TW200900858A - Radiation-sensitive resin composition, spacer for liquid crystal display element, protective film, and method for producing spacer for liquid crystal display element or protective film - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition containing a copolymer [A] of an unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride and an unsaturated compound different from them, a polymerizable unsaturated compound [B], a radiation-sensitive polymerization initiator [C] and a nitroxyl compound [D] such as bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate. This radiation-sensitive resin composition has excellent resolution performance and enables to form a fine pattern.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive linear resin composition which is extremely suitable for the formation of a spacer and a protective film in a liquid crystal display element, and a spacer and a protective film are formed therewith. Method and liquid crystal display element. [Prior Art] In the liquid crystal display device, it is conventional to maintain a space between the two substrates (cell gap), and to use a spacer such as a glass bead having a predetermined particle diameter. The spacers are randomly distributed on a transparent substrate such as a glass substrate. Therefore, when a spacer is present in the pixel formation region, a glare phenomenon of the spacer occurs, or the incident light is scattered and caused to act as a spacer. The problem of reduced contrast of liquid crystal display elements. Therefore, in order to solve such a problem, a method of forming a spacer by photolithography has been started. In the method, the sensitive radiation linear resin composition is applied to the substrate. The transparent mask is exposed through ultraviolet light, for example, after being exposed to ultraviolet light to form a dot-like or strip-shaped spacer, because the pixel formation region In addition, the spacer can be formed only in the place where it is set, and the above-mentioned problem can be basically solved (refer to Japanese Laid-Open Patent Publication No. 2001-302712). However, in recent years, in liquid crystal display elements, high definition has been made in order to improve image quality. With the high definition of the liquid crystal display element, in order to reduce the size of each pixel, the sensitive radiation resin composition used for the formation of the spacer has been required to form a finer pattern than the conventional one. -5-200900858 In the radiation sensitive resin composition used for forming only the protective film covering the pixel formation region, similarly, it has been required to form a pattern which is finer than the conventional one. In order to form a fine pattern, the problem is the diffraction phenomenon of the light exposed at the opening of the mask, and the diffusion and scattering of the exposed light by the sensitive linear resin composition itself. That is, the use of a so-called negative-sensitive radiation linear resin composition in the case of forming a spacer or a protective film, by diffraction, diffusion and scattering of the exposed light, is due to the mask of the exposed area Since the wider range of the opening portion is exposed, the size of the pattern formed is more significantly increased than the size of the opening portion of the mask, and it is difficult to form a desired fine pattern. Conventionally, a compound containing phosphorus or sulfur or hydrogen is used in order to suppress photopolymerization of a linear radiation-sensitive resin composition outside the original exposed region by diffraction, diffusion, and scattering of such exposed light. A sensitized radiation linear resin composition such as an anthracene derivative. However, these compounds have an effect on the point of forming a fine pattern, but the sensitivity is remarkably lowered, and it is not suitable for a sensitive radiation linear resin composition for a liquid crystal display element which is expected to be highly sensitive. SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation sensitive linear resin composition which is excellent in the resolution of a fine pattern. Another object of the present invention is to provide a liquid crystal display spacer or a protective film formed of the above-mentioned radiation-sensitive linear resin composition, and a liquid crystal display element comprising the above-mentioned -6 - 200900858. Still another object of the present invention is to provide a method of forming a spacer for a liquid crystal display or a protective film. According to the present invention, the first aspect of the invention includes that [A] (al) is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and is different from (a2) and (a1). A copolymer of other unsaturated compounds, [B] a polymerizable unsaturated compound, [C] a radiation-sensitive linear polymerization initiator, and a [D] cerium-based compound, which is a radiation-sensitive linear resin composition. According to the present invention, the second aspect of the problem can be solved by a spacer or a protective film for a liquid crystal display element formed of the respective sensitive radiation linear resin compositions. According to the present invention, the third aspect of the subject matter can be solved by a method for forming a spacer for a liquid crystal display element or a protective film which is characterized by 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 claim 5 of the patent application range on the substrate, (b) exposing to at least a portion of the film, and (c) exposing the film after exposure a step of developing, and (d) a step of heating the film after development. According to the present invention, the fourth aspect of the subject matter can be solved by the spacer for a liquid crystal display element, a protective film, or a liquid crystal display element having both of the above - 7 - 200900858. BEST MODE FOR CARRYING OUT THE INVENTION <Sensitive Radiation Linear Resin Composition> Hereinafter, each component of the radiation sensitive linear resin composition of the present invention will be described in detail. [A] a copolymer [A] copolymer contained in the linear radiation-sensitive resin composition of the present invention, wherein (al) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "Compound (al)") is a copolymer of another unsaturated compound (hereinafter referred to as "compound (a2)") which is different from (a2) and (al). In the present invention, the [A] copolymer is at least one selected from the group consisting of [A1] compound (al) and an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter, referred to as "compound (a2- 1 )" a copolymer (hereinafter referred to as "copolymer [α]"), a polymer obtained by reacting an unsaturated isocyanate compound (hereinafter referred to as "[Α] polymer"), and [Α2] a compound (al) And a copolymer of an unsaturated compound having an oxiranyl group or an oxetanyl group (hereinafter referred to as "compound (a2 - 2)") (hereinafter referred to as "copolymer [β]") Groups are better. As the compound (a 1 ), for example, acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinic acid, 2-methylpropenyl methacryloxyethyl succinic acid, 2-propylene oxime Oxygen B-8- 200900858 monohydrogenic acid such as hexahydroabietic acid, 2-methylpropenyl methacryloyloxyethyl hexahydrophthalic acid; citraconic acid, mesaconic acid, itaconic acid maleic acid a dicarboxylic acid such as fumaric acid; an acid anhydride of the dicarboxylic acid; and the like. The obtained polymerization in the compound (a 1 ) relative to the copolymerization reactivity

