TW201100960A - Radiation sensitive resin composition, spacers or protective film of liquid crystal display and method for forming thereof - Google Patents

Abstract

The present invention relates to a radiation sensitive composition for forming a spacer of liquid crystal display element and a method for forming thereof. Event the slit coating method is used, spots made of small concavoconvex can not be produced on the coating film capable of coating at a high speed and saving the composition solvent. The present invention is performed by mean of the radiation sensitive composition which comprises (A) an alkali-soluble resin, (B) a polymeric unsaturated compound, (C) a radiation sensitive polymeric initiator and (D) a solvent represented by the following formula (1), wherein R1 and R2 represents a straight chain or branched chain alkyl group comprising 4 or 5 carbon atoms.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive resin composition, a spacer or a protective film of a liquid crystal display element, and a method of forming the same. [Prior Art] In the liquid crystal display device, in order to keep the interval (cell gap) between the two substrates constant, spacer particles such as glass beads or plastic beads having a predetermined particle diameter are used. Since these spacer particles are randomly spread on a transparent substrate such as a glass substrate, if spacer particles are present in the pixel-forming region, the spacer particles are generated, the incident light is scattered, and the contrast of the liquid crystal panel is lowered. problem. Therefore, in order to solve these problems, a method of forming a spacer in a region other than the pixel region by photolithography using a radiation sensitive resin composition is used (Patent Document 1). The liquid crystal display element has a structure in which a spacer is disposed on a color filter formed on a substrate, and then a counter substrate having a counter electrode is disposed thereon, and liquid crystal molecules are disposed in a cell gap. Therefore, in order to maintain cell gap fixation in all areas of the substrate, the spacer must have a high film thickness uniformity. In particular, in recent years, liquid crystal display elements have higher requirements for film thickness uniformity due to the current high precision of image quality and the follow-up (high-speed correspondence) of high-speed animation. . Further, in the production of a liquid crystal display device, it is necessary to increase the size of the glass substrate from the viewpoint of improving productivity and adapting to a large screen. The size of the glass substrate passes through the first generation of 300mmx400mm, the second generation of .201100960 370mm><470mm, the third generation of 620mmx750mm, the fourth generation of 960mm><l,100mm, the fifth generation of l,100mmxl,300mm Is becoming the mainstream. In addition, in the future, a large-sized substrate size of the sixth generation of 1,500 mmxl, 8 50 mm, the seventh generation of 1,850 mm x 2,100 mm, and the eighth generation of 2,200 mm x 2,600 mm is required. When the substrate size is small, for example, 37 〇mm x 47 〇mm or less, it is applied by spin coating, but in this method, a large amount of sensitizing resin composition solution must be applied' and it is not suitable for large substrates. Coated cloth. Further, when the substrate size is 960 mmxl or less, it is applied by slit and spin coating, but it is difficult to adapt to the substrate size after the fifth generation. The coating method adapted to the substrate size after the fifth generation is suitable for a so-called slit coating method in which a composition is ejected from a slit nozzle (patent * Documents 2 and 3). This slit coating method has an advantage that the amount of the composition required for coating can be reduced as compared with the spin coating method, and contributes to a reduction in the manufacturing cost of the liquid crystal display element. However, this slit coating method has the following problems: Θ The substrate is vacuum-adsorbed, and the coating nozzle is swept from a certain direction in a state where the substrate is supported by a minute pin to form a coating film, so that it is produced in the coating film. The spot called "desktop vacuum adsorption spot" caused by the vacuum-adsorbed hole, the spot called "support pin spot" caused by the support pin, and the strip-like shape appearing in the direction in which the coating nozzle is swept is called "vertical bar spot". The spot or the like is an obstacle to achieving the above-described height flat type. Further, from the viewpoint of further reducing the manufacturing cost of the liquid crystal display element, it is strongly required to reduce the amount of liquid for coating the composition to be used (saving liquid 201100960). CITATION LIST Patent Literature [Patent Document 1] JP-A-2001-261761 (Patent Document 2) JP-A-2006-184841 (Patent Document 3) JP-A-2001-25645 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to prevent speckle formation from being formed on a coating film even when a slit coating method is used as a coating method, and can be coated at a high speed during slit coating. It can save a solution of the radioactive resin composition. Further, a radiation-sensitive resin composition capable of forming a liquid crystal display element or a protective film with high sensitivity as a spacer or a protective film for liquid crystal display can maintain the currently required abrasion resistance, and has a high recovery rate. And flexible compression properties, particularly spacers or protective films of liquid crystal display elements having a high degree of uniformity and a method thereof. Means for Solving the Problems According to the present invention, the above objects and advantages of the present invention, firstly, a radiation sensitive resin composition characterized by 'comprising: (A) 100 parts by mass of an alkali-soluble resin, the alkali-soluble resin being mass% ( &1) and 40~95% by mass (&2) of the copolymer 'where (&1) is selected to use a small concave-sensing spacer element at the same time as a film of a 5-6 〇 from a 201100960 carboxylic acid a compound of a dicarboxylic acid and a dicarboxylic acid anhydride, (a2) being selected from a hydroxyalkyl ester of (meth)acrylic acid, a dihydroxyalkyl (meth)acrylate or (meth)acrylic acid (6) -hydroxyhexyloxy)alkyl ester, unsaturated compound having an epoxy group, cycloalkyl (meth)acrylate, aryl (meth)acrylate, aralkyl (meth)acrylate, no a saturated dicarboxylic acid dialkyl ester, at least one compound having an oxygen-containing 5-membered heterocyclic ring or an oxygen-containing 6-membered heterocyclic ring (meth) acrylate, a vinyl aromatic compound, and a conjugated diene compound; B) 30 to 250 parts by mass of polymerizable unsaturated compound; 〇(C) l~60 mass a radiation-sensitive linear polymerization initiator; and (D) a solvent in which 1 and r2 represented by the following formula (1) are a linear or branched alkyl group having 4 or 5 carbon atoms, which is relative to radiation The amount of all the solvents in the resin composition is from 5% by mass to 90% by mass. R*i 〇R2 (1) The above objects and advantages of the present invention, and the second object are achieved by a radiation sensitive resin composition characterized in that the solvent represented by the above formula (1) is a solvent other than the solvent ( The following 'also referred to as (E) solvent) are selected from the group consisting of alcohols, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, and One or more solvents of propylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, ketones, and ester solvents. The above objects and advantages of the present invention, and the third, are achieved by (A) an alkali-soluble resin which is a radiation-sensitive resin composition of a copolymer having an epoxy group or a (meth) acryloxy group. 201100960 The above objects and advantages of the present invention, and fourthly, are achieved by a spacer or a protective film of a liquid crystal display element formed of the above-described radiation-sensitive composition. The above-described objects and advantages of the present invention are achieved by a method comprising at least a spacer for a liquid crystal display element or a protective film in the following steps, (1) coating the above-mentioned radiation-sensitive resin composition on a substrate. a step of applying a film of 0, (2) a step of exposing at least a portion of the film, (3) a step of developing the film after exposure, and (4) a step of heating the film after development. According to the present invention, there is provided a radiation-sensitive resin composition which does not cause spots formed by minute irregularities on a coating film even when a slit coating method is used as a coating method, and can be applied at a high speed during slit coating. A solution for sensing a radiation-sensitive resin composition, a spacer or a protective film capable of forming a liquid crystal display element with high sensitivity; and a spacer or a protective film for providing a liquid crystal display element and a method for forming the same, wherein the liquid crystal display element is used as a liquid crystal display element The spacer can maintain the currently required abrasion resistance and compression performance with high recovery and flexibility, and has a high film thickness uniformity as a protective film. [Embodiment] Hereinafter, the present invention will be specifically described. < (A) Alkali-Soluble Resin > 201100960 The (A) alkali-soluble resin contained in the radiation-sensitive resin composition of the present invention is preferably a base developer as long as it is a developer for use in a development step to be described later. The alkali-soluble resin is not particularly limited. As such an alkali-soluble resin (A), an alkali-soluble resin having at least one selected from the group consisting of a carboxyl group and a carboxylic anhydride group is preferred, and a copolymer having an epoxy group or a (meth) propylene methoxy group is more preferred. Things. The alkali-soluble resin of the present invention is preferably at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as a compound 〇 (al)) and (a2) (al). A copolymer of an unsaturated compound (hereinafter referred to as "compound (a2)"). Particularly preferred examples of the (A) alkali-soluble resin include [A1] an unsaturated compound containing a compound (al) and having at least one hydroxyl group in one molecule (hereinafter, referred to as "a compound (a2-) a polymer obtained by reacting an unsaturated isocyanate (hereinafter referred to as "polymer (Α)")) on a copolymer of a monomer (hereinafter referred to as "copolymer (α)") of l)"), Ο [ Α2] a copolymer of a monomer containing a compound (al) and an unsaturated compound having an epoxy group (hereinafter referred to as "compound U2-2)" (hereinafter referred to as "copolymer (call)"), [ A3] a monomer formed from a compound (al), a compound (al), a compound (a2-l), and an unsaturated compound other than the compound (a2-2) (hereinafter, referred to as "compound (a2-3)") Copolymer (hereinafter referred to as "copolymer (γ)") or the like. In the production of the copolymer (α ), the compound (a2-3) may be simultaneously present, and the copolymer (α ) is formed into a copolymer of the compound (al), the compound (a2-l) and the compound (a2-3); .201100960 In the production of the copolymer (β), the compound (a2-3) may be coexisted in addition to the compound (al) and the compound (a2-2) to form a copolymer (β) and a compound 〇1), a compound (a2-2). And a copolymer of the compound (a2-3). Examples of the compound (al) used in the production of a copolymer (°〇, a copolymer, and a copolymer (γ) include a monocarboxylic acid, a dicarboxylic acid, a dicarboxylic acid anhydride, and the like. The acid may, for example, be acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, or propylene oxyethyl hexahydroortho Terephthalic acid, 2-methylpropenyloxyethylhexahydrophthalic acid, etc.; as the above dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, etc.; Examples of the carboxylic acid anhydride include an anhydride of the above dicarboxylic acid, etc. Among them, acrylic acid, methacrylic acid, and 2-propylene are preferable from the viewpoints of copolymerization reactivity and solubility of the obtained copolymer to a developer. Ethyloxyethyl succinic acid, 2-methacryloxyethyl succinic acid or maleic anhydride. The compound (al) may be used singly or in combination of two or more kinds. Copolymers (〇0, copolymers (P) and The content of the repeating unit derived from the compound (al) in the copolymer (γ) is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, particularly preferably 8 to 40% by mass. When the yield of the repeating unit derived from the compound (a 1) is 5 to 60% by mass, A balanced radiation-sensitive resin composition having a higher level of various properties such as radiation sensitivity, developability, and storage stability. -10- 201100960 The compound (a2·1) used as a copolymer (α) can be exemplified ( a hydroxyalkyl ester of methyl)acrylic acid 'dihydroxyalkyl ester of (meth)acrylic acid, (6-hydroxyhexyloxy) ketone of (meth)acrylic acid, etc. as a specific example thereof' It can be exemplified that the hydroxyalkyl ester as (meth)acrylic acid is, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxy(meth)acrylate. Butyl ester and the like; as the dihydroxyalkyl ester of (meth)acrylic acid, for example, 2,3-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, Methyl methacrylate, 3,4-dihydroxybutyl acrylate, etc.; (6-hydroxyl) as (meth)acrylic acid The decyloxyalkyl ester is, for example, 2-(6-hydroxyhexyloxy)ethyl (meth)acrylate, 3-(6-hydroxyhexyloxy)propyl (meth)acrylate or the like. Among these compounds (a2-l), 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferred from the viewpoints of copolymerization reactivity and reactivity with an isocyanate compound. Ester, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-O hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, methacrylic acid 2,3 - Dihydroxypropyl ester, (6-hydroxyhexyloxy) alkyl (meth) acrylate. In the compound U2-1), the above (meth)acrylic acid (6-hydroxyhexyloxy) The alkyl ester and 2-hydroxyethyl methacrylate are particularly preferable from the viewpoint of improving developability and improving the compression properties of the resulting spacer. As a commercial product of a mixture of 2-(6-hydroxyhexyloxy)ethyl methacrylate and 2-hydroxyethyl methacrylate, 201100960 PLACCEL FM1D, FM2D (trade name, Daisy) can be respectively cited. Produced by Chemical Industry Co., Ltd.). In the copolymer (in the above formula, the above compound (a2-l) may be used singly or in combination of two or more kinds.

