation-sensitive linear dry film (J-2) was produced, 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 not as good as the 1st. The results of the assessment are as shown in Table 2. Then carry out various evaluations according to the following methods. The results of the assessment are shown in Table 2. (1) Evaluation of sensitivity - 52- 200909459 The same as the formation of the spacer. When the spacer is formed, the residual film ratio after post-baking (film thickness after post-baking XI 00 / film thickness after exposure) is More than 90% of the exposure is set to sensitivity. When the exposure amount is 1,000 J/m2 or less, the sensitivity is good. (2) Evaluation of the elastic recovery rate The obtained spacers were subjected to a micro-compression tester (trade name: DUH-201, manufactured by Shimadzu Corporation (Japan)), with a plane indenter of 50 μm in diameter at the load speed and The load speed is set to 2.6 mM / sec, the load is loaded to 50 mN, and after the load is held for 5 seconds, the load-deformation curve and the load-deformation curve at the time of the load are generated. . 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 (%) = L 2 X 1 0 0 / L 1 Elastic recovery rate (%) and deformation amount L 1 (μπι) ' is shown in Table 2 when the deformation amount L1 is 0.2 μηι or more. Sex can be said to be good. (3) Evaluation of the abrasion resistance of the substrate on the substrate on which the spacer was formed was carried out by applying a liquid crystal alignment agent to AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal alignment agent. The film was dried at 80 ° C for 1 hour to form a coating film of a liquid crystal alignment agent having a film thickness of 0.5 μm. After -53-200909459, the coating film was brushed by a brush having a roll of a cloth made of polyamidamine under the conditions of a rolling speed of 500 rpm and a stage moving speed of icm/second. deal with. It is also evaluated whether or not the peeling of the pattern occurs at this time. (4) The evaluation of the adhesion is the same as the formation of the above-mentioned spacer except that the mask is not used, and after the formation of the cured film, 'in the adhesion test of JIS K - 5 4 0 0 (1 9 8 0) 8.5, The evaluation was carried out using the 8.5·2 checkerboard tape method. The number of checkerboard objects remaining in one of the checkerboards at this time is shown in the second table. (5) The heat resistance was evaluated in the same manner as the above-described spacer except that the mask was not used, and after the cured film was formed, heating was further performed in a heating furnace at 24 ° C for 60 minutes, and the measurement was performed before and after the additional heating. The film thickness was evaluated by the residual film ratio (film thickness X 00 after additional heating/thickness before heating). (6) Evaluation of preservation stability The sensitive radiation linear resin composition was placed in a constant temperature layer of 40 ° C for one week, and the rate of change of viscosity at this time was measured. When the viscosity increase rate is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor. -54- 200909459