Methyl propylene oxide ethyl ketone acid maleic anhydride or the like is preferred. In the copolymer [α] and the copolymer oxime], the compound (al) may be used singly or in combination of two or more kinds. In the copolymer [«] and the copolymer [3], the content of the repeating unit derived from the compound (ai) is preferably from 5 to 60% by weight, more preferably from 1 to 50% by weight, particularly preferably 1 5 to 4 0% by weight. When the content of the repeating unit derived from the compound (a 1 ) is less than 5% by weight, the solubility in the alkali developing solution of the obtained polymer tends to decrease, and on the other hand, when it exceeds 60% by weight, there is a relative The solubility of the alkali developer of the polymer becomes excessive. Further, as the compound (a2-l), for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl methacrylate (meth) acrylate (4-) methacrylate Base ester, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7- mercapto (meth) acrylate, 8-hydroxy octyl (meth) acrylate Base ester, 9-hydroxydecyl (meth)acrylate '(meth)acrylic acid 10_based fluorene vinegar '(A 200900858 yl) acrylate 11-hydroxyundecyl ester, (meth)acrylic acid 12-hydroxyl a hydroxyalkyl (meth) acrylate like dodecyl ester; further exemplified as '4-hydroxy-cyclohexyl (meth) acrylate, 4-hydroxymethyl-cyclohexyl methyl (meth) acrylate , (meth)acrylic acid 4_ylidylethyl-cyclohexylethyl ester, (meth)acrylic acid 3-hydroxy-bicyclo[2. 2. 1] hept-5-ene-2-yl ester, (meth)acrylic acid 3-hydroxymethyl-bicyclo[2. 2. 1]hept-5-en-2-ylmethyl ester, (meth)acrylic acid 3-hydroxyethyl-bicyclo[2. 2. 1]hept-5-en-2-ylethyl ester, (meth)acrylic acid 8-trans-bicyclo[2. 2. 1]hept-5-en-2-yl ester, 2-hydroxy-octahydro-4,7-methane (methano)-indol-5-yl ester, 2-hydroxyl (meth)acrylate Base-octahydro-4,7-methane-indol-5-ylmethyl ester, 2-hydroxyethyl-octahydro-4,7-methane-indol-5-ylethyl (meth)acrylate, Methyl) 3-hydroxy-adamantane-1-yl acrylate, 3-hydroxymethyl-adamantan-1-ylmethyl (meth)acrylate, 3-hydroxyethyl-methyl glycerol (meth) acrylate a hydroxyalkyl (meth)acrylate having an alicyclic structure like -1-ethylethyl ester; 1,2-dihydroxyethyl (meth)acrylate; 2,3-di(meth)acrylate Hydroxypropyl ester, 1,3-dihydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 3-[3- (2,3-) Dihydroxyalkyl (meth)acrylate, such as dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropyl; 2-(6-hydroxyhexyloxy)ethyl acrylate, 3-(6-Hydroxyhexyloxy)propyl acrylate, 4-(6-hydroxyhexyloxy)butyl acrylate, 5-(6-hydroxyhexyloxy)acrylate ) amyl ester, acrylic acid 6--10-200900858 (6-hydroxyhexyloxy) hexyl acrylate (6-hydroxyhexyloxy) alkyl acrylate; 2-(6-hydroxyhexanyl methacrylate Oxy)ethyl ester, 3-(6-hydroxyhexyloxy)propyl methacrylate, 4-(6-hydroxyhexyloxy)butyl methacrylate, 5-(6-methacrylic acid) -Hydroxyethylhexyloxy)pentyl ester, (6-hydroxyhexyloxy)alkyl methacrylate such as 6-(6-hydroxyhexyloxy)hexyl methacrylate (hereinafter, The above (6-hydroxyhexyloxy)alkyl (meth)acrylate is referred to as "other compound (a 2 -1 )"). Among these compounds (a2 -1 ), in terms of copolymerization reactivity and reactivity with an isocyanate compound, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate hydroxybutyl acrylate , 2-hydroxyethyl methacrylate - 3 - hydroxypropyl methacrylate, 4 - hydroxybutyl methacrylate, 4-hydroxymethyl - cyclohexyl methyl acrylate, 4-hydroxymethyl methacrylate The base-cyclohexylmethyl ester, 2,3-dihydroxypropyl vinegar of 2,3-dihydroxypropyl acrylate, the other compound (a2q) and the like are preferred. Further, in the compound (a2 -1 ), the other compound (a2 -1 ) is particularly preferable from the viewpoint of improving the visibility of the spacer or the compression performance of the obtained separator. Among the other compounds (a2-l), in particular, 2-(6-hydroxyhexyloxy)ethyl acrylate 2-(6-hydroxyhexyloxy)ethyl methacrylate is preferred. A commercial product of a mixture of 2-(6-hydroxyhexyloxy)ethyl methacrylate and 2-ethylideneethyl methacrylate can be sold under the trade name PLACCEL·FM1D' FM2D (;Daicei Chemical Industry Co., Ltd. System) etc. purchased in the city -11 - 200900858. The 'compound (a2-l)' in the copolymer [α] may be used singly or in combination of two or more. The content of the repeating unit derived from the compound (a2·1) in the copolymer [α] is preferably from 1 to 50% by weight, and further preferably from 3 to 40% by weight, particularly preferably from 5 to 30% by weight. / (*° When the content of the repeating unit derived from the compound (32-1) is less than 1% by weight, 'the decrease in the introduction rate of the polymer to the unsaturated isocyanate compound' has a tendency to lower the sensitivity' on the one hand over the weight% The storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound tends to be lowered. Further, in the copolymer [calling], the 'compound (a2-2)' may, for example, be a (meth) propyl storage. Acid glycidyl propyl '(methyl) acrylate 2 · methyl epoxide vinegar, 4- hydroxy butyl (meth) acrylate epoxy propyl ether ' (meth) acrylate 3, 4 - epoxy Butyl ester '6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth) acrylate 3,4-epoxy ring (meth)acrylic acid epoxy (cyclo)alkyl ester such as hexyl methyl ester; α-ethyl acrylate propyl acrylate isopropyl acrylate propylene acrylate, α-n-butyl propylene acrylate Ester 'α·ethyl propyl succinic acid 6,7_epoxy heptane vinegar, α-ethyl acrylate acid 3,4-epoxycyclohexanol Alkyl ester; o-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether's p-epoxypropyl ether of vinylbenzyl epoxypropyl ether; 3-(methacrylofluorene) Oxycyclobutane, 3-(methacryl-12-200900858 醯oxymethyl)-3-ethyloxetan' 3-(methacryloxymethyl)-2-methyl Oximedin' 3_(methyl propyl oxymethyl) difluoromethyl oxetane, 3-(methylpropanyloxymethyl)_2-pentaethoxyethyl oxetane ' 3-(methylpropionyloxymethyl)benyl oxetane, 3-(methacrylomethoxymethyl)_2,2-difluorooxetane, 3_(methyl propylene醯Oxymethyl)·2,2,4-trifluorooxetine' 3-(methacrylofluorenyloxy)_2,2,4,4_tetrafluorooxetane' 3_ (A Acryloxyethyl)oxetane, 3-(methacrylomethoxyethyl)_3-ethyloxetane 2-ethyl-3-(methacryloyloxyethyl) Oxetane, 3-(methacrylomethoxyethyl)-2-trifluoromethyloxetane, 3-(methylpropionyloxyethyl)-2-pentafluoroethyloxalate Cyclobutane, 3_(methyl Oxyxyethyl)-2-phenyloxetine, 2,2-difluoro-3-(methacrylomethoxyethyl)oxetane 3-(methylpropane oxime) Methyl acrylate such as ethyl) 2,2,4·trifluorooxetane, 3-(methacrylofluorenyloxy) 2,2,4,4-tetrafluorooxetane; 3-(Aromatic oxymethyl) oxetanium, 3-((anthraceneoxymethyl)-3-ethyloxetan' 3-(acrylomethoxymethyl)_2_methyloxy Heterocyclic butane, 3_(propylene oxime oxymethyl)-2-^_Tianyi and μ wind methyl oxindole, 3-(propylene oxymethyl) 2 - pentafluoroethyl oxalate , 3~(acrylic acid methyl)·2_phenyloxetane, 3·(propyleneoxymethyl)>_^_difluorooxocyclobutane, 3-(acrylofluorene) Base) — ' ~2,2,4 —difluorooxetane' 3·(propylene 醯oxymethyl)-2,2,4,4_tetraoxetane, 3_ (acrylic oxygen) Ethyl)oxetane, 3_(%% acetophenoxyethyl)_弘ethyloxetane' 2-ethyl_3-(propylene oxime and ethyl) oxetane , -13- 200900858 3-(Allyloxyethyl)-2-trifluoromethyloxetane' 3_( Oxide oxyethyl)-2-pentafluoroethyl oxetane, 3-(propionyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-( Propylene oxiranyl ethyl) oxetane, 3-(propylene oxiranyloxy) 2,2,4-trifluorooxetane' 3-(acryloxyethyl)-2,2,4 An acrylate such as 4-tetrafluorooxetane. Among these are especially glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxy ring of methacrylic acid. The point of polymerization of hexylmethyl ester, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, etc. good. In the copolymer [/3], the compound (a2-2) may be used singly or in combination of two or more. In the copolymer [/3 ], the content of the repeating unit derived from the compound (a2-2) is preferably 0. 5 to 70% by weight, further preferably 1 to 60% by weight, particularly preferably 3 to 50% by weight. The content of the repeating unit from the compound (a2-2) is less than 0. When the weight is 5, the heat resistance of the obtained copolymer tends to decrease. When the amount exceeds 70% by weight, the storage stability of the copolymer tends to decrease. Further, in the copolymer [α] and the copolymer [0], the compound (a2-1) and the other compound (a2) which are different from the compound (a2-2) can be referred to as "the compound" (hereinafter). A2-3)"" is used as a component of the copolymer. Specific examples thereof include, for example, methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl acrylate, and C-A-14-200900858 alkyl butyl acrylate. Ester; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate Etc. alkyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5. 2. 1. 02'6] decane-8-ester, acrylic acid 2-(tricyclic [5. 2. 1. 02'6] decane 8-octyloxy)ethyl ester, acrylate cyclic ester of isobornyl acrylate, etc.; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclomethacrylate [5. 2. 1. 02,6]decane-8-ester, 2-(tricyclo[5. 2. 1. 02'6] decyl-8-yloxy)ethyl ester, methacrylic acid alicyclic ester of isobornyl methacrylate or the like; aryl or arylalkyl acrylate of phenyl acrylate, benzyl acrylate or the like; An aryl or aralkyl ester of methacrylic acid such as phenyl methacrylate or benzyl methacrylate; diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Dialkyl dicarboxylate; tetrahydrofuran-2-acrylate, tetrahydropyran-2-acrylate, 2-methyltetrahydropyran-2-yl acrylate, etc. Or an oxy-containing 6-membered ring acrylate; tetrahydrofuran-2- methacrylate, tetrahydropyran-2- methacrylate, 2-methyltetrahydropyran-2- methacrylate, etc. Oxygen-containing 5-membered ring or oxy-containing 6-membered ring methacrylate; styrene, α-methylstyrene, m-methylstyrene, p-methylbenzene-15- 200900858 ethylene, p-methoxybenzene a vinyl aromatic compound such as ethylene; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene conjugated diene compound, acrylonitrile methacrylate Nitrile 'propylene amide, methyl propylene sulphur ethylene, vinyl chloride, vinyl acetate, and the like. Among these, in terms of copolymerization reactivity, methyl propyl ester, 2-methylglycidyl methacrylate, methacrylic acid to tricyclo[5·2·1,02'6]癸Alkyl-8-yl ester, styrene, p-ethylene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene copolymer [〇:] and copolymer [/3], compound (a2-3 It is used alone or in combination of two or more. The copolymer [α] and the copolymer [/3] are derived from the compound (the content of the repeating unit, preferably 10 to 70% by weight, and 20 to 50% by weight, Preferably, the compound is 30 to 50% by weight. The compound (the ratio of the unit of the repeating unit is less than 10% by weight, the tendency of the copolymer is low, and when it exceeds 70% by weight, the amount of the compound (a), the compound (a2 - 1) and the compound (a2-2) are low in content. The copolymer [α ] and the copolymer [/3 ] are produced by polymerization in the presence of a polymerization initiator in a suitable solvent. The solvent used in the polymerization is For example, an alcohol such as methanol n-propanol or isopropanol; an ether such as tetrahydrofuran or dioxane; ethylene glycol monomethyl ether; ethylene glycol monoethyl ether Ethamamine, n-butyl chloroformate, methyl methoxy benzene, etc. are preferred.), can be a single a2-3) and preferably a2-3), the amount of the compound is reduced to free Base, ethanol, mono-n-propyl-16- 200900858 ether, ethylene glycol mono-n-butyl ether, etc. ethylene glycol monoalkyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol single ethyl Ethylene glycol monoalkyl ether acetate such as ethylene ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; ethylene glycol monomethyl Ethylene terephthalate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate, etc. Propionate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. Diethylene glycol alkyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether and other propylene glycol monoalkyl ether; dipropylene glycol monomethyl ether , dipropylene glycol monoethyl ether, dipropylene glycol Dipropylene glycol alkyl ether such as methyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl Propylene glycol monoethyl ether acetate such as ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl Propylene propionate, propylene glycol monoalkyl ether propionate such as propylene glycol mono-n-butyl ether propionate; aromatic hydrocarbon such as toluene or xylene; methyl ethyl ketone, 2-pentanone, 3-pentyl a ketone, a cyclohexanone, a ketone such as 4-hydroxy-4-methyl-2-pentanone; -17- 200900858 methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-A N-propyl oxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-Butyl ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxy N-butyl propyl propionate, methyl 2-n-butoxypropionate, 2-n-butoxy Ethyl acetate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- N-propyl methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate , n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, 3-n-propyl N-butyl oxypropionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-n-butoxypropionic acid An alkoxypropionic acid alkyl ester such as n-butyl ester, or methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl glycolate, glycolic acid N-butyl acrylate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-hydroxypropyl butyl acetate, lactic acid Methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ester, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, Methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Ester, n-butyl ethoxyacetate, methyl n-propoxyacetate, -18- 200900858 ethyl n-propoxylate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, n-butyl Methyl oxyacetate, ethyl n-butoxide, n-propyl n-butoxyacetate, other esters such as n-butyl n-butoxyacetate. Among these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate or the like is preferred. These solvents may be used singly or in combination of two or more. Further, the radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile). , 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-valeric acid), dimethyl An azo compound such as -2,2 '-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as phenylhydrazine peroxide, lauryl peroxide, tertiary butyl peroxytrimethyl acetate, 1,1 - bis (tertiary butyl peroxy) cyclohexane; Hydrogen peroxide, etc. Further, when a peroxide is used as the radical polymerization initiator, it may be used as a redox initiator together with a reducing agent. These radical polymerization initiators may be used singly or in combination of two or more. The copolymer [α ] and the copolymer [Θ ] thus obtained can be used as a [Α] polymer as it is, and can be produced as a [Α] polymer once separated from the solution. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [α] and the copolymer [yS ] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000~ 200900858 50,000. When the Mw is less than 2,000, the alkali developability of the obtained film, the residual film ratio, etc. may be lowered, and the shape of the pattern may be impaired, and the heat resistance may be deteriorated. On the other hand, when the temperature exceeds 100,000, the resolution may be lowered or damaged. The shape of the shape of the figure. In the present invention, the [A] polymer is obtained by reacting an unsaturated isocyanate compound in the copolymer [α]. As the unsaturated isocyanate compound, for example, 2-propenyloxyethyl isocyanate, 3-propenyloxypropyl isocyanate, 4-propenyloxybutyl isocyanate, 6-propenyloxyhexyl isocyanate, 8-propenyloxyl oxide can be exemplified. Octyl isocyanate, 10-propenyloxime isocyanate, 2-(2-isocyanate ethoxy)ethyl acrylate, 2-[2-(2-isocyanate ethoxy)ethoxy]ethyl acrylate, acrylic acid 2 -{2-[2·(2-isocyanate ethoxy)ethoxy]ethoxy}ethyl ester, 2-(2-isocyanate propoxy)ethyl acrylate, 2-[2-(2-isocyanate) Acrylic acid derivative such as propoxy)propoxy]ethyl ester; 2-methylpropenyloxyethyl isocyanate, 3-methylpropenyloxypropyl isocyanate, 4-methylpropenyloxybutyl isocyanate, 6 _Methethyloxyhexyl isocyanate, 8-methylpropenyl octyl octyl isocyanate, ι〇_methacrylofluorenyl isocyanate, 2-(2-isocyanate ethoxy)ethyl methacrylate, methyl 2-[2-(2-isocyanate ethoxy)ethoxy]ethyl acrylate, -20- 200900858 methyl 2-{2-[2-(2-isocyanate ethoxy)ethoxy]ethoxy}ethyl acrylate, 2-(2-isocyanate propoxy)ethyl methacrylate-methyl acrylate A methacrylic acid derivative such as 2-[2-(2-isocyanatepropoxy)propoxy]ethyl ester. Further, as a commercial item of 2-propenyl oxirane ethyl isocyanate, the product name is Karenz AOI (manufactured by Showa Denko Co., Ltd.), and 2-methyl propylene oxirane ethyl isocyanate is commercially available under the trade name Karenz MOI. (product of Showa Denko Co., Ltd.), a commercial product of 2-(2-isocyanate ethoxy)ethyl methacrylate, is commercially available as Karenz MOI-EG (manufactured by Showa Denko KK). Among these unsaturated isocyanate compounds, in terms of reactivity with the copolymer [α], 2-propenyloxyethyl isocyanate, 2-methylpropenyloxyethyl isocyanate, 4-methylpropene oxime Oxybutyl butyl isocyanate, 2-(2-isocyanate ethoxy)ethyl methacrylate or the like is preferred. In the polymer, the unsaturated isocyanate compound may be used singly or in combination of two or more. In the present invention, the reaction of the copolymer [α] with an unsaturated isocyanate compound is, for example, a copolymer containing a catalyst such as di-n-butyltin dilaurate (IV) or a polymerization inhibitor such as p-methoxyphenol [α The solution can be carried out by adding an unsaturated isocyanate compound while stirring at room temperature or under heating. [Α] The amount of the unsaturated isocyanate compound used in the production of the polymer is 1 equivalent to the hydroxyl group of the compound (a2_i) in the copolymer [α], -21 - 200900858 is preferably 0 · 1 to 9 5 m %, further preferably 1 to 8 〇 mol%, particularly preferably 5 to 75 mol%. When the amount of the unsaturated isocyanate compound is less than 1% by mole, the effect of improving the heat resistance of the sensitivity and the improvement of the elastic property is small. When the amount exceeds 95% by mole, the unreacted unsaturated isocyanate compound remains. There is a tendency that the storage stability of the obtained polymer solution or the radiation sensitive linear resin composition is lowered. [Α] The polymer and the copolymer [β] can each be used singly, and the storage stability of the obtained linear radiation-sensitive resin composition, and the strength and heat resistance of the spacer are further improved. Α] Polymers and copolymers [Ρ] are further preferred. In the present invention, in the case of using [Α] a polymer and a copolymer [β], the amount of the copolymer [β] used is preferably 0. by weight based on 100 parts by weight of the [Α] polymer. 