In the copolymer (α), the content of the repeating unit derived from the compound (a2-l) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, particularly preferably from 5 to 30% by mass. When the content of the repeating unit derived from the compound (a2-l) is 1 to 5 〇 _ _ %, the copolymer obtained by the reaction with the unsaturated isocyanate compound has good stability and stability, and the resulting radiation-sensitive resin composition is obtained. The storage stability is good. The epoxy group in the compound (a2-2) used for the production of the copolymer (β) may, for example, be an oxiranyl group (having a 1,2-epoxy structure) or an propylene oxide group (having 1,3-) Epoxy structure). Examples of the unsaturated compound having an oxiranyl group include an oxiranyl (meth) acrylate (cyclo)alkyl ester and an α-alkyl acrylate oxiranyl (cyclo)alkyl ester. A glycidyl ether compound having an unsaturated bond or the like; and examples of the unsaturated compound having an oxypropylene group include a (meth) acrylate having an oxypropylene group. As specific examples thereof, it can be exemplified as the (meth)acrylic acid oxiranyl (cyclo)alkyl ester, which is, for example, glycidyl (meth)acrylate or 2-methyl (meth)acrylate. Glycidyl ester, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, (meth)acryl-12-201100960 acid 3,4-epoxycyclohexylmethyl ester, etc.; as α-alkyl acrylate oxirane ( The cycloalkyl esters are, for example, α-ethyl glycidyl acrylate, glycidyl α-n-propyl acrylate, glycidyl a-n-butyl acrylate, α-ethyl acrylate 6,7-epoxy heptyl Ester, 3,4-epoxycyclohexyl ester of α-ethyl acrylate, etc.; as a glycidyl ether compound having an unsaturated bond, for example, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, Vinylbenzyl glycidyl ether or the like; as a (meth)propionate having an oxypropylene group 3-((Meth)acryloxymethyl) propylene oxide, 〇3-((meth) propylene methoxymethyl)-3-ethyl propylene oxide, 3-((meth) propylene醯oxymethyl)-2-methyl propylene oxide, 3-((meth)acryloxyethyl)-3-ethyl propylene oxide, 2-ethyl-3-((methyl) Propylene oxiranyl ethyl) propylene oxide, 3-methyl-3-(meth) propylene methoxymethyl propylene oxide, 3-ethyl-3-(methyl) propylene methoxymethyl ring Oxypropane and the like. Among them, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexyl methacrylate Methyl ester, 3-methyl-3-methylpropenyloxymethyl propylene oxide or 3-ethyl-3-methylpropenyloxymethyl propylene oxide is preferred in terms of polymerizability. When the copolymer (β) is produced, the compound (a2-2) may be used singly or in combination of two or more. In the copolymer (β), the content of the repeating unit derived from the compound (a2-2) is preferably from 0.5 to 70% by mass, more preferably from 1 to 60% by mass, particularly preferably from 3 to 50% by mass. When the content of the repeating unit derived from the compound (a2-2) is from 0.5 to 70 -13 to 201100960% by mass, the heat resistance of the copolymer, the storage stability of the copolymer and the radiation sensitive resin composition, and the resulting interval can be obtained. A radiation-sensitive resin composition having a higher level of balance of compression properties of the object. The compound (a2-3) which can be used arbitrarily when producing a copolymer (γ) or a copolymer (〇0 and copolymer (β)) may, for example, be an alkyl (meth)acrylate, ( a cycloalkyl (meth) acrylate, an aryl (meth) acrylate, an aryl alkyl (meth) acrylate, a dialkyl ester of an unsaturated dicarboxylic acid, having an oxygen-containing 5 member heterocyclic ring or an oxygen containing 6 a heterocyclic (meth) acrylate, an ethylenyl aromatic compound, a conjugated diene compound, and other unsaturated compounds. Specific examples thereof may be mentioned as an alkyl (meth) acrylate. The ester is, for example, methyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl (meth) acrylate, ( Trimethyl butyl methacrylate or the like; as the cycloalkyl (meth) acrylate, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (methyl) ) tricyclo[5.0.1.02,6] 癸-8-yl ester, (methyl) Acrylic acid 2-(tricyclo[5.2.1.02,6]dec-8-yloxy)ethyl ester, isophorone (meth)acrylate, etc.; as aryl (meth)acrylate, such as acrylic acid a phenyl ester or the like; as the arylalkyl (meth)acrylate, for example, benzyl acrylate or the like; and as the unsaturated dicarboxylic acid dialkyl ester, for example, diethyl maleate or diethyl fumarate Ester, etc.; as a (meth) acrylate having an oxygen-containing 5-membered heterocyclic ring or an oxygen-containing 6-membered heterocyclic ring, for example, (meth)acrylic acid tetrahydrofuran-2-yl ester, (meth)acrylic acid tetrahydropyran- 2-based ester, -14-201100960 2-methyltetrahydropyran-2-yl (meth)acrylate, etc.; as an ethyl aromatic compound, for example, styrene, α-methylstyrene, etc.; The co-heptadiene compound 'is, for example, 1,3 to butadiene, isoprene or the like; and the other unsaturated compound is, for example, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide or the like. Among these compounds (a2 - 3 ), from the viewpoint of copolymerization reactivity, n-butyl methacrylate and 2-methyl methacrylate are preferred. Glycidol, benzyl methacrylate, tricyclo[5.2.1.02,6]non-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, In the production of the copolymer (〇0, copolymer (β) and copolymer (γ), the compound (a2-3) may be used singly or in combination of two or more kinds. In the copolymer (β), the content of the repeating unit derived from the compound (a2-3) is preferably 3% by mass, more preferably 20 to 50% by mass, particularly preferably 30 to 50% by mass. When the content Ο of the repeating unit of a2-3) is 10 to 70% by mass, the molecular weight of the copolymer can be easily controlled, and a radiation-sensitive resin composition having a higher level of balance such as developability and radiation sensitivity can be obtained. The copolymer (〇0, copolymer (β) and copolymer (γ) are preferably produced by polymerizing a mixture of the monomers described above in a suitable solvent, preferably in the presence of a radical polymerization initiator. Examples of the solvent used for the polymerization include diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate, etc. These solvents may be used alone or in combination of two or more kinds - 15-201100960. The radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis-(2,4-dimethyl). An azo compound such as valeronitrile or 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by a gel chromatography (GPC) of the copolymer (〇0, copolymer (β), and copolymer (γ) is preferably 2,000. ~100,000, more preferably 5,000 to 50,000. The total ruthenium (0 〇, copolymer (卩) and copolymer (丫) is 2,000 to 00, In the case of 10,000, a radiation-sensitive resin composition having a higher level of balance between heat resistance, developability, and radiation sensitivity can be obtained. The polymer (A) can be obtained by reacting a copolymer (0 Å and an unsaturated isocyanate compound). The copolymer obtained as above (〇0 can be used as the polymerization reaction solution to directly produce the polymer (A), or the copolymer (after temporarily separating from the solution, used to produce the polymer (A). Examples of the saturated isocyanate compound include a (meth)acrylic acid derivative, and specific examples thereof include 2-(meth)acryloxyethyl isocyanate and 4-(meth)acryloxylated butyl group. The isocyanate, 2-(2-isocyanate ethoxy)ethyl (meth)acrylate, etc. As a commercial item, respectively, the commercial item as 2-propenyl methoxyethyl isocyanate is mentioned. Karenz AOI (manufactured by Showa Denko Co., Ltd.) is commercially available as karenz Μ 01 (manufactured by Showa Denko Co., Ltd.) as a product of 2-methyl propylene oxirane ethyl isocyanate. 16 - 201100960 The product of 2-(2-isocyanate ethoxy)ethyl acrylate is karenz MOI-EG (reactive with the copolymer (α) in these unsaturated isocyanate compounds manufactured by Showa Denko Co., Ltd. In terms of aspects, preferred is 2-propenyloxyethyl isocyanate, 2-methylpropenyloxyethyl isocyanate, 4-methylpropenyloxybutyl isocyanate or 2-(2-isocyanate B) methacrylate In the production of a polymer, the unsaturated isocyanate compound may be used singly or in combination of two or more. 0 The reaction of the copolymer (α) and the unsaturated isocyanate compound, if necessary, in a suitable catalyst In the presence of a copolymer of a polymerization inhibitor (〇0, it is preferably carried out by adding an unsaturated isocyanate compound while stirring at room temperature or under heating. For example, di-n-butyltin dilaurate (IV) may be mentioned as the catalyst, and examples of the polymerization inhibitor include p-methoxyphenol. The use ratio of the unsaturated isocyanate compound in the production of the polymer (Α) is preferably 〇_1 to 95 mol%, more preferably 〇_1 to 95 mol%, based on the hydroxyl group of the compound (a2-l) derived from the copolymer (α). 1.0 to 80 mol%, particularly preferably 5.0 to 75 mol%. When the use ratio of the unsaturated isocyanate compound is from 〜1 to 95 mol%, the reactivity with the copolymer (α) and the heat resistance and elastic properties of the radiation-sensitive resin composition can be further improved, which is preferable. In the radiation sensitive resin composition of the present invention, the polymer (Α) 'copolymer (β) and the copolymer (γ) may be used singly, respectively, but the polymer (Α) and the copolymer (β) are preferably used. Use, or use copolymer (β) and copolymer (丫) from -17 to 201100960. By using the polymer (A) and the copolymer (β) together, the storage stability of the resulting radiation-sensitive resin composition and the strength and heat resistance of the obtained spacer can be further improved, which is preferable. When the polymer (Α) and the copolymer (Ρ) are used together, the use ratio of the polymer (Α) is preferably 0.5 to 50 parts by mass based on 100 parts by mass of the copolymer (β). Preferably, it is 1 to 30 parts by mass, and particularly preferably 3 to 20 parts by mass. When the ratio of use of the polymer (Α) is _0.5 to 50 parts by mass, the storage stability of the radiation sensitive resin composition and the radiation level of the obtained separator or the heat resistance of the protective film are higher. Resin composition. On the other hand, by using the copolymer (?) and the copolymer (?) together, it is preferable to obtain an advantage of improving the storage stability of the radiation sensitive composition. When the copolymer (β) and the copolymer (γ) are used together, the copolymer (β) is preferably used in an amount of 10 to 150 parts by mass, more preferably 100 parts by mass of the copolymer (γ). It is 20 to 130 parts by mass, and particularly preferably 30 to 100 parts by mass. < (Β) Polymerizable Unsaturated Compound> The (Β) polymerizable unsaturated compound contained in the radiation sensitive resin composition of the present invention is irradiated in the presence of a (C) radiation sensitive polymerization initiator to be described later. Radiation-polymerized unsaturated compounds. The polymerizable unsaturated monomer is not particularly limited, and is preferably a monofunctional, bifunctional or trifunctional or higher (meth) acrylate from the viewpoint of improving polymerizability and improving the strength of the obtained spacer. . -18- 201100960 The monofunctional (meth) acrylate may, for example, be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate or diethylene glycol. Monoethyl ether methacrylate, (2-propenyloxyethyl) (2-hydroxypropyl) phthalate, (2-methylpropenyloxyethyl) (2-hydroxypropane) Phthalate, ω-carboxypolycaprolactone monoacrylate, and the like. As a product of the product, for example, ARONIX Μ-101, Μ-111, Μ-114, Μ-5300 (above, _ East Asia Synthetic Co., Ltd.); KAYARAD TC-1 10S TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.); VISCOTE 158, the same 23 1 1 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.). Examples of the bifunctional (meth) acrylate include ethylene glycol diacrylate, propylene glycol diacrylate 'ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol dimethacrylate. , tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, ^ 1,6-hexanediol dimethacrylate, 1,9-nonanediol II Acrylate, 1,9-nonanediol dimethacrylate, and the like. As a product, the product name is, for example, ARONIX Μ-210, Μ-240, Μ-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, and R- 604 (above, manufactured by Nippon Kayaku Co., Ltd.), VISCOTE 260, same as 3 12, same as 3 3 5HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.) Ltd. manufactured) and so on. -19-201100960 The trifunctional or higher (meth) acrylate may, for example, be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or pentaerythritol trimethacrylate. Ester, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol Hexamethyl acrylate 'ethylene oxide modified dipentaerythritol hexaacrylate, tris(2-propenyl methoxyethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate, amber Acid-modified pentaerythritol hexaacrylate; and a compound having a linear alkyl group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule and having three A polyfunctional urethane acrylate compound obtained by reacting four or five (meth) acryloxy compounds. The product of the trifunctional or higher (meth) acrylate is represented by a trade name, and examples thereof include ARONIXM-309, M-400, and M-405.