ΐ^Ω. &lt;R mW tlmil Ptj 1 1 I 1 1 t 1 1 1 1 1 1 &lt; 1 1 1 inch I t &gt; 1 Q job »1mt1 w QI 1 (Ν (N (Ν胡π κη vr » &lt;n yr\ m + κη νη κη to rs ra r4 rj r^i Ο κη (Ν Η ri rj r&gt;i ^Τ) r4 rj csi tN ri ri (S _ Umi) paste m + 4* ΐ + Ηη in inch up un κη &lt;n + + vn yr\ &quot;f1 m csi *? Vi + m *? ΚΓ) c4 (Ν + «JO IT) ΚΓ) + κη κη *? in &lt;n + l〇 ΚΓί &quot;ί ό ΐ* κη 链卜卜卜卜Γ^* ΰ Γ- Γ*' Bu Bu ό Bu ό Bu Bu r- 卜 Bu Bu U ύ ύ 1 u 1 U 1 U 1 U U 1 u 1 U 1 U ύ U ό ύ ύ + 0 i ό i ό ό + \〇ύ + VO ό ύ ΰ u ΰ ύ + ό ό ό + + ύ ώ m ό ύ ό limtl w + &lt;n 6 + + + vn + + yr\ + vp + ό + in + W^) ύ + + ό ύ + + ό + ν/ρ + ύ + 戈 + in ΰ + 0 + ΰ + U + U + υ rn Γ Ί ό + ό + rn r ^ m Λ ό + U + ό + ύ + ύ + ύ + 5 ό ό 3 3 ΰ + ό 3 ό + + 3 ό ό 5 ό 3 3 ό ύ ύ Wn _ oo § + + i O g S ο ο S + § S ο o ο ο ο Ο ο ο ο φ tlmil ptl gg έ 00 , one + gg + g + g · — chain CQ type (Ν rn CO + CQ + CN OQ + DQ + ώ ώ + ώ + ώ + (N ώ ώ ώ &lt;Ν ώ ώ 1 m CQ + CN ώ (Ν ώ CQ ώ ώ 1 &quot; ώ ώ ώ ώ ώ ώ 1 CQ ώ + + CQ + + ώ ώ CQ ώ &lt; _ o ο Ο ο g ο O Ο ο ο ο ο ο O o 1 90/10 1 ο O ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 3 3 &lt; * - 1 &lt; 1 &lt;&lt; 1-^ &lt; 5 (Ν &lt; rn &lt;&lt;&lt; 1 &lt; CfN &lt; ά &lt; νη &lt;&lt; 00 &lt; Α-10 5 Α·^7 Oml1 τη Β (η 3s 〇〇s /*·--s Γ^Τ /*sx*~V Μ /—S w ζΛ ζΛ i 1 1 ζΛ I w soil ΙΛ color i (Ν m circumference & 4·=? inch卜οο 0 1 i (Ν imi 对 ii (Ν 匡ΓΛ κ ηη 〇 留 留 镒镒镒镒Μ 镒镒镒镒Μ * w * IK * |Κ 鹣IK i®\ n IK u IK 13⁄4 * jj AJ -U -Ο -LA Λ3 jj JA -55- 200909459 Preservation stability (N 04 rn (N η (N 寸 (N o inch * o r4 1 κη (N 00 V&quot;) (N (N 1 1 Heat resistance ON (N (N Ο m Os ON m O oo On On κη 00 κη On ε; § § κη § Adhesion (/100) 〇Ο ο Ο 1 ooo Ο oooo 100 〇oooo 〇Ο Ο ^― &lt; ο 100 o ο ο Ο Ο Wear-resistant brush test with or without peeling i 挨壊 壊 壊 壊 壊裢壊 壊裢壊 壊 壊 壊 弹性 弹性 弹性 弹性 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.24 0.22 0.23 0.24 1 0.25 0.22 0.20 0.20 0.28 0.22 0.21 0.28 0.12 0.11 0.11 0.17 0,09 1 0.10 Elastic recovery rate (%) 00 00 VO VO 〇〇SO VO VO iT) so VO m oo \D (N oo Ό irj 00 ν〇ο VO 00 VO 00 so SensitivityΓΜ ε 900 850 900 900 900 900 900 850 ; 800 1000 900 800 900 500 I [3000 900 12000 100 0 800 400 500 Sensitivity radiant dry film 1 1 &gt; 1 1 1 1 1 1 t 1 t 1 1 1 1 1 1 (Ν ·—i CT) A Composition species (S-1) (S-2) ( S-3) (S-4) (S-5) (S-6) (S-7) (S-8) I (S-9) 1 (S-10) I (S-Π) | (S -12) | (S-13) 1 (S-14) I (s-1) 1 (s-2) 1 (s-3) 1 (s-4) I (s-5) I (s-6 (s-7) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 I Embodiment 8 | Embodiment 9 Embodiment 10 Example 11 | Example 12 I | I Example 14 1 Comparative Example 1 1 Comparative Example 2 1 1 Comparative Example 3 I | Comparative Example 4 I 1 Comparative Example 5 I 1 Comparative Example 6 1 Comparative Example 7 | -56- 200909459 Effect of the Invention: Polymerization of the Invention The invention relates to a liquid crystal display sensitive radiation linear resin composition, a formation of a protective film for a crystal display element, a sensitive layer coating for forming a colored layer, and a radiation hardening type adhesive. The resolution is even better than the pattern shape of 〇0 0, so it can be used for the storage stability of the composition, and the brushing property and the adhesion spacer to the transparent substrate. The liquid crystal display element of the present invention exhibits excellent reliability in terms of elementality, flexibility, abrasion resistance, and various properties. [Simple description of the drawing] Figure 1 is a diagram for explaining the liquid pattern. Fig. 2 is a view showing the constituent components used in the formation of the spacer for the reactive unsaturated portion of the polymer side chain in the polymer side chain, and the sensitized radiation linear resin group ray used in the liquid forming. A constituent material such as a resin composition