5 to 50 parts by weight, more preferably 1 to 40 parts by weight, particularly preferably 3 to 30 parts by weight. The amount of copolymer [β] used is less than 0. When the amount is 5 parts by weight, the effect of improving the strength or heat resistance of the separator is small. On the other hand, when it exceeds 50 parts by weight, the storage stability of the linear radiation-sensitive resin composition tends to be lowered. _[Β] Polymerizable unsaturated compound - [Β] A polymerizable unsaturated compound is formed by an unsaturated compound polymerized by exposure of a radiation in the presence of a linear polymerization initiator of a radiation. The above-mentioned [Β] polymerizable unsaturated compound is not particularly limited, and a compound having four or more polymerizable unsaturated bonds in one molecule (hereinafter referred to as "polymerizable unsaturated compound [ΒΠ") and one In the molecule, -22-200900858 compounds having 1 to 3 polymerizable unsaturated bonds (hereinafter referred to as "polymerizable unsaturated compound [B2]") each contain at least. 1 type is better. Examples of such a polymerizable unsaturated compound [B 1 ] include, for example, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol. a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and a molecule other than a methyl (meth) acrylate, a tris(2-(methyl) propylene oxy oxy) phosphate, or the like An amine oxime (meth) acrylate compound obtained by reacting a compound having one or more hydroxyl groups and having 3 to 5 (meth) acryloxy groups in the reaction. The commercial product of the polymerizable unsaturated compound [B 1 ] may, for example, be aronix M-400, the same M-402, the same M-405, the same M-450, the same M-1310, the same M- 1 6 00. , with M- 1 960, the same as · 7 1 0 0, the same as - 8 0 3 0, the same as -80060, the same as -800, the same as -853 0, the same as -8560, the same as the -9050,aronix ΤΟ-1450,同ΤΟ-1382 (above, manufactured by Toagosei Co., Ltd.), KAYARADDPHA, same as DPCA-20, DPCA-30, DPCA-60, DPCA-120, and MAX-3510 (above, Nippon Chemical Co., Ltd.) System), bisuko_to 295, same as 300, with 360, with GPT, with 3PA, with 400 (above, Osaka Organic Chemical Industry Co., Ltd.), or urethane acrylate-based compound can be exemplified by New frontier R-U50 (p. (Industrial Pharmaceutical Co., Ltd.), KAYARAD DPHA-40H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.), UN-9000H (manufactured by Kokusai Industrial Co., Ltd.), etc. The above polymerizable unsaturated compound [B2] may, for example, be ω·carboxy-23- 200900858 polycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate ' 1,6-hexyl Alkanediol di(meth)acrylate, iota, 9-decanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate' Polypropylene glycol di(meth)acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, 2-hydroxy-3-(methyl) Propylene oxime propyl methacrylate, 2-(2'-vinyloxyethoxy)ethyl (meth) acrylate, trimethylolpropane tri(meth) acrylate, neopentyl alcohol three ( Methyl) acrylate or the like. The commercial product of the polymerizable unsaturated compound [B2] may, for example, be aronix M-5 3 00, the same M-5600, the same M-5 700, M-210, the same M-220, the same M-240, Same as M-270, same as M-6200, same as M-3 05, same as M-309, same as M-310, with M-315 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, with HX- 620, same as R-526, same as R-167, same as R-604, same as R-6 84, same as R-5 5 1, with R-712, UX-2201, UX-230 1, UX-3204, UX- 3 3 0 1, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, manufactured by Sakamoto Chemical Co., Ltd.), Art-resin UN-9000PEP, With UN-9200A, with UN-7600, with UN-3 3 3 ' with UN-1 00 3, with UN-1 25 5, with UN-6060PTM, with UN - 6 0 6 0 P (above, Roots Industrial Co., Ltd. ") Same as SH-500B Viscoat 260' with 312' with 3 3 5 HP (above, Osaka Organic Chemical Industry Co., Ltd.). In the present invention, the [B] polymerizable unsaturated compound may be used singly or in combination of two or more. -24- 200900858 The use ratio of the [B] polymerizable unsaturated compound in the sensitive radiation linear resin composition of the present invention is preferably from 40 to 250 parts by weight, more preferably from 100 to 250 parts by weight, based on 100 parts by weight of the [A] copolymer. 60 to 180 parts by weight. In the case of using the polymerizable unsaturated compound [B 1 ] and the polymerizable unsaturated compound [B 2 ], the ratio of the polymerizable unsaturated compound [b 1 ] is preferably 4 0 to 9 9 The weight % is more preferably 6 0 to 9 5 wt%. By containing the [B] polymerizable unsaturated compound in such ratios, the sensitive radiation linear resin composition of the present invention can form a fine pattern close to the size of the opening of the mask, and can be easily obtained even in a low exposure amount. Fully hardenability. -[C]sensitive radiation linear polymerization initiator - [C] sensitive radiation linear polymerization initiator, which can be started by visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray radiation, etc. [B] The active species of the polymerization of the polymerizable unsaturated compound are formed by the components which are generated. Examples of such a [C] radiation-sensitive linear polymerization initiator include 〇 醯 醯 肟 化合物 compounds, acetophenone compounds, bisimidazole compounds, benzoin compounds, diphenyl ketone compounds, α - II. A ketone compound, a polynuclear oxime compound, an xanthone compound, a phosphine compound, a triterpenoid compound or the like. The sensitive radiation linear resin composition of the present invention is preferably a [C] photosensitive radiation polymerization initiator. In the sensitive radiation linear resin composition of the present invention, [C] sensitive radiation linearity -25 - 200900858 The polymerization initiator is used in an amount of '0% by weight relative to the [B] polymerizable unsaturated compound, preferably 0. 01 to 120 parts by weight, more preferably 1 to 100 parts by weight. When the amount of the linear radiation polymerization initiator used is less than 0.1 part by weight, there is a tendency that the residual film ratio at the time of development is lowered. On the one hand, when it exceeds 120 parts by weight, alkali development with respect to the unexposed portion at the time of development The solubility of the liquid tends to decrease. The above ruthenium-oxime oxonium compound may, for example, be exemplified by ^[9-ethyl-6-phenylindenyl-9. H--oxazol-3-yl]-nonane-1,2-decane-2-indole-0-benzoate, 1-[9-ethyl-6-phenylhydrazinocarbazole-3- ]-decane-1,2-decane-2-indole-0-acetate, 1-[9-ethyl-6-benzoinyl- 9. H.  -isoxazole-3-yl]-pentane-1,2-pentane-2-indole-0-acetate' 1-[9-ethyl-6-phenylindenyl-9. H. -oxazol-3-yl]-octane-1-one oxime-0-acetate, 1-[9-ethyl-6-(2-methylbenzoinyl)-9. H·-carbazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9. H--oxazol-3-yl]-ethane-1-one oxime-indole-acetate, 1-[9-ethyl-6-(1,3,5-trimethylbenzoinyl)-9 . :«. -oxazol-3-yl]-ethane-1-one oxime-0-benzoate, 1-[9-butyl-6-(2-ethylphenylhydrazino)-9. H. -oxazol-3-yl]-ethane-1-one oxime-indole-benzoate, ethanone, 1-[9-ethyl-6-[2-methyl-4-(2 ,2-dimethyl-1,3-dioxolanyl)methoxybenzoinyl-9. H.-carbazol-3-yl]-, 1-(anthracene-ethene), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0- Phenyl oxime), 1,2-butanedione-l-[4-(phenylthio)phenyl]-2-(0-phenylhydrazine), 1,2-butanedione- 1-[4-(Phenylthio)phenyl]-2-(0-acetoxime), 1,2-octanedione-1-[4-(methylthio)phenyl]-2 -(0-benzoquinone), 1,2-octanedione-1-[4-(phenylthio)benzene-26- 200900858 base]_2- (〇-(4-methylphenylhydrazine) )) '1,2-octanedione, 1-[4-(phenylthio)-, 2-(indole-benzoquinone) and the like. Among these ◦-醯 肟 肟 compounds, especially ^[9-ethyl-6·(2-methylphenyl fluorenyl)-9. H.  -oxazol-3-yl]-ethane-1-one oxime-indole-acetate, ethanone, 1-[9-ethyl-6-[2-methyl-4-(2,2 - monomethyl-1,3-dioxolanyl)methoxybenzoinyl]oxazole·3·yl]-j·(〇-acetamidine), 1,2-octanedione-1 -[4-(phenylthio)phenyl]-2-(anthracene-benzoquinone), anthracene, 2-octanedione, 1-[4-(phenylthio)-, 2_ (〇 -Benzene oxime) is preferred. The above oxime-oxime oxime compounds may be used singly or in combination of two or more. In the present invention, a high-sensitivity radiation-sensitive linear resin composition can be obtained by using a ruthenium-oxime oxime-based compound, and a spacer or a protective film having good adhesion can be obtained. In the sensitive radiation linear resin composition of the present invention, as the [C] radiation-sensitive linear polymerization initiator, together with the 0-anthracene-oxygen type polymerization initiator, one or more other radiation-sensitive linear polymerization initiators may be used. . The above other radiation-sensitive linear polymerization initiator is preferably, for example, an acetophenone compound or a biimidazole compound. The acetonitrile compound may, for example, be a hydroxyketone compound or an α-amino ketone compound. The above α-hydroxyketone compound may, for example, be 丨-phenyl-2_hydroxy-2-methylpropan-1-one ' 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-; l•嗣' 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2_propyl-27- 200900858) ketone, hydroxycyclohexyl phenyl ketone, and the like. The α-amino ketone compound may, for example, be 2-methyl-1-(4-methylthiophene)-2-morpholino propyl-1-one, 2-methyl-1. -[4-(transethylethylthio)phenyl]-2 -morpholino propan-1-one, 2-phenyl-2-phenylamino-1-(4-? Morpholinophenyl)butane-1-ketone, 2-(4-methylphenylhydrazino)-2-(dimethylamino)-1-(4-morpholinophenyl)-butyl Alkan-1-one and the like. Further, examples of the acetophenone-based compound other than the above may, for example, be 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, 2,2-dimethoxy- 2-phenylethyl benzene and the like. Among these acetophenone compounds, especially 2-methyl-1-(4-methylthiophene)-2-morpholinopropan-1-one, 2-methyl ip- Thio)phenyl]-2-morpholino propyl-1-one, 2-(4-methylphenylhydrazino)-2-(dimethylamino)-1-(4- Morpholinophenyl)-butan-1-one is preferred. The above acetophenone-based compound may be used singly or in combination of two or more. In the present invention, the sensitivity of the spacer shape and the compressive strength can be further improved by using an acetophenone-based compound. Further, as the above bisimidazole compound, for example, 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)- can be exemplified. 1,2,_bisimidazole '2,2,-bis(2-bromophenyl)_4,4,5,5,_tetra(4-ethoxycarbonylphenyl)-1,2,-double Imidazole, 2,2,-bis(2-chlorophenyl)-4,4,5,5,-tetraphenyl-1,2'-bisimidazole, 2,2,-bis (2,4-di Chlorophenyl)-4,4,5,5'-tetraphenyl-1,2,-bisimidazole, 2,2,-bis(2,4,6-trichlorophenyl)-4,4, ,5,5,-Tetraphenyl-1,2,-bisimidazole, 2,2,-bis(2-bromophenyl)-4,4,5,5,-tetraphenyl-28- 200900858 1,2'-bisimidazole '2,2,-bis(2,4-dibromophenyl)-4,4',5,5,-tetraphenyl-1,2'-bisimidazole '2,2 ,-bis(2,4,6-tribromophenyl)-4,4,5,5'-tetraphenyl-1,2'-bisimidazole, and the like. Among these bisimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2,-bisimidazole, 2,2,- Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2,-bisimidazole, 2,2,-bis(2,4,6-trichlorobenzene Base 4,4',5,5'-tetraphenyl-1,2,-bisimidazole, etc., especially 2,2,-bis(2,4-dichlorophenyl)-4,4 ,,5,5,-Tetraphenyl-1,2'-bisimidazole, 2,2,-bis(2-chlorophenyl)-4,4,5,5,-tetraphenyl-1,2 , - Biimidazole is preferred. These biimidazole-based compounds may be used singly or in combination of two or more kinds. In the present invention, the sensitivity "resolution" and adhesion can be further improved by using a bisimidazole compound. Further, in the case of using a bisimidazole-based compound in combination, an aliphatic or aromatic compound having a dialkylamine group (hereinafter referred to as "amine-based sensitizer") may be added for the purpose of sensitization. . The amine-based sensitizer may, for example, be N-methyldiethanolamine, 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino). Diphenyl ketone, p-dimethylamino benzoic acid ethyl ester 'p-dimethylamino benzoic acid isoamyl ester, and the like. Among these amine-based sensitizers, 'especially 4,4'-bis(diethylamino)diphenyl ketone is preferred. The above amine-based sensitizers ' can be used singly or in combination of two or more kinds. Further, in the case of using a bisimidazole-based compound and an amine-based sensitizer, a thiol-based compound may be added to the hydrogen-hydrogen compound. The biimidazole-based compound is cleavable by the above-mentioned amine-based sensitizer and is cleaved, and an imidazole radical can be generated. However, the high polymerization initiation energy cannot be exhibited as described above, and the resulting spacer has a reverse tapered shape. There are many situations with inappropriate shapes. However, in the case where a bisimidazole-based compound and an amine-based sensitizer are coexistent, by adding a thiol-based compound, hydrogen is supplied from the thiol-based compound as a result of the imidazole radical, and the imidazole radical is converted into At the same time as the imidazole, a component having a high sulfur radical energy having a polymerization initiation energy is generated, whereby the shape of the spacer can be made into a more appropriate tapered shape. The above thiol compound may, for example, be 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio-5-methoxy group. An aromatic compound such as benzothiazole, 2-hydrothio-5-methoxybenzimidazole; 3 - thiopropyl propionic acid, methyl 3-hydrothiopropyl propionate, 3 · thiopropyl propionate An aliphatic monothiol such as ester, octyl 3-hydrothiopropionate; 3,6-dioxa-1,8-octane dithiol, isopentanol tetrakis (hydrothioacetate), An aliphatic thiol having two or more functional groups such as isopentanol tetrakis(3 · thiopropyl propionate). Among these thiol compounds, especially 2-hydrothiobenzothiazole is preferred. These thiol-based compounds may be used singly or in combination of two or more kinds. In the sensitive radiation linear resin composition of the present invention, in the case of using a lanthanum-anthraquinone-based compound and other radiation-sensitive linear polymerization initiators, the ratio of use of other sensitive radiation linear polymerization initiators is linearly distributed in sensitized radiation. -30- 200900858 In the initiator, it is preferably 30 to 98% by weight 'and further preferably 40 to 95% by weight. When the ratio of use of other sensitive radiation linear polymerization initiators is less than 30% by weight, there is a possibility that a fine pattern cannot be formed, and on the other hand, when it exceeds 98% by weight, the sensitivity is lowered. Further, in the case of using a bisimidazole-based compound and an amine-based sensitizer, the amount of the amine-based sensitizer added is preferably 0% by weight based on 100 parts by weight of the bisimidazole compound. 1 to 150 parts by weight, more preferably 1 to 120 parts by weight. The amount of the amine-based sensitizer is less than 0. When the amount is 1 part by weight, there is a tendency that the effect of improving the resolution and the adhesion is lowered. On the other hand, when it exceeds 150 parts by weight, the shape of the obtained spacer tends to be impaired. In the case of using a bisimidazole compound and a thiol compound, the amount of the thiol compound added is preferably from 1 to 80 parts by weight, more preferably from 5 parts by weight to the diimidazole compound. ~60 parts by weight. When the amount of the thiol-based compound added is less than 1 part by weight, the effect of improving the shape of the obtained separator may be lowered, and the residual film ratio may be lowered. On the other hand, when it exceeds 80 parts by weight, the resulting spacer may be damaged. The tendency of the shape. -[D]Nitrate-based compound-[D]Nitrate-based compound is a diffraction phenomenon of exposed light at the opening of the reticle, and diffusion of exposed light by the sensitive linear resin composition itself The scattering is caused by a component of the photopolymerization reaction of the linear radiation-sensitive resin composition outside the original exposed region. By containing these components, a fine pattern close to the size of the opening of the mask can be formed without impairing the sensitivity or the shape of the resulting spacer. -31 - 200900858 In the case of such a [D] nitrate-based compound, for example, a compound represented by each of the formulas (1 1), (1-2) and (1-3) can be exemplified.