Same as M-450, same as M-7 00, same as M-8030, same as M-8060, same as TO- 1 450 (above, manufactured by Toagosei Co., Ltd.), KAYARAD ΤΜΡΤΑ, same DPHA, same as DPCA-20, same DPCA-30, same as DPCA-60, same as DPCA-120, with DPEA-12 (above, manufactured by Nippon Kayaku Co., Ltd.), VISCOTE 295, same as 300, with 360, with GPT, with 3PA, with 400 (above, Manufactured by Osaka Organic Chemical Industry Co., Ltd., and as a commercial product containing a polyfunctional urethane acrylate compound, NEW -20-201100960 FRON TIER R-1150 (First Industrial Pharmaceutical Co., Ltd.) Manufactured, KAYARAD DPHA-40H (manufactured by Sakamoto Chemical Co., Ltd.), etc. Among them, it is particularly preferable to contain ω-carboxy polycaprolactone monoacrylate ' 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol hexamethylene phthalate A commercially available product of an enoate or a polyfunctional urethane acrylate compound. The (Β) polymerizable unsaturated compound as described above may be used alone or in combination of two or more. The use ratio of the (fluorene) polymerizable unsaturated monomer in the radiation sensitive resin composition of the present invention is preferably from 30 to 250 parts by mass, more preferably from 30 to 250 parts by mass per 1 part by mass of the alkali-soluble resin. 50 to 200 parts by mass. (Β) Polymerizability Ο When the amount of the unsaturated monomer is from 30 to 250 parts by mass, the sensitivity of the radiation sensitive resin composition and the heat resistance and elastic properties of the obtained spacer are better. < (C) Radiation-Temperature Polymerization Initiator> The [C] radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition of the present invention is capable of inducing radiation to cause polymerization of a polymerizable unsaturated compound. The active ingredient of the species. Examples of such a [C] radiation-sensitive polymerization initiator include an anthracene-fluorene-based compound, an acetophenone compound, a bipyridyl compound, and a benzophenone compound. Specific examples of the above-mentioned fluorene-fluorenyl-21-201100960 compound can be exemplified by ethyl ketone-1-(9-ethyl-6-(2-methylbenzomethyl)-9H-carbazole- 3-yl)-1-(0-ethylindolyl)' 1-(9-ethyl-6-benzylidene-9.H--oxazol-3-yl)oct-1-one oxime- 〇-acetate, 1-(9-ethyl-6-(2-methylbenzylidene)-9.H.-carbazol-3-yl)-ethan-1-one oxime Formate, i-(9-n-butyl-6-(2-ethylbenzylidenyl)-9·Η·-咔D--3-yl)-eth-1-one oxime-0-benzene Formate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9·Η·-carbazol-3-yl]-1-(0 -Ethyl hydrazide), ethyl ketone-1-(9-ethylqyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9·Η.-carbazole-3- -1(0-ethylhydrazine), ethyl ketone-1-(9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9·Η.-carbazole -3 -yl)-1-(0-ethenylhydrazine), ethyl ketone·1-(9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3) - Dioxopentyl) methoxybenzimidyl}-9·Η·-carbazol-3-yl)-1-(0-ethylindenyl) and the like. Among them, as a preferred ruthenium-indenyl ruthenium compound, ethyl ketone-1-(9-ethyl-6-(2-methylbenzhydryl)-9Η-oxazol-3-yl group can be mentioned. )-1-(0-acetamidoxime), ethyl ketone-1-(9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxy oxime~ methionyl)-9·Η ·-oxazol-3-yl)·1-(0-acetamidoxime) or ethyl ketone-1-(9-ethyl-6-{2-methyl-4-(2,2-dimethyl) -1,3-Dioxypentyl)methoxybenzylidene}-9·Η·-oxazol-3-yl)-1-(0-ethenylhydrazine). These 0-fluorenyl hydrazine compounds may be used alone or in combination of two or more. The acetophenone compound ', for example, an α-amino ketone compound or an α-hydroxy ketone compound. Specific examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 2-dimethyl group. Amino-22-201100960 -2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-indoleone, 2-methyl-1-(4- Methylthiophenyl)-2- oxopropan-1 ketone, etc.; as a specific example of the α-hydroxyketone compound, for example, 丨_phenyl-2-hydroxy-2-methylprop-1- Ketone, ΐ-(4.isopropylphenyl)_2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) Ketone, hydroxycyclohexyl phenyl ketone, and the like. · Among these acetophenone compounds, preferred α-aminoketone compounds, particularly preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenylbutanone-one or 2 -Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one. As a specific example of the above biimidazole compound, 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)_1,2,-biimidazole, 2,2' - bis(2-chlorophenyl)-4,4',5,5,-tetraphenyl-1,2,-biimidazole, 2,2'-bis(2,4-dichlorophenyl) -4,4,,5,5'-tetraphenyl-1,2,-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4,,5, 5,-tetraphenyl-1,2'-biimidazole, etc. Among these biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5' is preferred. -tetraphenyl-1,2'-biimidazole, 2,2,-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'- Biimidazole or 2,2,-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, particularly preferably 2, 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 2'-Biimidazole. When a biimidazole compound is used as the (C) radiation-sensitive polymerization initiator in the radiation sensitive resin composition of the present invention, an aliphatic or aromatic group selected from a dialkylamine group may be added. At least one of a compound (hereinafter referred to as "amine group-23-201100960 sensitizer") and a thiol compound. The above amine-based sensitizer has a radiation sensitivity for increasing the biimidazole compound and an increase of the imidazole radical. The compound which produces a function of efficiency is added for the purpose of improving the sensitivity and resolution of the radiation sensitive resin composition to further improve the adhesion of the formed spacer or the protective film to the substrate. As the amine-based sensitizer, For example, N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and p-dimethylene can be mentioned. Ethyl benzyl benzoate, isoamyl dimethyl dimethyl benzoate, etc. Among these amine sensitizers, 4,4′-bis(diethylamino)di Benzophenone. These amine based sensitizers can be used alone or in combination 2 The amount of the biimidazole compound 'amine-based sensitizer added is preferably from 0.1 to 5 parts by mass, more preferably from 1 to 20 parts by mass, based on 1 part by mass of the amine-based sensitizer. When the amount is 〇. 1 to 50 parts by mass, the effect of improving sensitivity, resolution, and adhesion can be obtained. ο As the above thiol compound, it has a hydrogen radical for the imidazole radical, thereby producing a sulfur radical. The functional compound of the component is irradiated with radiation, and the polymerization initiation energy of the imidazole radical generated by the cracking is moderate, since the polymerization initiation energy is not very high, so if it is directly used for forming a spacer of the liquid crystal display element, Then, the cross-sectional shape of the spacer may have a bad shape such as a reverse tapered shape. However, 'by adding a thiol compound to it, a hydrogen radical is supplied from the thiol compound to the imidazole radical, thereby converting the imidazole radical into a neutral immi-ki', while producing -24-201100960 has a higher polymerization initiation energy. The composition of the sulfur radicals ' thus, the shape of the spacer can be accurately a better tapered shape. Examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, and 2- An aromatic thiol compound such as mercapto-5-methoxybenzimidazole; 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, etc. Aliphatic monothiol compound; 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), etc. Aliphatic