or a radiation curing agent is also extremely useful as a resin composition, and has a high sensitivity and an exposure amount of J/m 2 or less, and can be sufficiently formed to have a good linear radiation resin having good sensitivity. A member for a liquid crystal display element such as a spacer having flexibility, abrasion resistance, and heat resistance is provided with a spacer such as sensitivity, elastic recovery, adhesion to a transparent substrate, and heat resistance, so that a high-crystal display can be exhibited for a long period of time. A schematic diagram of another example of the structure of the mode crystal display element as an example of the structure of the element. -57- 200909459 Fig. 3 is a diagram showing an example of the load-deformation curve at the time of load and at the time of slow load in the evaluation of the elastic recovery rate. -58-

Claims (1)

200909459 X. Patent Application No. 1 - A sensitive radiation linear resin composition characterized by: [A] an aggregate composed of a polymerization unit of a monomer and having a group represented by the following formula (1) The single system comprises at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides; [B] polymerizable unsaturated compounds; and [C] linear polymerization of sensitive radiation Starting agent H2 c R1——C- CMMMO i 2R X 4 2H c- ο- cyo * }. (In the formula (1), R1 is a hydrogen atom or a methyl group, R2 is a stretching ethyl group or a stretching propyl group, and η is An integer from 1 to 5, and "*" is the key combination). 2. The radiation sensitive linear resin composition of claim 1, wherein the [Α] polymer is a compound carboxylic acid represented by the following formula (2) and (a 1 ) unsaturated carboxylic acid and A polymer obtained by reacting at least one selected from the group consisting of unsaturated carboxylic anhydrides and (a2) a copolymer containing an unsaturated compound having one or more hydroxyl groups in one molecule, R1 ch2 = c - C —〇—c2h4-(or2~)-n=c=o (2) -59- 200909459 (in equation (2), 'R1, R2, and n are synonymous with Ri, R2, and η of equation (1), respectively) 3. 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 element, characterized by comprising at least the following steps in the order described below: (a) a film of a radiation-sensitive linear resin composition of claim 3 a step of forming 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 (d) heating the film after development The steps. (6) A liquid crystal display element characterized by comprising: a spacer for a liquid crystal display element of claim 4, wherein the polymer is composed of a polymerization unit of a monomer and has the same The base of the following formula (1) is composed of at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. -60-200909459 R1 CH2::C C- Ο 〇2Η4~^〇 R2*^nh O 〇 (In the formula (1), R1 is a hydrogen atom or a methyl group, R2 is an exoethyl group or a propyl group, and n is an integer of 1 to 5. Further, "*" is a bonding bond). 8. The polymer according to claim 7, wherein the compound represented by the following formula (2) and (al) are composed of a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; At least one selected one and (a2) a polymer obtained by reacting a copolymer of an unsaturated compound containing one or more hydroxyl groups in one molecule, R1 CH2=C-C-Ο-C2H4-(〇R2-)- N=C=0 (2) (In the formula (2), R1, R2 and η are synonymous with R1, R2 and η of the formula (1), respectively. -61 -