(wherein, each R is independently of each other, and represents an alkyl group having 1 to 12 carbon atoms; Z and T are represented as a group necessary for completion of a 5- or 6-membered ring, E represents a 2 or 3-valent organic group, and η represents 2 or 3 integer). As the appropriate R aspect in the formula (1 -1), for example, a methyl group, an ethyl group or the like can be exemplified. Further, the compound represented by the formula (1-2) may, for example, be a compound represented by the following formulas (1-2-1) and (1-2-2), and the like. -32- 200900858 Ο

(1-2-2) (wherein X represents a hydrogen atom, a hydroxyl group, a decyloxy group, a decylamino group or a quinone imine group.) Further, in the compound represented by the formula (1-3), the appropriate substance For example, a compound represented by each of the following formulas (1-3-1) and (1-3-2) can be mentioned.

(1-3-1) Cyclohexanediyl, cyclohexenediyl or carbon number 6 to 12 (wherein Y represents a methylene group, a carbon number of 2 to 12 alkylene group or an alkenylene group (alkenylene) ) 200900858 The extension of the base).

(In the formula, R1 represents an alkyl group having 1 to 12 carbon atoms.) Specific examples of such a nitrate-based compound include the following compounds. Further, the structural formula of each compound is as shown below, attached to the English letter after the compound name. Di-tertiary butyl fluorenyl (a), 1-hydroxy-2,2,6,6-tetramethylpiperidine (b), 1-hydroxy-2,2,6,6-tetramethylper Acridine-4-ol (c), 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-one (d), I-hydroxy-2,2,6,6-tetramethyl Piperidin-4-yl acetate (e), 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate (f), 1-hydroxy- 2,2,6,6-tetramethylguanidin-4-yl stearate (g) ^ 1-yl-based-2,2,6,6-tetramethylphosphonium II-4-phenylene Acid ester (h), l-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl-4-tris-butyl benzoate (i), bis(1-hydroxy-2) , 2,6,6-tetramethylpiperidin-4-yl) succinate (j), bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-34- 200900858 pyridine-4- Adipate (k), bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate (1), bis(1-hydroxy-2, 2,6,6-Tetramethylpiperidin-4-yl)-n-butylmalonate (m), bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl ) phthalate (η), bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)isophthalate (〇), bis(1-hydroxy- 2.2.6.6- Tetramethylpiperidin-4-yl)-p-benzene Dicarboxylate (p), bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate (q), Ν,Ν'-double (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate diamine (r), N-(l-hydroxy-2,2,6,6-tetramethyl Isopiperidin-4-yl) caprolactam (s), N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)dodecyl amber imine (t ), 2,4,6-tris-[n-butyl-> 1-(1-hydroxy-2.2.6.6-tetramethylpiperidin-4-yl)-3-triterpene (1〇. -35 - 200900858

-36- 200900858

Ο

\i/ ο -37- 200900858

(P)

(q) (r)

ο (1) (s) ο

(u) -38- 200900858 Among these nitrate-based compounds, in particular, bis(l-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2, 4,6-tri-[n-butyl-N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)-s-triterpene, or 4,4'-ethylene Bis(1-hydroxy-2,2,6,6-tetramethylhexahydropyridin-3-one) is preferred. For example, IRGASTAB UV10, IRGASTAB UV22 (above, manufactured by Chiba Special Chemicals Co., Ltd.), etc., may be mentioned as a commercial product of such a nitroxide compound. In the sensitized radiation linear resin composition of the present invention, the amount of the [D] nitroxyl group compound is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 重量 by weight based on 100 parts by weight of the [A] copolymer. Share. When the amount of the [D] quinone-based compound is less than 0.001 part by weight, the desired effect may not be obtained. On the other hand, when it exceeds 2 parts by weight, the sensitivity is lowered to impair the shape of the pattern. - [E] Chain Transfer Agent - In the sensitive radiation linear resin composition of the present invention, it is preferred to further contain the [E] chain transfer agent. By using the [E] chain transfer agent and the [D] nitridyl compound, it is possible to form a fine pattern close to the size of the opening of the mask. In the case of the chain transfer agent, the compound which can be used as a chain transfer agent in the radical polymerization reaction is not particularly limited, and examples thereof include a compound represented by the following formula (2), a mercaptan, and the like. . -39- 200900858