G thiol compound, etc. Among these thiol compounds, particularly preferred is 2-mercaptobenzothiazepine D. The amount of the thiol compound added is preferably from 0.1 to 50 parts by mass, more preferably from 1 to 20 parts by mass, per part by mass of the biimidazole compound. When the amount of the thiol compound added is 0.1 to 50 parts by mass, the adhesion of the obtained spacer to the substrate can be improved, and the shape is good. In the radiation sensitive resin composition of the present invention, when the biimidazole compound is used as the (C) radiation sensitive polymerization initiator, it is preferred to add the above amine based sensitizer and the thiol compound. The ratio of use of the (C) radiation-sensitive polymerization initiator in the present invention is preferably from 1 to 60 parts by mass, more preferably from 2 to 50 parts by mass, per 100 parts by weight of the (A) alkali-soluble resin, further Good for 5 to 40 parts by mass. By using the (C) radiation-sensitive polymerization initiator in the range of 1 to 60 parts by mass, a spacer having high hardness and adhesion can be formed even at a low exposure amount. -25-201100960 <(D) Solvent> The radiation sensitive resin composition of the present invention is characterized by containing a solvent represented by the following formula (1).

Ri 〇 R2 (1) (In the formula (1), R1 and R2 are a linear or branched alkyl group having 4 or 5 carbon atoms.) The compound represented by the formula (1) includes, for example, Di(n-butyl)^ether, di(isobutyl)ether, di(tertiary butyl)ether, (n-butyl)isobutyl ether, decanobutyl-tertiary butyl ether, isobutyl - Tert-butyl ether, di(n-pentyl) ether, n-pentyl-3-methylbutyl ether, n-pentyl-2-methylbutyl ether, n-pentyl-1-methylbutyl ether , n-pentyl-2,2-dimethylpropyl ether, n-pentyl-1,2-dimethylpropyl ether, n-pentyl-1, b-dimethylpropyl ether, di(3-methyl Butyl)ether, 3-methylbutyl-2-methylbutyl ether, 3-methylbutyl-1-methylbutyl ether, 3-methylbutyl-2,2-dimethyl Propyl ether, 3-methylbutyl-1,2-dimethylpropyl ether, 3-methylbutyl-1,1-dimethylpropyl ether, bis(2-methylbutyl)ether , 2-Methylbutyl-1-methylbutyl ether, 2-methylbutyl-2,2-dimethylpropyl ether, 2-methylbutyl-1,2-dimethylpropane Ether, 2-methylbutyl-1,1-dimethylpropyl ether, bis(1-methylbutyl)ether, 1-methyl Butyl-2,2-dimethylpropyl ether, 1-methylbutyl-1,2-dimethylpropyl ether, 1-methylbutyl-1,1-dimethylpropyl ether , bis(2,2-dimethylpropyl)ether, 2,2-dimethylpropyl-1,2-dimethylpropyl ether, 2,2-dimethylpropyl-1,2- Dimethyl propyl ether, bis(1,2-dimethylpropyl)ether, 1,2-dimethylpropyl-1,I-dimethylpropyl ether, di(1,丨-dimethyl Propyl)ether, n-butyl-n-pentyl ether, n-butyl-3-methylbutyl ether, -26- 201100960 n-butyl-2-methylbutyl ether, n-butyl-1-methyl Butyl ether, n-butyl-2,2-dimethylpropyl ether, n-butyl-1,2-dimethylpropyl ether, n-butyl-1,1-dimethylpropyl ether, Isobutyl-n-pentyl ether, isobutyl-3-methylbutyl ether, isobutyl-2-methylbutyl ether, isobutyl-1-methylbutyl ether, isobutyl-2 , 2· dimethyl propyl ether, isobutyl-1,2-dimethylpropyl ether, isobutyl-1,1-dimethylpropyl ether, tert-butyl-n-pentyl ether, Tert-butyl butyl-3-methylbutyl ether, tertiary butyl-2-methylbutyl ether, tertiary butyl-1-methylbutyl ether, tri-tert-butyl-2,2-di Methyl propyl Ether, 1,2-dimethyl-tert.butyl ether, 1,1-dimethyl-square-tert.butyl ether and the like. Among them, in particular, from the viewpoint of improving the coating property of the slit, it is preferred to use di(n-butyl)ether, di(isobutyl)ether, di(tertiary butyl)ether, n-butyl-isobutylene. Ether, n-butyl-tertiary butyl ether, isobutyl tert-butyl ether, di(n-pentyl) ether, n-pentyl-isoamyl ether, diisoamyl ether, di (three) Butyl) ether. The content of the solvent (D) 〇 ^ is preferably from 5% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass based on the total amount of the solvent in the radiation-sensitive resin composition. When the content of the total amount of the solvent in the solvent-based radiation-sensitive resin composition is from 5% by mass to 40% by mass, the balance between the viscosity of the radiation-sensitive resin composition and the solid content concentration is higher. Further, a coating film having excellent film thickness uniformity can be obtained. In the present invention, a solvent other than the solvent (D) (hereinafter also referred to as (E) solvent) may be used together with the solvent (D). As such (E) solvent, -27-201100960 can be used as an alcohol, a glycol ether, an ethylene glycol-based ether acetate, a diethylene glycol monoalkyl ether, a diethylene glycol di-hoc ether, a dipropylene glycol dioxane. Ethyl ether, propylene glycol monoalkyl ether 'propylene glycol alkyl ether acetate, propylene glycol anhydride ether propionate, ketone, vinegar, and the like. Specific examples of these other solvents may be, for example, those in which the alcohol is benzyl alcohol or the like, and the glycol ether is ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; Alcohol alkyl ether acetate, which is ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; as diethylene glycol monoalkyl ether 'is Ο diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, etc.; as diethylene glycol dialkyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as dipropylene glycol II The alkyl ether is dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc.; as the propylene glycol monoalkyl ether, it is propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether , propylene glycol butyl ether, etc.; hydrazine as propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate vinegar, propylene glycol ethyl ether acetate, etc.; as propylene glycol alkyl ether propionate, propylene glycol methyl ether propionic acid Vinegar, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, etc.; as a ketone, is a Ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, etc.; as an ester, ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, butyl -28-201100960 butyl acrylate, methyl lactate, ethyl lactate, propyl lactate, lactic acid Butyl ester, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl ester, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropane Propyl acrylate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropane Butyl acrylate, methyl 3-propoxypropionate, and the like. ^ Among them, particularly preferred are benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol. Monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone , dipropylene glycol dimethyl ether, propylene glycol methyl ether propionate, and the like. The content of the solvent (E) is preferably 60% by mass to 95% by mass, and more preferably 70% by mass to 95% by mass based on the total amount of the solvent in the radiation sensitive resin composition. (E) When the content of the solvent is 60% by mass to 95% by mass based on the total amount of the solvent in the radiation sensitive resin composition ,, the viscosity of the radiation sensitive resin composition and the solid concentration equilibrium level are higher, and it is possible to obtain A radiation sensitive resin composition which is more excellent in high-speed coating properties. <Surfactant> The radiation sensitive resin composition of the present invention preferably contains a surfactant. The surfactant is preferably a fluorosurfactant or an organic quinone surfactant. The fluorosurfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkyl group at least at any of the terminal, main chain and side chain -29 to 201100960, and examples thereof include 1,1,2,2·tetrafluoro-n-octyl (^,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) Ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoro-n-pentyl) acid, octaethylene glycol di(1,1,2,2-tetrafluoro-positive Butyl)ether, hexapropylene glycol di(^,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether , perfluoro-n-dodecylsulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9, 10,10-Decafluoro-n-dodecane, and sodium fluoroalkylphenylsulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerol tetra(fluoroalkylpolyoxyethylene Ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxide, carboxylic acid fluoride Alkyl esters and the like. In addition, as a commercial item of the fluorinated surfactant, for example, BM-1000, BM-1100C or higher, manufactured by BM CHEMIE Co., Ltd., MEGAFAC F142D, F172, F173, F183, F178, and ^ F191, same as F471, same as F4 76 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), FTERGENTFT-100, same-110, same-140A, same-150, same-250, same-251, same-300, Same as -310, same-400S, FTERGENT FTX-218, and -251 (above, manufactured by NEOS Co., Ltd.). Examples of the above organoquinone surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH-193, -30-201100960 and SZ. -603 2. Surfactant sold under the trade names of SF-8428, DC-57, and DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.). These surfactants can be used singly or in combination of two or more. These surfactants can be used individually or in mixture of 2 or more types. The surfactant is used in an amount of 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the amount of the surfactant is 0.1 to 5 parts by mass, the coating film unevenness can be reduced.

G <Other optional additives> In the radiation sensitive resin composition of the present invention, any additives other than the above, such as an adhesion aid, may be mixed as needed within a range not impairing the effects of the present invention. Store stabilizers, etc. The above-mentioned binder is a component for improving the adhesion of the formed spacer and the substrate. As such an adhesion promoter, a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacrylium oxime group, a vinyl group, an isocyanate group or an epoxy group is preferable, and examples thereof include Trimethoxymethyl decyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy Decane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These binders may be used alone or in combination of two or more. The amount of the adhesion aid to be used is preferably in the range of -31 to 201100960 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, per 100 parts by mass of the alkali-soluble resin. When the amount of the adhesion aid is in the range of 1 to 20 parts by mass, development residue does not occur in the development step, and the adhesion of the pattern can be improved. Examples of the storage stabilizers include sulfur, hydrazines, hydroquinones, polyoxygen compounds, amines, and nitronitroso compounds. More specific examples are exemplified by 4-methoxyphenol, hydrazine-nitroso-...phenylhydroxyaluminum aluminum, and the like. ^ These storage stabilizers may be used alone or in combination of two or more. The amount of the storage stabilizer is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per part by mass of the alkali-soluble resin. When the amount of the storage stabilizer is in the range of 0.01 to 10 parts by mass, the storage stability of the radiation sensitive resin composition is good. <Preparation of Radiation-sensitive Resin Composition> The radiation-sensitive resin composition of the present invention can be polymerized by the above (Α) alkali-soluble resin, (Β) polymerizable unsaturated compound, (C) radiation-sensitive Ο W polymerization The initiator, the (D) solvent, and the (E) solvent are each prepared by uniformly mixing the other components added as described above at a predetermined ratio. The radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in the form of a solution. The composition solution thus prepared is used after a micropore screening method such as a pore size of 5 μπι. When the radiation sensitive resin composition of the present invention is prepared in a solution state, the solid content concentration (from -32 to 201100960 minutes other than the solvent component occupied in the composition) is also the above (A) alkali-soluble resin, (b) The ratio of the total amount of the polymerizable unsaturated compound, (C) radiation sensitive polymerization initiator, and other components arbitrarily added to the solvent (D) and the solvent (E) may be based on the purpose of use and the desired film thickness. Etc., set to an arbitrary concentration (for example, 5 to 50% by mass). Further preferably, the solid content concentration varies depending on the method of forming a coating film on the substrate. When the spin coating method is employed as the coating method, the solid content concentration is more preferably 20 to 50% by mass, particularly preferably 30 to 40% by mass. In the case of the _ slit coating method, the solid content concentration is further preferably from 10 to 35% by mass, and particularly preferably from 15 to 30% by mass. <Method of Forming Spacer or Protective Film> Next, a method of forming a spacer or a protective film using the radiation sensitive resin composition of the present invention will be described. The method of forming the spacer or the protective film of the present invention can be carried out by performing the following procedures described in the following order. (1) a step of forming a 〇w coating film of the radiation sensitive resin composition of the present invention on a substrate, (2) a step of irradiating at least a part of the coating film with radiation, and (3) developing a coating film after irradiation with radiation The step 'and (4) the step of heating the developed coating film. Hereinafter, each of these steps will be described in order. (1) a step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate. A transparent conductive film is formed on one surface of the transparent substrate. The radiation sensitive resin composition of the present invention is formed on the transparent conductive film-33-201100960. The coating of the object. Examples of the transparent substrate used herein include a glass resin substrate and the like; more specifically, a soda lime glass or an alkali-free glass substrate; and polyethylene terephthalate or polybutylene terephthalate; A resin base formed of a plastic such as milled, polycarbonate, or polyimide is a transparent conductive film provided on one surface of a transparent substrate, and a NESA film formed of tin oxide (Sn02) (PPG of the United States: ^ standard), When an ITO film formed of indium oxide-tin oxide (In203-SnO 2 ) is formed into a film by a coating method, the transparent conductive cloth may be coated with heat (prebaking) after the solution of the radiation sensitive resin composition of the present invention. ), forming a film. The coating method of the composition solution is preferably a spray coating method, a roll coating method, a spin coating method (spin coating method), a narrow method, a bar coating method, or an inkjet coating method, and is preferably a slit coating method. In particular, when the slit coating method is employed, the advantageous effects of the present invention are exhibited to a large extent, which is preferable.预 After coating, prebaking and postbaking are preferred. The conditions of the prebaking and the conditions of the components of the radiation-sensitive resin composition according to the present invention, the ratio of use, and the like are appropriately set. Prebaking 7 0 to 10 0 ° C, for example, under conditions of 1 to 10 minutes. It can be carried out by a suitable heating device such as a hot plate or a cleaning oven. The baking temperature is preferably from 180 to 240 ° C, more preferably from 200 to 23 ° ° C. The time varies depending on the type of heating device used. When a hot post-baking heating device is used, the post-baking time is preferably from 1 〇 to 6 0 - 34 - a diester or a plate such as a substrate or a glass. For example, by the registrar 〇 film coating, the spin coating method can be applied in the final baking, for example, after baking as a post-baking plate as minutes, and 201100960 is preferably 15 to 40 minutes. When using a cleaning oven, the post-baking time is preferably from 20 to 120 minutes, more preferably from 30 to 90 minutes. The film thickness of the coating film thus formed is preferably from 1 to 8 μm, more preferably from 0.1 to 6 μm, still more preferably from 0.1 to 5 μm. (2) Step of irradiating at least a part of the coating film with radiation Next, at least a part of the formed coating film is irradiated with radiation. In this case, when only a part of the coating film is irradiated with radiation, it can be carried out, for example, by a method of interfering with a mask having a predetermined pattern. The spacer or the protective film differs depending on the size of the opening of the photomask to be used, and the method of formation is also different. For example, if a photomask having a dot pattern mask of 〜30 μη is used, a spacer can be formed. If a photomask having a quadrangular pattern of one side of 50 μm or more is used in accordance with the pixel size, a protective film is formed. Examples of the radiation used for the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among them, the W-rays in the range of 250 to 550 nm are preferable, and the radiation containing ultraviolet rays of 365 nm is particularly preferable. The irradiation amount (exposure amount) of the radiation is measured by an illuminometer (OAI model 365, manufactured by Optical Associates Inc.) to measure the intensity of the irradiated radiation at a wavelength of 3 6 5 nm, preferably 1 〇〇 to 5,000 J/m 2 . More preferably, it is 200 to 3,000 J/m 2 °. The radiation sensitive resin composition of the present invention has higher radiation sensitivity than the conventionally known composition, and can obtain desired radiation even when the radiation dose is 800 J/m 2 or less. The film thickness, good shape, excellent adhesion and high hardness of the spacer or protective film. (3) Step of developing the coating film after irradiation with radiation Next, the coating film irradiated with radiation is developed to remove unnecessary portions (non-exposed portions) to form a predetermined pattern. As the developer to be used for development, for example, an inorganic basic compound such as sodium hydroxide, potassium hydroxide or sodium carbonate; an aqueous solution of an organic basic compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide; . In the aqueous solution of the above basic compound, at least one selected from the group consisting of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added in an appropriate amount. The developing method may be any method such as a liquid deposition method, a dipping method, or a shower method; the development time is preferably from 1 1 to 180 seconds. The developing temperature can be normal temperature. After the development treatment, it is preferably dried, for example, by running water for 30 to 90 seconds, and then air-dried by compressed air or compressed nitrogen to obtain a desired pattern. (4) Step of heating the developed coating film Next, the patterned coating film is heated by a suitable heating means such as a hot plate or an oven at a predetermined temperature, for example, l〇〇~250 °C for a predetermined time. For example, heating on a hot plate for 5 to 30 minutes and heating in an oven for 30 to 180 minutes gives a spacer having a desired pattern. By the above-mentioned procedure, it is possible to form a spacer for a liquid crystal display element which is excellent in various properties such as a spot having no minute unevenness in the coating film and uniformity of film thickness. -36-201100960 EXAMPLES Hereinafter, the present invention will be more specifically described by way of Synthesis Examples and Examples, but the present invention is not limited by these Synthesis Examples and Examples. Further, in the following, the weight average molecular weight (Mw) and the number average molecular weight (?n) of the polymer were measured by a gel chromatograph (GPC) under the following conditions. Measuring device: manufactured by Tosoh Co., Ltd., "HLC8220 system"