••(2) (wherein R2 is independently of each other' represents hydrogen or an alkyl group having 3 or less carbon atoms). The R aspect in the formula (2) may, for example, be a methyl group, an ethyl group, a n-propyl group or an isopropyl group. Specific examples of the chain transfer agent include, for example, a compound represented by the above formula (2): 2,4-diphenyl-4-methyl-1-pentene, etc.: butyl thiol, butyl-3 -Hexylthiopropionate '3-hydrothiopropionic acid, 3-hydrothiopropylpropionic acid methyl acetonate, ethyl 3-hydrothiopropionate, octyl 3-oxothiopropionate, isooctyl-3 - an aliphatic monothiol such as thiopropyl propionate; 3,6-dioxa-1,8-octane dithiol, isopentanol tetrakis (hydrothioacetate), isopenic An aliphatic thiol having two or more functional groups such as tetraol tetrakis(3-hydrothiopropionate). Among the chain transfer agents, a compound represented by the above formula (2) is preferred, and 2,4-diphenyl-4-methyl-1-pentene is particularly preferred. The amount of the [E] chain transfer agent used in the sensitive radiation linear resin composition of the present invention is preferably 3 parts by weight or less with respect to the [A] by weight of the copolymer, and further preferably 〇. 5 to 2 parts by weight. . When the amount of the [E] chain transfer agent is more than 3 parts by weight, the decrease in sensitivity may impair the shape of the pattern. -Additive -40-200900858 In the range of undesired effects, the sensitive radiation linear resin composition of the present invention can be used in combination with a surfactant, an adhesion aid, and a storage stabilizer. Additives such as agents. The surfactant has an effect of improving coatability. A fluorine-based surfactant and a polyoxyn-based surfactant are preferred. In the case of the fluorine-based surfactant, in the case where the terminal has a terminal or a part of the main chain, the fluorine-containing compound or the fluorine-based rubbing base is used, and specific examples thereof include 1,1,2,2-tetrafluoro. Octyl (1, n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) alcohol di(1,1,2,2-tetrafluoro-n-butyl)ether, six Ethylene glycol (hexafluoro-n-pentyl) ether, octapropylene glycol di(1,1,2,2-tetra-ether 'hexapropanediol di(1,1,2,2,3,3-hexafluoro-n-pentane) 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,1< dioxane, perfluoro-n-dodecyl fluorene Sodium, or sodium fluoroalkylphenylphosphonium hydride, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, base (baeaine) , fluoroalkyl polyoxyethylene ether, perfluoroalkyl perfluorinated hospital alkoxylate (alkoxylate), fluorine based hospital, and fluorine-based surfactant commercial products, commodity BM-1 000, the same 1 1 〇〇 (above, BM CHEMIE mega fuck F142D, same as F172, with F173, with F1 83 with F191, with F471, with F476 (above, manufactured by Otsuka Oil Company), Fluorad FC 170C, with F C-171, in addition to the loss of the present invention, is also a component having improved heat resistance, and a conjugate of a side chain. 1,2,2-tetra-o-ether, octaethylene 1,1,2,2 , 3,3-membered-n-butyl) yl)ether, decafluoro-n-dodecanoate, halothane, diglycerol tetrafluoroalkyl beet polyoxyethylene, ester, etc.. For example, company system), , the same F178, ink chemical industry FC-430, with -41 - 200900858 FC-431 (above, Sumitomo 3M company), Safron S-112, with S-113, with S-131, with S-141, with S-145 , with S-382, with SC-101, with SC-102, with SC-103, with SC-104, with SC-105, with SC-106 (above, Asahi Glass Co., Ltd.), f-top EF301, with EF303 , with EF352 (above, new Akita Chemical Co., Ltd.), ffergent FT-100, with FT-110, with FT-140A, with FT-150, with FT-25 0, with FT-251, with FTX-251, same FTX-218, same as FT-3 00, with FT-310, with FT-400S (above, manufactured by Neos). For the polyoxo-based surfactant, commercially available products have trade names such as Toray Silicone DC3PA, same as DC7PA, same as SH11PA, same as SH21PA, same as SH28PA, same as SH29PA, same as SH30PA, with SH-190, and SH-193, Same as SZ-6032, same as SF-8428, same as DC-57, with DC-190 (above, manufactured by Toray. Dow Corning Co., Ltd.), TSF-4440, same as -4300, same 4445, same 4446, same ~· 4 4 6 0 'The same 4452 (above, GE Toshiba Poly Oxygen Co., Ltd.) and so on. Further, examples of the surfactant other than the above may include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl phthalate, and polyoxyethylene oleyl ether; and polyoxyethylene Polyoxyethylene aryl ethers such as octyl phenyl ether, polyoxyethylene n-decyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate or polyoxyethylene distearate For example, KP34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow-No. 57, Νο·95 (manufactured by Kyoei Chemical Co., Ltd.), etc., etc., are used as a non-ionic surfactant or the like. . These surfactants can be used singly or in combination of two or more. The amount of the surfactant to be added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the [A] polymer. When the amount of the surfactant is more than 5 parts by weight, there is a tendency that film dry spots are likely to occur during coating. The adhesion aid has a function of improving the adhesion between the separator and the substrate, and a functional decane coupling agent is preferred. The functional decane coupling agent may, for example, be a compound having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group. More specifically, trimethoxydecyl benzoic acid, r-methyl propylene oxypropyl trimethoxy decane 'ethylene triethoxy decane, ethylene trimethoxy decane, γ-isocyanate propyl three can be exemplified. Ethoxy decane, γ-glycidylpropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These adhesion aids may be used singly or in combination of two or more. The amount of the adhesion aid is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less based on 1 part by weight of the [Α] polymer. When the amount of the adhesion aid is more than 20 parts by weight, residual development tends to occur. Examples of the storage stabilizer include, for example, sulfur 'hydrazines, hydroquinones, polyoxygen compounds, amines, nitroso compounds, and the like. More specifically, 4-methoxyphenol, hydrazine-nitrocene is exemplified. Base-oxime-phenylhydroxylamine aluminum and the like. These storage stabilizers may be used alone or in combination of two or more. The compounding amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.001 to 0.5 part by weight - 43 to 200900858 parts, per 100 parts by weight of the [Α] polymer. When the amount of the stabilizer is more than 3 parts by weight, the sensitivity may be lowered to impair the shape of the pattern. The heat resistance improving agent may, for example, be an N-(alkoxymethyl)acetylene urea compound or an N-(alkoxymethyl)melamine compound. The N-(alkoxymethyl)acetylene urea compound may, for example, be N',N",N'",N""-tetrakis(methoxymethyl)acetylene urea, ,,", 14, ",^^'"-tetrakis(ethoxymethyl)acetylene urea, N',N",N'",N""-tetrakis(n-propoxymethyl)acetylene urea, N',N", N'", N""-tetrakis (i-propoxymethyl) acetylene urea, N', N", N'", N""-tetrakis (n-butoxymethyl) acetylene urea, N', N", N'", N""-tetrakis (tertiary butoxymethyl) acetylene urea, etc. Among the N-(alkoxymethyl)acetylene urea compounds, especially N', N", N'", N""-tetrakis (methoxymethyl) acetylene urea is preferred. Further, the N-(alkoxymethyl) melamine compound may, for example, be a chemical compound. -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(i-propoxymethyl)melamine, N N,N',N',N",N"-hexa(n-butoxymethyl)melamine, N,N,N',N',N",N"-hexa(t-butoxymethyl ) melamine and the like. Among these N-(alkoxymethyl)melamine compounds, in particular, it is preferred to use phthalocyanine, and it is commercially available, and the commercial name is For example, Nikalac N-2702 is the same as MW-3 0M (manufactured by Sanwa Chemical Co., Ltd.). -44 - 200900858 The heat resistance improver may be used alone or in combination of two or more. The amount of the heat resistance improving agent is preferably 30 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the [A] polymer. When the compounding amount of the heat resistance improving agent exceeds 30 parts by weight, the storage stability of the radiation sensitive linear resin composition tends to be lowered. The sensitive radiation linear resin composition of the present invention is preferably used as a composition solution dissolved in a suitable solvent. In terms of the solvent, the components constituting the linear radiation-sensitive resin composition are uniformly dissolved, and do not react with the respective components, and the substances having moderate volatility can be used, and the solubility of each component and the reactivity of each component can be used. And from the viewpoint of easiness of formation of a coating film, an alcohol, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkane Ethyl ether acetate, dipropylene glycol alkyl ether, alkyl alkoxypropionate, acetate, etc., especially benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol 'B Glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate 'diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate 'dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 2-methoxyethyl acetate, etc. are preferred. These solvents may be used singly or in combination of two or more. In the present invention, a high boiling point solvent can be used together with the solvent. The high boiling point solvent may, for example, be N-methylmethanoamine, N,N-dimethylformamide, N-methylformamide, N-methylethenamine, N,N-di Methylacetamide, N-methylpyrrolidone, dimethyl hydrazide, benzyl-45- 200900858 ethyl ether 'β-n-hexyl ether, acetone acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, Ethylene glycol monophenyl ether acetate and the like. These high-boiling solvents may be used singly or in combination of two or more. - Further, the composition solution prepared as described above is filtered by using a micropore filter having a pore diameter of about 0.5 μm. # The radiation-sensitive linear resin composition of the present invention, particularly the spacer for a liquid crystal display element or the formation of a protective film, can be used extremely suitably. Method of Forming Spacer or Protective Film Next, a method of forming a spacer or a protective film of the present invention will be described using the radiation sensitive linear resin composition of the present invention. The formation of the spacer or protective film of the present invention contains at least the following steps in the following order. V (a) a step of forming a film of the sensitive radiation linear resin composition of the present invention on a substrate, (b) a step of exposing at least a portion of the film, and (c) a step of developing the film after exposure And (d) the step of heating the film after development. Hereinafter, each of the steps will be described in order. - (A) Step - When forming a protective film, red, green, and blue are formed on the transparent substrate - 46 - 200900858 The color layer is formed into a pixel, and on the colored layer, a sensitive radiation linear resin composition is preferably used. After coating as a composition solution, the coated surface is heated (prebaked) to form a film. Further, at the time of forming the spacer, a transparent conductive film is formed on one surface of the transparent substrate formed by the pixel or further on the transparent substrate formed by the upper protective film, and the sensitive radiation is linearly formed on the transparent conductive film. The resin composition is preferably formed as a composition solution, and then the coated surface is pre-baked to form a film. The transparent substrate to be used herein may, for example, be a glass substrate, a resin substrate or the like. More specifically, a glass substrate such as soda lime glass or alkali-free glass may be mentioned; polyethylene terephthalate or a poly-pair A resin substrate made of plastics such as butyl phthalate (PBT), polyether oxime, polycarbonate, or polyimide. For the transparent conductive film provided on one surface of the transparent substrate, for example, a NESA film made of tin oxide (Sn02) (registered trademark of PPG Corporation of the United States), an ITO film formed of indium oxide-tin oxide (In203-Sn02), or the like can be used. In the method of coating the composition solution, in the method of forming the film of the radiation sensitive linear resin composition of the present invention, for example, (1) a coating method, and (2) a dry film method can be used. For the coating method of the composition solution, for example, a spray method, a roll coating method, a spin coating method (spin c〇at), a slit die coating method, a bar coating method, an inkjet coating method, or the like can be employed. The method is particularly preferably a spin coating method or a slit die coating method. Further, in the case of forming the film of the sensitive radiation linear resin composition of the present invention, in the case of using the (2) dry film method, the dry film is based on a substrate - 47 - 200900858 film, preferably a flexible substrate. On the film, a linear layer of a sensitive radiation layer of the sensitive radiation linear resin composition of the present invention is laminated (hereinafter referred to as "photosensitive dry film"). The photosensitive dry film is formed on a base film, and the sensitive radiation linear resin composition of the present invention is preferably dried as a liquid composition and dried to form a linear layer of the sensitive radiation. As the base film of the photosensitive dry film, for example, a film of a synthetic resin such as polyethylene terephthalate (PET), polyethylene 'polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the matrix film is suitably in the range of from 1 5 to 1 25 μm. The thickness of the resulting sensitive radiation linear layer is preferably about 1 to 30 μm. Further, when the photosensitive dry film is not used, it is laminated on the sensitive radiation linear layer and the outer film can be laminated and stored. Further, the film is not peeled off when it is not used, and is easily peeled off during use, and it is necessary to have appropriate mold release property. In the case of coating a film which satisfies such a condition, for example, a coating film of a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film or the like can be used for coating a polyfluorene-based release agent. A cloth or a baking film. The thickness of the overcoat film is usually about 25 μm. Further, the conditions for prebaking vary depending on the type of each component, the blending ratio, etc., but usually at 70 to 120 ° C for about 1 