Separation column: manufactured by Tosoh Co., Ltd., TSKgel GMHHR-N ❹

4 series connection use column temperature: 40 °C elution solvent: tetrahydrofuran (manufactured by Wako Pure Chemical Industries Co., Ltd.) Flow rate: 1.0 mL/min. Sample concentration: 1.0% by mass Sample injection amount: 1 〇〇μ m ^ Detector: Differential refractometer standard material: monodisperse polystyrene In addition, the solution viscosity of the radiation sensitive resin composition was measured at 30 ° C using an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. <(A) Synthesis of alkali-soluble resin > Synthesis Example 1 In a flask equipped with a condenser and a stirrer, 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. ), 3 parts of pentaerythritol tetrakis(3-mercaptopropionic acid-37-201100960 ester), 250 parts by mass of methyl 3-methoxypropionate, and then 14 parts by mass of methacrylic acid, 40 parts by mass of methacrylic acid shrinkage Glyceride, 6 parts by mass of styrene and 35 parts by mass of tricyclo[5·2·1·02,6]癸-8-yl methacrylate, after nitrogen substitution, then 5 parts by mass of 1,3-butane The olefin was stirred slowly while raising the temperature of the solution to 70. (:, the polymerization was carried out for 4 hours while maintaining the temperature to obtain a copolymer solution having a solid concentration of 28.1%. This was used as the copolymer (A-1). The Mw of the obtained copolymer (α-!) was 1 〇, 5 00. Synthesis Example 2 In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile, 250 parts by mass of propylene glycol monomethyl ether acetate, and then 18 were added. Parts by mass of methacrylic acid, 25 parts by mass of tricyclo[5.2.1.02,6]non-8-yl methacrylate, 5 parts by mass of styrene, 30 parts by mass of 2-hydroxyethyl methacrylate, 22 parts by mass After benzyl methacrylate was replaced with nitrogen, the temperature of the solution was raised to 7 ° C while stirring slowly, and the temperature was maintained for 5 hours to carry out polymerization to obtain a copolymer (α-1) having a solid concentration of 28.8%. Solution: The Mw of the obtained copolymer (a-ι) was measured by GPC to be 13,000.