to 15 minutes. - (B) Step - Next, exposure is performed on at least a portion of the formed film. In this case, when one part of the film is exposed, it is usually exposed through a photomask having a setting pattern of -48-200900858. In terms of the radiation used for exposure, it is possible to use, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc., and radiation having a wavelength in the range of 190 to 450 nm, especially containing ultraviolet light at 3 65 nm. Light transmission is better. The exposure amount is measured by the illuminance meter (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 3 65 nm of the exposed radiation, and is usually 100 to 1 〇, 〇〇〇 J / M2 is preferably 500 to 3,000 J/m2. - (C) Step - Next - By developing the film after exposure, unnecessary portions can be removed to form a set pattern. In terms of the developer used for development, an alkali developer is preferred, and an example thereof is an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia or the like; An aliphatic primary amine such as n-propylamine; an aliphatic secondary amine such as diethylamine 'di-n-propylamine; trimethylamine 'methyldiethylamine, dimethylethylamine , an aliphatic 3-grade amine such as triethylamine; succinct' piperidine, N-methylpiperidine, N-methylpyrrolidine, anthracene, 8 _ aza-a ring [5·4·0] _7 - 11-membered alicyclic tertiary amine such as ι,5-diazabicyclo[4.3_0]-5-decane; pyridine, trimethylpyridine (c〇1Udine), dimethyl hydrazine An aromatic tertiary amine such as steep porphyrin; an alkanolamine such as ethanol dimethylamine, methyldiethanolamine Ξethanolamine; a tetrabasic ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide An aqueous solution of an alkaline compound. -49- 200900858 Further, in the aqueous solution of the basic compound, methanol, a water-soluble organic solvent or a surfactant may be added in an appropriate amount, and a development method may be used, and the method may be a liquid-filling method, a dipping method, or a washing method. The development time is usually about 10 to 1 80 seconds. After the development, for example, the running water is washed for 30 to 90 seconds, and then compressed air or compressed nitrogen is air-dried to form a desired pattern. - (D) step - Next, the resulting pattern is set by a hot plate, oven, etc., at a set temperature, for example, at 100 to 23 ° C, and is set, for example, on a hot plate. 30 minutes, in the oven for 30 to 30 minutes, heating (post-baking), to obtain a set spacer or a snow-proof liquid crystal display element. The liquid crystal display element of the present invention can be produced, for example, by the following method I (b) . (a) First, a pair of (two sheets) substrates having a transparent conductive film (electrode) on one side are prepared, and on one of the substrates, the sensitive radiation linear resin composition of the present invention is used in accordance with the above-mentioned spacer or protection. Membrane or both. Then, the substrates having the liquid crystal alignment energy are formed on the electric film, the spacer, or the protective film of the substrates, and the surface on which the alignment film is formed is aligned as the liquid crystal alignment direction of the inner self-alignment film. In the anti-parallel manner, the gap (cell gap) is disposed in the opposite direction, and the film is immersed by 180°, for example, by heating time, for example, on the surface of the substrate. :a) or transparent conductive film method transparent guide film. The cell gaps, which are separated by a (alignment -50-200900858 film) and a spacer, are filled with liquid crystal, and the filling holes are sealed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to the outer surfaces of the liquid crystal cell so that the liquid crystal display direction of the alignment film of the alignment film formed on one side of the substrate is uniform or orthogonal to obtain the liquid crystal display of the present invention. 7K software. (b) First, a transparent conductive film, a spacer or a protective film or both of them and the alignment film are formed in the same manner as the above first method to form a transparent substrate. Coating the ultraviolet curable sealant along the end of the rear substrate, using a dispenser, and then using a liquid crystal dispenser to drip the liquid crystal into tiny droplets, and attaching the two substrates under vacuum. Hehe. Then, the high-pressure mercury lamp was used to irradiate the ultraviolet rays on the sealant portion to close the two substrates. Finally, the polarizing plates are bonded to the outer surfaces of the liquid crystal cells to obtain the liquid crystal display element of the present invention. For the liquid crystal used in each of the above methods, for example, a nematic liquid crystal or a smetic liquid crystal can be used. Among them, a nematic liquid crystal is preferable, and for example, a shift base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or an ester liquid crystal can be used. A triphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal or the like. Further, for these liquid crystals, for example, cholesterol type cholesteric liquid crystal such as cholesterol chloride, cholesterol citrate non-cholesterol or cholesterol carbonate or a trade name "C-15" or "CB-15" may be added. (The above, manufactured by Merck) is used for the sale of palmicides. Further, a ferroelectric liquid crystal such as p-oxybenzylidene-p-amino-2_-51 - 200900858 methylbutyl cinnamate may be used. Further, in the case of using a polarizing plate on the outer side of the liquid crystal cell, the polarizing plate or the ruthenium film which is obtained by stretching the alignment of the polyvinyl alcohol while absorbing the iodine, which is called the ruthenium film, is held by the cellulose acetate protective film. It is made into a polarizing plate or the like. The above-mentioned sensitive radiation linear resin composition of the present invention has a high resolution, and a fine pattern can be formed in a high-definition liquid crystal display element. [Embodiment] Hereinafter, embodiments of the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. Here, the parts and % refer to the weight basis. In the following synthesis examples, the measurement of the weight average molecular weight Mw of the copolymer was carried out by gel permeation chromatography (GPC) according to the following apparatus and conditions. Device: GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: GPC-KF-801 > GPC-KF-802, GPC-KF-803 and GPC-KF-804 bonded mobile phase: containing 0.5% by weight of tetrahydrofuran phosphate Example 1 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were charged, followed by 18 parts by weight of methacrylic acid, methacrylic acid ring -52-200900858 oxypropyl ester 40 parts by weight '5 parts by weight of styrene and trimethyl [5_2.1.02'6] decane-8-yl group 32 parts by weight of the ester, after substituting with nitrogen, further charged 5 parts by weight of 1,3-butadiene, slowly stirring and allowing the temperature of the solution to be maintained at # to 7 ° C for 5 hours to be polymerized. A solution of the copolymer [Α_Γ] was obtained. The solid concentration of this solution was 3 3 _ 0% by weight, and the Mw of the copolymer t A_ J ] was 1 1,000. Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2,-azobis(isobutyronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether were charged, followed by 2-A 35 parts by weight of acryloyloxyethyl succinic acid, 25 parts by weight of n-butyl methacrylate and 35 parts by weight of benzyl methacrylate, substituted with nitrogen, and further charged with 5 parts by weight of 1,3-butadiene 'When stirring slowly, the temperature of the solution was raised by 90 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a [A ] copolymer solution having a solid content concentration of 28% by weight. This was used as a copolymer [A-2]. With respect to the obtained copolymer [A-2], when Mw was measured, it was 12, 〇00. Synthesis Example 3 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2,-azobisisobutyronitrile, 250 parts by weight of 'acetic acid 3_methoxybutyl ester, and then 18 parts by weight of methacrylic acid were charged. , tricyclo[meth] methacrylate [5.2.1. 〇 2,6] decane _ 8-yl ester 25 parts by weight 'styrene 5 parts by weight, methacrylic acid 2 hydroxy-53- 200900858 ethyl ester 30 parts by weight and After 22 parts by weight of benzyl methacrylate was replaced with nitrogen, the mixture was slowly stirred to raise the temperature of the solution to 80 ° C, and the temperature was maintained for 5 hours to be polymerized to obtain a copolymer having a solid component concentration of 28.8% by weight. -l] solution. With respect to the obtained copolymer [α -1 ], when Mw was measured, it was 1 3,0 0 0. Next, 12 parts by weight of 3-methoxypropenyloxyethyl isocyanate (trade name: Karenz®, manufactured by Showa Denko Co., Ltd.) was added to the copolymer [α-1] solution in an amount of 1 part by weight, 4-methoxy group. After 0.1 part by weight of phenol, the reaction was carried out at 40 ° C for 1 hour and further at 60 ° C for 2 hours with stirring. The reaction between the isocyanate group derived from 3-methylpropenyloxyethyl isocyanate and the hydroxyl group derived from the copolymer [α-1] can be confirmed by IR (infrared absorption) spectrum. From the IR spectrum of the solution after reacting at 40 ° C for 1 hour and the solution after further reacting at 60 ° C for 2 hours, it was confirmed that 2,270 cm derived from isocyanate groups derived from 3-methylpropenyl methoxyethyl isocyanate ·1 The peak near the peak is reduced. A [A] copolymer solution having a solid content concentration of 3 1.0% by weight was obtained. As a copolymer [A-3] ° Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2,-azobis(isobutyronitrile) and 3-methoxybutyl B were charged. The acid ester was 22 parts by weight. Next, 5 parts by weight of styrene was charged with 15 parts by weight of 'acrylic acid, 15 parts by weight of n-butyl methacrylate, 20 parts by weight of methyl propyl benzyl acrylate and 3-(methacryloxymethyl)-3 -B. 40 parts by weight of oxetane, after taking -54 - 200900858 nitrogen, and then 5 parts by weight of 1,3-butadiene, stirring slowly, increasing the temperature of the solution by 8 01:, this temperature A solution of the copolymer [A-4] was obtained by carrying out polymerization for 5 hours. The solid solution concentration of the obtained copolymer solution was 30.5 wt%, and the Mw of the copolymer [A-4] was 10,700. Synthesis Example 5 In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether were charged. Next, 5 parts by weight of styrene, 20 parts by weight of methacrylic acid, 15 parts by weight of tetrahydrofurfuryl methacrylate, 30 parts by weight of glycidyl methacrylate and 3-(methacryloxymethyl)- 25 parts by weight of 3-ethyloxetane, after being substituted with nitrogen, further charged 5 parts by weight of 1,3-butadiene, and slowly stirred while raising the temperature of the solution to 7 (TC). The polymerization was carried out for 5 hours while maintaining the temperature to obtain a solution of the copolymer [A-5]. The solid solution concentration of the obtained copolymer solution was 28.3% by weight, and the Mw of the copolymer [A_5] was 11,000. Examples 1-23 and comparison Example 1-2 <Preparation of Sensitive Radiation Linear Resin Composition> The components (A) to (E) shown in Table 1, and further, the adhesion aid γ-glycidylpropyldimethoxy sand 2.5 parts by weight of a surfactant, 0.5 parts by weight of a surfactant FTX-218 (trade name: manufactured by Neos Co., Ltd.), and 5 parts by weight of a storage stabilizer, 4-methoxyphenol oxime, were mixed, and the solid content concentration was 20% by weight. After dissolving in propylene glycol monomethyl ether acetate, it is filtered by a microporous filter of -55-200900858 pore size 0.5 μηη. A composition solution was prepared. Further, in Comparative Example 2, further, the polymerization inhibitor was compounded with phenothiazine 〇-56 - 200900858 c component parts by weight 10/5/5/2.5 10/5/5/2.5 10/ 5/5/2.5 10/5/5/2.5 5/5/20 5/5/20 5/5/20 5/5/20 5/5/20 5/5/20 5/5/20 3/5 /15/0.5 5/5/20/0.5 Category C-1/C-2/C-3/C-4 C-1/C-2/C-3/C-4 C-1/C-2/ C-3/C-4 C-1/C-2/C-3/C-4 C-2/C-5/C-6 C-2/C-5/C-6 C-2/C- 5/C-6 C-2/C-5/C-6 C-2/C-5/C-6 C-2/C-5/C-6 C-2/C-5/C-7 C -2/C-5/C-7/C-8 C-2/C-5/C-7/C-8 Part B parts by weight 1 50/100 50/100 50/100 50/100 130/10 130 /10 130/10 130/10 130/15 120/15/10 130/10/15 120/10/15 120/10/15 Category 1 B-1/B-2 B-1/B-2 B-1 /B-2 B-1/B-2 Bl/B-3 Bl/B-3 Bl/B-3 Bl/B-3 Bl/B-4 Β-1/Β-3/Β-4 Β-1 Β Β Β Β Β Β Β Β Β Β Β Β Ο Η Ο Ο Ο 50/50 Category 1 A-1 < A-1/A-2 Α-3 < 丨Α-1 < Α-1 Α-1 Η < 1 < Τ-Η < A-1/1-2 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Example 10 Example 11 Example 12 Example 13 -57- 200900858 Table 1 (continued) D component E component Other component type Weight part kind Weight part type Weight part Example 1 D-1 0.1 — — — — Example 2 D-1 0.05 — — — — Example 3 D-1 0.05 — A — Example 4 D-1 0.05 — — — — Example 5 D-1 0.1 — — — — Example 6 D-1 0.3 — — - Example 7 D-1 0.5 - - - - Example 8 D-1 0.5 E-1 1 - - Example 9 D-1 0.5 E-1 1 - - Example 10 D-1 0.5 E-1 1 - Example 11 D-1 0.5 E-1 1 - - Example 12 D-1 0.5 E-1 1 - - Example 13 D-1 0.5 E-1 1 - - -58- 200900858 sin Parts by weight 5/5/20/0.5 5/5/20 5/5/15 5/5/15 3/5/15/0.5 5/5/20 5/5/20 5/5/15 5/5/ 15/0.5 5/1/5/20 10/5/5/2.5 10/5/5/2.5 Category C-2/C-5/C-7/C-8 C-2/C-5/C- 6 C-2/C-5/C-7 C-2/C-5/C-7 C-2/C-5/C-7/C-8 C-2/C-5/C-7 C -2/C-5/C-7 C-2/C-5/C-7 C-2/C-5/C-7/C-8 C-2/C-3/C-5/C- 7 C-1/C-2/C-3/C-4 C-1/C-2/C-3/C-4 Part B Weight 120/10/10 120/15/10 120/10/15 120/ 10/15 130/10/15 1 120/10/15 120/15/15 ^ 130/10/15 120/15/15 120/10/15 50/100 50/100 Type B-1/B-3/ B-4 B-1/B-3/B-4 B-1/B-3/B-4 B-1/B-3/B-4 B-1/B-3/B-4 B-1 /B-3/B-4 B-1/B-3/B-4 B-1/B-3/B-4 B-1/B-3/B-4 B-1/B-3/B -4 B-1/B-2 B-1/B-2 Part A Part Weight 50/50 〇〇100 〇〇〇〇rH 〇〇1—1 〇rH 〇Type A-1/A-2 A-3 A-3 A-3 A-3 A-1/A-4 A-1/A-4 A-5 A-5 A-5 I1 is called <T i < Embodiment 14 Embodiment 15 Example 16 Implementation EXAMPLES Example 18 Example 19 Example 20 Example 21 Example 22 Example 23, Comparative Example 1 Comparative Example 2 -59- 200900858 Table 1 (Continued) D component E component Other or sub-type weight parts Type by weight Species and parts by weight Example 14 D-1 0.7 E-1 1 - Example 15 D-1 0.5 E-1 1 - Example 16 D-1 0.5 E-1 1 - Example 17 D-1 0.5 E -1 1.5 - Example 18 D-1 0.5 E-1 1 - Example 19 D-1 0.5 E-1 1 - Example 20 D-1 0.7 E-1 0.7 - Example 21 D-1 0.5 E-1 1 ~ - Example 22 D-1 0.5 E-1 1 - Example 23 D-1 0.5 E-1 0.5 - — Comparative Example 1 — — — — — ~ Comparative Example 2 — — — — F-1 0.1 -60- 200900858 (B )

Bl: diisopentyl alcohol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) B-2: Polymerizable unsaturated monomer containing a polyfunctional amine ethyl acrylate compound (trade name KAYARAD DPHA- 40H, manufactured by Nippon Kayaku Co., Ltd.) B-3 : 1,9-decane diacrylate (trade name: Light, C1, N-A, manufactured by Kyoei Co., Ltd.) Β-4: ω - Residue polycaprolactone single-acrylic acid vinegar (trade name: aronix M-53 00, manufactured by Toagosei Co., Ltd.) (C) Ingredients (2-1: 1-[9-ethyl-6-(2-methyl) Benzoyl)-9.11.-carbazol-3-yl]-ethane-1-one oxime-indole-acetate (trade name: Irgacure OXE02', manufactured by Chiba Specialty Chemicals Co., Ltd.) C-2: 2,2' - bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole C-3: 4,4'-bis(diethylamino)diphenyl Ketone C-4: 2-Hydroxythiobenzothiazole C-5: 1,2-octanedione, 1-[4-(phenylthio)-, 2-(0-benzoquinone) )] (trade name Irgacure OXE01, manufactured by Chiba Specialty Chemicals Co., Ltd.) C_6 : 2 -Methyl-l-[4-(methylthio)phenyl]-2-morpholinyl (morpholino) propane-1- Ketone (trade name Irgacure 907, Yate-61 - 200900858 Manufactured by Chemicals Co., Ltd.) C-7: 2-methyl-1-[4-(transethylethylthio)benzyl]-2-morphinyl (morpholino) propyl-1-嗣