Next, 12 parts by mass of 3-methylpropenyloxyethyl isocyanate (trade name: karenz M01 'manufactured by Showa Denko Co., Ltd.) and 0.1 part by mass of 4-methoxy group were added to the copolymer (α-1) solution. After phenol, the reaction was carried out at 40 ° C for 1 hour, and then the reaction was stirred at 60 ° C for 2 hours. The isocyanate group derived from 3-methylpropenyloxyethyl isocyanate and the hydroxyl group of the copolymer (heart 1) were confirmed to react by IR (infrared absorption) spectrum. After reacting at 40 ° C -38 - 201100960 for 1 hour, and then reacting at 6 (TC for 2 hours, the IR spectrum of the reaction solution was measured, and the vicinity of 2270 CHT1 from the isocyanate group of 3-methacryloxyethyl isocyanate was measured. The peak was decreased, and it was confirmed that the reaction proceeded. A polymer (A-1) solution having a solid concentration of 31.0% was obtained as a polymer (A-1). Synthesis Example 3 A flask equipped with a condenser and a stirrer 6 parts by mass of 2,2,-0 azobis(isobutyronitrile), 250 parts by mass of methyl 3-methoxypropionate, and then 14 parts by mass of methacrylic acid and 20 parts by mass of methacrylic acid were added. Tetrahydrofurfuryl ester, 5 parts by mass of styrene, and 56 parts by mass of benzyl methacrylate, after nitrogen substitution, 5 parts by mass of 1,3-butadiene was added, and the temperature of the solution was raised to 70 while stirring slowly. The copolymer was stirred at a temperature of 5 ° C for 5 hours to obtain a (A) copolymer solution having a solid concentration of 27.9%, which was used as a copolymer (A-2). The obtained copolymer (A-2) had a Mw of 11, 400. Synthesis Example 4 0 In a flask equipped with a condenser and a stirrer, 6 parts by mass of 2,2'-azo was added. Bis(isobutyronitrile) and 250 parts by mass of methyl 3-methoxypropionate, and then 5 parts by mass of styrene, 14 parts by mass of methacrylic acid, 33 parts by mass of benzyl methacrylate and 23 parts by mass of A N-butyl acrylate, 20 parts by mass of 3-(methacryloxymethyl)-3-ethyl propylene oxide, after nitrogen replacement, further adding 5 parts by mass of 1,3-butadiene While stirring, the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 4 hours to carry out polymerization to obtain a (A) copolymer solution having a solid concentration of 27.9%, which was used as a copolymer (A-3). -39- 201100960 When Mw of the obtained copolymer (A-3) was measured by GPC, it was 1,200. Examples 1 to 19 and Comparative Examples 1 to 3 (I) Preparation of a radiation sensitive resin composition was added as (A) a base. The solution of the copolymer (A-1) obtained in the above Synthesis Example 1 in an amount equivalent to 1 part by mass (solid content) of the copolymer (A-1) in terms of the soluble resin, as (B) polymerizable unsaturated a mixture of 150 parts by mass of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name KAYARAD DPHA, day) Chemical Co., Ltd. made 40 parts by mass of succinic acid modified pentaerythritol hexaacrylate, 10 parts by mass of ω-carboxypolycaprolactone monoacrylate (trade name: ARONIX Μ-5 3 00 (East Asia Synthetic Co., Ltd.) Manufactured as 10 parts by mass of ethyl ketone-1-(9-ethyl-6-(2-methylbenzomethyl)-9Η-oxazol-3-yl) as a (C) radiation-sensitive polymerization initiator -1-(0-ethylhydrazine) ("IRGACURE ΟΧΕ02" manufactured by Ciba Specialty Chemicals Co., Ltd.), 3 parts by mass of 2-(4-methylbenzyl)-2-(dimethylamino) 1-(4-morpholinophenyl)-butan-1-one (trade name: IRGACURE 3 7 9 'manufactured by Ciba Specialty Chemicals Co., Ltd.), 3 parts by mass of 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 185 parts by mass of diisoamyl ether as (D) solvent, 500 mass as (Ε) solvent Part by weight of methyl 3-methoxypropionate, 5 parts by mass of γ-glycidoxypropyltrimethoxydecane* as a surfactant, 0.2 parts by mass of FTERGENT FTX-2 18 (manufactured by NEOS Co., Ltd.), dissolved After the solid content concentration is 23.5% by mass, · 5μπι square aperture through screening programs microporous filters prepared radiation-sensitive resin composition. The prepared radiation sensitive resin group -40- 201100960 The viscosity of the product was 3.0 (mPa.s). The radiation sensitive resin composition prepared above was evaluated in the following order. The results are shown in Tables 1 and 2. (1) Measurement of the viscosity of the composition solution The measurement was carried out at 25 ° C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., VISCONIC ELD.R.). The results are as shown in Table 1 and Table 2. ○ (2) Determination of the concentration of solid components in the composition solution 〇 Precision weighing 〇. 3 g of the composition solution into the alumina vessel, adding about ig diethylene glycol dimethyl After ether, it was dried on a hot plate at 175 ° C for 60 minutes, and the solid content concentration was determined from the weight before and after drying. Here, since the ratio of the amount of liquid used for the slit coating to the concentration of the solid component is large, when the viscosity of the composition is 3.0 mPa 's, when the solid content concentration is low, the amount of liquid used is increased. Therefore, when the viscosity of the composition and the 3.OmPa's are uniform, when the solid content concentration is 23%, the amount of the liquid used for the slit coating can be judged to be large, and the effect of solving the solution cannot be achieved. The results are shown in Tables 1 and 2. (3) Evaluation of applicability (spots, spots of smoke, spots of pin marks) On a 550 mm x 650 mm chrome-forming glass, a slit die coater (TR632 159-CL, Tokyo should be used) Chemical Industry Co., Ltd.) Coating the prepared composition solution, drying it under reduced pressure to 0.5 Torr, prebaking on a hot plate at 100 ° C for 2 minutes to form a coating film, and then at 2,000 J/m 2 The film was exposed to an exposure amount to form a film having a film thickness of 4 μm from the upper surface of the -41 to 201100960 glass on which the chromium film was formed. The surface of the film was irradiated with a sodium lamp, and the surface of the coated film was visually confirmed. Clearly confirm that there are vertical spots (one or more straight spots in the direction of coating or the direction in which they intersect), smoke spots (cloud spots), spots of pin marks (points formed on the substrate support pins) In the case of a spot, it is referred to as X; when it is confirmed that only a small amount is referred to as Δ; when it is hardly found, it is referred to as 〇; when no spot of vertical stripes, smoke spots, or pin marks is found, it is referred to as ◎. The results are shown in Tables 1 and 2. (4) Evaluation of coatability (uniformity) The film thickness of the coating film formed on the glass on which the chromium film was formed was measured using a probe type measuring instrument ([1^1^11<; 8 3200) Measurement Uniformity was calculated from the film thicknesses of the nine measurement points. It is assumed that the short axis direction of the substrate is X and the long axis direction is Υ, and the nine measurement points are (X [mm], Y [ Mm]) are (275, 20), (275, 30), (27 5, 60), (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, Ο 63 0). The formula for calculating the uniformity is as follows: FT(X, Y)max of the following formula is the maximum 値, FT (X, Y) among the film thicknesses of the nine measurement points. )min is the minimum 値 among the film thicknesses of the nine measurement points, and FT(X, Y)avg. is the average 値 in the film thickness of the nine measurement points. When the uniformity is 2% or less, the film thickness uniformity can be judged. Good. The results are shown in Tables 1 and 2. (Formula for the calculation of uniformity) Uniformity (%) = {FT(X, Y)max-FT(X, Y) mi η}x100/{ 2xFT(X ' Y)avg.} -42- .201100960 (5) Evaluation of high-speed coating properties using a slit coater at 550 mm x 650 m The coating was performed on an alkali-free glass substrate of m, and the coating condition was such that the distance between the substrate and the nozzle (GAP) was 150 μm, and the coating liquid was sprayed from the nozzle so that the film thickness after exposure was 2.5 μm, and the moving speed of the nozzle was 120 mm/sec. • Change in the range of ~220mm/sec., and determine the maximum speed of strip-like spots caused by liquid breakage. At this time, even if there is no strip-like spot at a speed of 200mm/SeC or more, it is judged as _ It can be adapted to high-speed coating. The results are shown in Tables 1 and 2. 〇(6) Evaluation of sensitivity On a 95 mm x 95 mm alkali-free glass substrate, after applying a radiation-sensitive resin composition by spin coating, at 90 °C The hot plate was prebaked for 3 minutes to form a coating film having a film thickness of 3.5 μm. Next, a circular pattern having a diameter of 12 μm was formed as a photomask of the opening portion on the obtained coating film, and the intensity at 365 nm was 250 W/ Ultraviolet light of m2, changing exposure time, exposure, and then developing with 0.05% hydrogen KOH potassium hydroxide solution at 25 ° C for 60 seconds, then washing with pure water for 1 minute, then in an oven at 23 ° C, after Baking for 30 minutes In this case, the residual film ratio after post-baking (film thickness after post-baking X100 / film thickness after exposure) is a minimum exposure amount of 90% or more as sensitivity. The exposure amount at this time is 800 J/ Below m2, the sensitivity is considered to be good. The results are shown in Tables 1 and 2. (7) The evaluation of the abrasion resistance is the same as the exposure of the "(6) sensitivity evaluation" except that the exposure amount is equivalent to the exposure amount of the sensitivity of the "-6-201100960 sensitivity" determined by "(6) Evaluation of sensitivity". Spacer. On the obtained substrate, a liquid crystal alignment agent AL3 046 (trade name, manufactured by JSR Corporation) was applied by a printer for liquid crystal alignment, and then dried at 180 ° C for 1 hour to form a coating film of a liquid crystal alignment agent having a film thickness. Next, the coating film was subjected to a rubbing treatment by a roll having a roll of a polyamide-made cloth and a roll speed of 500 rpm and a table moving speed of 1 cm/sec. At this time, confirm whether the pattern is worn or not. The results are shown in Tables 1 and 2. (8) Evaluation of compression performance In the same manner as in the above "(6) Evaluation of sensitivity", a remaining circular pattern was formed on the substrate at an exposure amount equal to or higher than the residual film ratio. The micro-compression tester (Fischer Scope H100C (manufactured by Fischer Inst)) measures the change in the amount of compression displacement with respect to the load by a 40 mN compression test using a flat head of 50 μm, ^ displacement by a load of 40 mN And calculate the recovery rate (%) when removing the load of 40mN. In this case, the recovery rate is 90% or more, and when the displacement at the negative j is 〇·15 μm or more, it is considered to be a spacer having a compression performance having high resilience. The results are as shown in Table 1 and Table 2, in the coating of the base film: a limited 0.0 5 μιη wiping machine, under the condition, peeling off. For 90% of the patterns in ruments I load, 3 at this time, the amount of vertical shift, the mouse 40mN complex rate and no. -44- .201100960

实施 Example 11 〇1 1 1 1 〇〇〇〇1 1 Example 丨10 ! 〇1 1 1 1 1 〇〇CS cn cn 1 Example 9 1 1 沄1 1 〇〇宕1 1 Example 8 1 〇 1 1 1 1 〇〇〇cn m 1 Embodiment 7 1 ο 1 1 1 1 150 1 〇〇〇cn cn 1 Embodiment 6 ο ι-Η 1 1 1 1 〇Η 1 〇〇〇 mm 1 Example 5 1 1 1 1 1 〇〇〇 1 Example 4 ο 1 1 1 I 150 1 〇〇〇 1 Example 3 1 1 1 1 〇 1 1 1 1 1 ΓΛ Example 2 1 1 1 1 〇 150 1 1 1 1 1 Example 1 1 1 1 1 〇^-Η 1 I 1 1 1 m 1 Composition (parts by mass) Cohesive 4 Copolymer A-2 Copolymer A-3 Polymer A-1 Copolymer α-1 1 1 Β -2 Β-3 Β-4 ύ m ό C-4 (Α) alkali soluble resin (Β) polymerizable unsaturated compound from s- Follow I Τ | 1 201100960