C-8 : 2,4-diethyl ketoxime (trade name: KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) (D) Component D-1: bis(1-hydroxy-2,2,6,6 -tetramethylpiperidin-4-yl) sebacate (E) component El: 2,4-diphenyl-4-methyl-1-pentene, other components F-1: phenothiazine In addition, the "one" in the column indicates that the ingredients are not used. <Evaluation> Evaluation of the modulated radiation sensitive linear resin composition was carried out as described above in the following manner. The evaluation results are shown in Table 2. -62- 200900858 £ Voltage holding ratio (%) 〇〇OS Os 00 Os 00 as 00 ON ON Adhesion (/100) 〇Η 〇〇〇〇〇〇〇〇〇〇100 〇〇〇〇〇〇〇〇100 〇〇〇〇100 100 100 〇〇〇〇100 100 〇〇〇〇〇〇100 Compression displacement (μηι) 0.46 0.45 1 0.45 0.45 0.46 0.47 0.47 0.48 0.49 0.50 _1 0.51 0.52 0.51 0.52 0.50 , 0.50 0.51 0.50 0.49 0.50 0.51 0.50 0.50 0.40 0.45 Space on the surface of the spacer 爿 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 resolution (pattern diameter) (μηι) (N 〇\ 00 rH 00 卜卜卜16.5 卜卜16.5 卜卜卜卜developability 〇X 〇 sensitivity (J/m2) 400 400 400 400 450 450 500 500 500 500 500 450 450 550 500 500 550 500 500 500 500 500 450 400 1100 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example Π Example 18 Example 19 Example 20 Example 21 丨 Example 22 Example 23 Comparative Example 1 Comparative Example 2 - 63- 200900858 (1) Evaluation of sensitivity On a non-alkali glass substrate, a rotator was used, and a solution of the above-prepared sensitive radiation linear resin composition was applied, and then pre-baked on a TC hot plate for 3 minutes. Then, a film having a film thickness of 4.0 μm is formed. Next, in the obtained film, the opening is transmitted through a mask having a circular pattern having a diameter of 1 μm, and an ultraviolet ray having an intensity of 250 W/m 2 at 365 nm is used for exposure. The time variable was exposed. Thereafter, it was developed by a 0.05% by weight aqueous solution of potassium hydroxide at 25 ° C for 60 seconds, and then washed with pure water for 1 minute, and further in an oven at 23 ° C for 20 minutes. Bake afterwards to form a spacer. At this time, the residual film rate after the post-baking (film thickness after the post-baking XI 〇〇 / film thickness after the exposure) was 90% or more as the sensitivity. When the sensitivity is 1, 〇〇〇 J/m2 or less, the sensitivity is good. (2) Evaluation of developability A spacer was formed on the substrate in the same manner as the evaluation of (1) sensitivity, except that the exposure amount was 1, 〇00 J/m2, and the development time was 40 seconds. At this time, the case where the pattern was formed was not caused by the residue, and the case where the residue was generated was evaluated by X. (3) Evaluation of resolution In addition to the exposure amount of 1,000 J/m2, other spacers were formed on the substrate in the same manner as (1) sensitivity evaluation. The diameter of the obtained pattern was measured using a laser microscope (VK-8500, manufactured by Keyence Corporation). At -64 - 200900858, the resolution of the pattern is less than 25 μm, and the resolution is good. The resolution is particularly good at less than 20 μm. (4) Observation of the surface state of the spacer A spacer was formed on the substrate in the same manner as (1) sensitivity evaluation except that the exposure amount was equal to the exposure amount determined by (1) the sensitivity evaluation. The obtained pattern was observed by a scanning electron microscope, and if the surface of the spacer was smooth, it was good (〇)', and the dry area was confirmed as a bad (X) ° (5) compression displacement. Evaluation (4) A spacer was formed on the substrate in the same manner as the observation of the surface state of the spacer. With respect to the obtained pattern, a small compression tester (DUH-201, manufactured by Shimadzu Corporation) was used, and the amount of deformation at a load of 50 mN was measured by a plane indentation having a diameter of 50 μm, and the measurement was carried out at a measurement temperature of 23 t. When the 値 is 0.45 or more, the amount of compression displacement is good. (6) Evaluation of the adhesion property The exposure amount is equal to the exposure amount determined by the sensitivity of the evaluation of the sensitivity (1), and the evaluation is performed on the substrate in the same manner as the evaluation of the sensitivity of (1). Hardened film. Thereafter, in the adhesion test of 〖IS K-5400 (1900) 8 _ 5, it was evaluated by the crosscut taping method of 8.5.2. At this time, the number of checkerboard eyes remaining in the eyes of one of the checkers is as shown in Table 2. -65- 200900858 (7) Evaluation of voltage holding ratio The SiO 2 film in which the sodium ion is prevented from dissolving is formed on the surface of the solution of the sensitive radiation linear resin composition prepared above, and the ITO (indium-tin oxide alloy) electrode is further formed. The solution was vapor-deposited on a soda lime glass substrate having a predetermined shape, and then spin-coated, and then prebaked in a clean oven at 90 ° C for 10 minutes to form a coating film having a film thickness of 2. μm. Next, using a high-pressure mercury lamp, the radiation having wavelengths of 3 65 nm, 405 nm, and 43 6 nm was exposed to an exposure amount of 1,000 J/m 2 on the coating film without passing through a photomask. Thereafter, the substrate was immersed in a developing solution of a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C for 1 minute, and after development, it was washed with ultrapure water, air-dried, and further dried at 23 (TC for 30 minutes). After the baking, the coating film is cured to form a permanent cured film. Next, the obtained substrate and the ITO electrode are only vapor-deposited into a substrate having a predetermined shape, and the sealing agent is mixed with a glass bead of 8 mm, and then injected into Merck. Liquid crystal cell MLC6608 (trade name) was used to produce a liquid crystal cell. Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the liquid crystal voltage retention rate measurement system VHR-1 A type (trade name) manufactured by Toyo Corporation was used. The voltage holding ratio of the liquid crystal cell is measured. At this time, the applied voltage is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio refers to (the liquid crystal cell potential difference after 16.7 milliseconds / the voltage applied in milliseconds) When the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell cannot maintain the applied voltage at the set level within 16.7 milliseconds, which means that the liquid crystal alignment cannot be performed sufficiently, and it is extremely easy. Since "seizure (seizure)" risk. -66-

Claims (1)

200900858 X. Patent Application No. 1 · A sensitive radiation linear resin composition characterized in that [A] (ai) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and (a2) a copolymer of other unsaturated compounds different from (a 1 ), [B] a polymerizable unsaturated compound, [C] a linear polymerization initiator for radiation radiation, and [D] a nitrate-based compound. 2. The sensitive radiation linear resin composition of claim 1, wherein the [D] nitrate compound is represented by the following formula (1-1), (1-2) or (1-3) Any of the compounds, R R- R -N— » · · ♦ · (1-1) R Ο R « · · · · (1-2) -67- 0 200900858 (1-3) (wherein each R is independently of each other and represents an alkyl group having 1 to 12 carbon atoms, and Z and T are groups which are necessary for completion of a 5- or 6-membered ring, and represent an organic group having 2 or 3 valences. , η indicates an integer of 2 or 3.) 3. The sensitive radiation linear resin composition of claim 1, wherein the [D] nitridyl compound is represented by the following formulas (1-2-1), (1-2-2), (1 - 3 - Any of the compounds shown in 1) or (1 - 3 - 2 ), (1-2-2) -68- 200900858 , R1 (1-3-2) (wherein X represents a hydrogen atom, a hydroxyl group, a decyloxy group, a decylamino group or a quinone imine group, γ represents a methylene group, an alkylene group having a carbon number of 2 to 12 or a olefinene group; Alkenyl ene, cyclohexanediyl, cyclohexenediyl or an extended aryl group having 6 to 12 carbon atoms, and R1 is an alkyl group having 1 to 12 carbon atoms. 4. The radiation sensitive linear resin composition according to any one of claims 1 to 3, which further comprises an [E] chain transfer agent. The sensitive radiation linear resin composition according to any one of claims 1 to 4, which is formed by a spacer for a liquid crystal display element or a protective film -69-200900858. 6. A spacer or protective film for a liquid crystal display element formed by the sensitive radiation linear resin composition of claim 5 of the patent application. 7. A method for forming a spacer for a liquid crystal display element or a protective film, characterized in that it comprises at least the following steps in the order described below: (a) a radiation-sensitive linear resin composition according to item 5 of the patent application scope The film is formed on the substrate, (b) the step of exposing at least a portion of the film, the step (c) of developing the film after exposure, and the step of heating the film after development. 8 - A liquid crystal display element having a spacer or a protective film as in claim 6 or both. I -70- 200900858 七无明说单单单符表 is the map of the generation of the map table on behalf of the map: the table of the map, the table, the generation of N, one or two days, Vw / Vw / no eight, if the case In the chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: none -4-