1 00 1 1 500 1 1 1 1 1 1 1 o cn 23.0 〇〇1 00 1 1 500 1 1 1 1 1 1 1 o cn 23.6 〇〇1 »n 00 1 1 500 1 1 1 1 1 1 1 o rn Rn tN 〇〇1 in 00 1 1 1 500 | 1 1 1 1 1 1 o cn *—H rn (N 〇〇1 fT) 00 1 500 1 1 1 1 1 1 1 1 o cn i 23.8 〇◎ 1 JQ 1 1 640 1 1 1 1 1 1 1 o cn cn CN 〇〇1 00 1 1 1 1 500丨1 1 1 1 1 1 1 o rn i 23.5 〇〇m 480 1 1 1 205 1 1 1 1 1 1 o Cn (N 〇〇CO in Ό 1 1 1 1 1 1 1 1 o 1 o cn 23.2 〇〇m 615 1 1 1 1 o 1 1 1 1 1 o cn 23.2 〇〇m W) 00 VO 1 1 1 1 1 1 1 1 1 1 o cn 0 〇in ύ Dl D-2 D-3 ( ώ El-2 El-3 El-4 E-2-1 E-2-2 1 1 E-20 1 E-2-4 Viscosity of composition solution (mPa.s) Solid content of composition solution (%) Smoke spot vertical strip (D) Solvent (E) Solvent spot evaluation '201100960

〇0.79 200 600 m cn Os 0,7 i 27.0% ◎ 0.84 200 600 m ON 1 0.15 27.0% 〇0.81 200 800 Christine 5: 0.22 丨27.0% 〇0.81 200 700 Destruction (N 0,7 1 1 27.0% 〇0.76 200 700 destroy cs On 0,7 I 27.0% 1 〇0.79 200 ο 卜 m cn OS 0.17 6.6% ◎ 0.82 200 700 destroy CN Os 0.17 27.0% 1.75 200 700 destroy (N ON 0.18 70.0% <! 200 ο 00 m -1 1 0.26 90.0% <3 1.82 200 800 mg 0.27 90.0% 1.97 200 800 m 0.35 100.0% Uniformity (%) of coating thickness of pin-spot coating High-speed coating property (m/sec.) Sensitivity (J/m2) Abrasion resistance recovery rate (%) Displacement amount (μηι) S ugly w _ f ^ e Chain 萚Q Ingot compression performance evaluation ugly Teng itf

DR .201100960

Comparative Example 3 〇1 1 1 1 1-Η 1 〇〇〇ΓΛ m 1 1 Comparative Example 2 〇1 1 I 1 沄r—< 1 〇〇〇m [ ! Comparative Example 1 〇1 1 1 1 沄1- H 1 〇〇〇cn m 1 1 Example 19 〇1 1 1 1 沄1 〇〇〇m 1 1 1 Example | 18 ο 1 1 1 1 1 〇〇〇m 1 1 Example 17 j ο 1 1 1 1 1 〇〇〇m 1 1 Embodiment 16 ο 1 1 1 1 沄1—4 1 〇〇〇m cn 1 1 Embodiment 15 ο 1 1 1 1 沄1 〇〇〇rn 1 1 Embodiment 14 1 ο Ρ ' < 1 1 1 1 1 〇〇〇cn ΓΛ 1 1 Example 13 ο y—^ 1 1 1 1 1 〇〇〇1 1 1 Example 12 1 ο 1 1 1 1 沄1 〇〇〇cn m 1 1 Composition (parts by mass) ! Copolymer Α-1 Copolymer Α-2 Copolymer Ad-J Polymer Al Copolymer α-1 1 ώ 1 Β-2 Β-3 Β-4 ΰ rs ό cn ύ ό 1 C-5 (Α) alkali soluble resin (8) Polymerizable unsaturated compound #1 =, 1 ® 1 1 .201100960

On 201100960

〇700 m Ν 〇0.17 Γ 0.0% 200 700 壊<Ν ON 0.17 i_ Γ 0.0% 700 m CN a\ 0.17 1 4.4% 〇CN 700 in (N Os 0.17 80.0% 〇〇b m (N 〇\ 0.17 1 47.0% 200 800 揉<N 0.24 1_ 1 27.0% i 〇800 Destroy <N 〇\ 0.23 27.0% 〇 (N as 800 (S as 0.18 1 27.0% 1 〇CN 800 m (S On 0.23 i_ 1- 27.0 % ί 〇〇00 堞<S Os 0.21 L 1 i 27.0% 1 丨200 800 Deer ON 0.22 L 丨27.0% 1 /—S Recovery rate (%) Displacement amount (μιη) s -B- Chain ω J g _ ms 锲Φ Forging chain Xiang Q Art m per mm 岖1 m Evaluation of wear resistance compression properties fr <N m 坩DR □Teng 撇,201100960 (B) Composition Bl: dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate A mixture of esters (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) B-2: a polyfunctional acrylate compound (trade name: KAYARAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.)

B-3: succinic acid-modified pentaerythritol hexaacrylate 0 B-4 : ω-carboxypolycaprolactone monoacrylate (trade name: ARONIX Μ-5300 (manufactured by Toagosei Co., Ltd.) (C) Component C-1: Ethyl ketone, 1-(9-ethyl-6-(2-methylbenzhydryl)-9Η-indazol-3-yl)-, 1-(0-ethenylhydrazine) (trade name IRGACUREOXE02' Ciba Refinery Co., Ltd.) C-2: 2-(4-Methylbenzyl)-2-(dimethylamino) "-(4-morpholinophenyl)-butan-1-one (trade name: IRGACURE 379, manufactured by Ciba Specialty Chemicals Co., Ltd.) C-3: 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole C-4: 4,4'-bis(diethylamino)benzophenone C-5 : 2-mercaptobenzothiazepine (D) Ingredient-51- 201100960 Dl : Dimorphism Amyl ether D-2: di(n-pentyl)ether D-3: di(n-butyl)ether (E) component E-1: methyl 3-methoxypropionate E-2: propylene glycol monomethyl Ether acetate E-3: diethylene glycol ethyl methyl ether 0 E-4: cyclohexanone E-5: dipropylene glycol dimethyl ether E-6: benzyl alcohol E-7: ethylene glycol monobutyl Ether acetate E-8: propylene glycol methyl ether propionate 4E] ^ The main element symbol square DESCRIPTION -52-

Claims (1)

201100960 VII. Patent application scope: 1. A radiation sensitive resin composition characterized by 'comprising: (A) 100 parts by mass of alkali-soluble resin, the alkali-soluble resin is 5 to 60% by mass (al) and 40 to 95 The mass % (a2) of the copolymer 'where U1) is a compound selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid and a dicarboxylic acid anhydride' (a2) is a hydroxyalkyl ester selected from (meth)acrylic acid, (A) a dihydroxyalkyl ester of acrylic acid or a (6-hydroxyhexyloxy)alkyl (meth)acrylate, an unsaturated compound having an epoxy group, an anthranilyl (meth)acrylate, Aryl methacrylate, aryl (meth) acrylate, dialkyl dicarboxylate, (meth) acrylate having an oxygen-containing 5-membered heterocyclic ring or an oxygen-containing 6-membered heterocyclic ring At least one compound of a vinyl aromatic compound and a conjugated diene compound; (B) 30 to 250 parts by mass of a polymerizable unsaturated compound; (C) 1 to 60 parts by mass of a radiation-sensitive polymerization initiator; and (D) Ri and L represented by the following formula (1) are 0 linear or branched chains having 4 or 5 carbon atoms The solvent of the alkyl group is from 5% by mass to 90% by mass based on the total amount of the solvent in the radiation sensitive resin composition; Ri - 〇 - R2 (1). 2. The radiation sensitive resin composition according to claim 1, characterized in that it comprises a diethylene glycol dialkyl ether, a propylene glycol alkyl-53-201100960 ether acetate, a ketone, an ester. At least one or more (Ε·1) solvent of the solvent, and a solvent of the above formula (1). 3. The radiation sensitive resin composition according to claim 1, wherein the composition comprises an alcohol, a glycol ether, a glycol alkyl ether acetate, and a diethylene glycol monoalkyl ether. One or more (Ε-2) solvents of dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol alkyl ether propionate, and a solvent of the above formula (1). Q 4. The radiation sensitive resin composition of claim 2, wherein: (Ε-1) the solvent is selected from the group consisting of diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, and propylene glycol One or more solvents of phenyl ether acetate, propylene glycol ethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and cyclohexanone. 5. The radiation sensitive resin composition of claim 3, wherein the solvent is selected from the group consisting of benzyl alcohol, ethylene glycol monobutyl ether &acetate; diethylene glycol One or more solvents of ethyl ether acetate, diethylene glycol diethyl ether, decane dipropylene glycol dimethyl ether, and propylene glycol methyl ether propionate. 6. The radiation sensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin is a copolymer having an epoxy group or a (meth) acryloxy group. 7. The radiation sensitive linear resin composition of claim 6, wherein -54-201100960 is characterized by: (c) a radiation-based polymerization initiator > a base compound. 8. The sensory lipid composition according to any one of claims 1 to 7, which is used for forming a film of a liquid crystal display element. A spacer or a protective film for a liquid crystal display element, wherein the photosensitive resin composition of the liquid crystal display element is characterized in that at least: a spacer for a liquid crystal display element or a protective film is characterized in that at least The steps described in the following order are as follows: (1) coating on a substrate as in claim 8: a step of forming a coating film of a resin composition, (2) a step of exposing at least a portion of the coating film, (3) exposing The subsequent step of developing the coating film, and (4) the step of heating the developed coating film. The species is 0-醯: ray tree 丨 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或Method, next step, radiation -55- 201100960 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: