TW200949442A - Photosensitive resin composition, spacer and method for processing them, and liquid crystal display element - Google Patents

Abstract

This invention provides a photosensitive resin composition that characterized in produces extremely small amount volatile matters while forms a spacer, and is suitable for high speed coating by slit coating method. The photosensitive resin composition comprises: (A) a polymer has at least one group selected from the group consisting of unsaturated carboxylic acid and carboxylic acid anhydride and at least one group derived from certain polythiol compounds represented by pentaerythritol-tetrakis (3-mercaptopropinate), wherein the ration (Mw/Mn) of the average molecular weight (Mw) calculated based on polystyrene from gel permeation chromatography to the number average molecular weight (Mn) based on polystyrene is 1.0 to 2.8; (B) a polymeric unsaturated compound; and (C) a photosensitive polymerization initiator.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive resin composition, a spacer, a method of manufacturing the same, and a liquid crystal display element. More specifically, it relates to a radiation-sensitive resin composition suitable as a material for forming a spacer used in a display element such as a liquid crystal display panel and a touch panel, a spacer for a display element formed of the composition, and a spacer having the spacer. Liquid crystal display element. [Prior Art] In the liquid crystal display device, spacer particles such as glass beads or plastic beads having a predetermined particle diameter have been conventionally used in order to maintain a constant space (box gap) between the two substrates. Since the spacer particles are randomly dispersed on a transparent substrate such as a glass substrate, once spacer particles are present in the pixel formation region, spacer phenomenon occurs, and incident light is scattered, and the contrast of the liquid crystal display panel is lowered. The problem. Therefore, in order to solve these problems, a method of forming a spacer by photolithography is employed. In the method, a radiation-sensitive resin composition is coated on a substrate to form a film, and the film is subjected to ultraviolet light exposure and development through a predetermined mask to form a dot-like or stripe-shaped spacer, since The predetermined portion other than the pixel formation region forms a spacer, and thus the above problem is basically solved. In recent years, from the viewpoint of increasing the area of liquid crystal display elements and improving productivity, the glass substrate mother board has been enlarged from the previous level of 680×800 mm to a level of 1 500×1 800 mm. In the production step of the liquid crystal display element, a composition for forming a spacer for the radiation sensitive resin -4-200949442 is usually applied to a transparent substrate, and the solvent is removed by baking on a hot plate, and exposure and development are carried out to form a spacer. However, as the size of the substrate increases, the problem of contamination of the baking furnace and the photomask due to volatilization of volatile components in the radiation-sensitive resin composition at the time of formation of the spacer causes a decrease in production tact and an increase in production cost, thereby concern. Further, when the radiation sensitive resin composition is applied to a large substrate of the fifth generation or later, a slit die coating method is employed, and from the viewpoint of shortening the production process, it is required to shorten the coating time. In order to shorten the coating time, it is necessary to speed up the coating speed, and once the coating speed is increased, the unevenness of the stripe coating is often caused on the surface of the coating film. Therefore, there is an urgent need to develop a radiation-sensitive resin composition which does not cause uneven coating even if the coating speed is increased. In order to solve the above problem, the applicant has disclosed in Patent Document 1 that contamination of a baking furnace, an exposure mask, and the like caused by sublimation of a photopolymerization initiator is suppressed by containing a specific photopolymerization initiator. Further, in Patent Document 2, the relationship between the viscosity 〇 of the radiation-sensitive resin composition and the solid content concentration is disclosed, and a coating film having a uniform film thickness and no sinus can be obtained in the slit die coating method. However, in recent years, in order to further increase the production cycle and reduce the production cost, it is urgently required to develop a smaller amount of volatile components generated when forming spacers than before, and to cope with high-speed coating of the slit die coating method. A radiation sensitive resin composition. [Patent Document 1] JP-A-2005-234362 [Patent Document 2] JP-A-2006-184841A No. 200949442 SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a spacer when it is formed. The amount of the volatile component is very small, and the radiation-sensitive resin composition can cope with the high-speed coating of the slit die coating method. Another object of the present invention is to provide a spacer formed of the above-described radiation sensitive resin composition, a method for producing the same, and a liquid crystal display device having excellent display quality. Other objects and advantages of the invention will be apparent from the description which follows. g According to the present invention, the above objects and advantages, the first 'achieved by a radiation sensitive resin composition, comprising: [A] having at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and the following The η-valent group represented by the formula (1), and the ratio of the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography to the polystyrene-equivalent number average molecular weight (Mn) (Mw/Mn) a polymer of 1.0 to 2.8; [B] a polymerizable unsaturated compound; and 0 [C] a radiation-sensitive polymerization initiator, X—(-Y—R1—S—+ ) (1 ) η (Formula (1) In the formula, R1 is a methylene group or an alkylene group or an alkylmethylene group having 2 to 10 carbon atoms, and γ is a single bond, -CO-, -0-C0-* (wherein The link is connected to R1) or -NHCO·* (wherein the bond with "*" is connected to R1) 'η is an integer from 2 to 10 and X is the number of carbon atoms optionally having one or more acid bonds a valence hydrocarbon group of 2 to 70, or η is 3 and X is -6-200949442. A trivalent group of the following formula (2), "+" is a linkage bond)

(In the formula (2), R" are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" is each represented by a linking bond). According to the present invention, the above objects and advantages, and secondly, to a method for producing a spacer for a display element, characterized in that it comprises the following steps at least in the following order, (1) forming a coating of the above-mentioned radiation sensitive resin composition a step of filming, (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, the above objects and advantages, and thirdly, are achieved by a spacer for a display element produced by the above-mentioned radiation φ linear resin composition. According to the present invention, the above objects and advantages, fourth, are achieved by a liquid crystal display element having the above-mentioned spacer. The radiation-sensitive resin composition of the present invention has a very small amount of volatile components generated at the time of production of the spacer, and does not occur on the obtained film even when applied at a high speed by a slit die coating method. The stripes are uneven. Further, the radiation sensitive resin composition of the present invention has high sensitivity, and it is possible to manufacture a display element having a sufficient residual film ratio even at a low exposure amount. [Embodiment] Hereinafter, the present invention will be described in detail. <Radiation-sensitive linear resin composition> The radiation-sensitive resin composition of the present invention includes at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and at least one group selected from the above formula (1) η valent group, and the ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography to the polystyrene-converted number φ average molecular weight (?η) is 1.0~ a polymer of 2.8 (hereinafter referred to as "polymer [A]"); [B] a polymerizable unsaturated compound (hereinafter referred to as "polymerizable compound [B]"); and [C] a radiation-sensitive polymerization initiator. [Polymer [A]] The polymer [A] contained in the radiation sensitive resin composition of the present invention has at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and the above formula (1) η valent group. The alkylene group having 2 to 10 carbon atoms of R1 in the above formula (1) is preferably an alkylene group having 2 to 6 carbon atoms, more preferably a linear chain having 2 to 6 carbon atoms. An alkylene group or a group represented by the following formula (3). CH3 - R111 - CH - * (3) (In the formula (3), Rin is a methylene group or a linear alkylene group having 2 to 4 carbon atoms, and a bond having "*" is bonded to S). The alkylmethylene group having 2 to 1 ring carbon atoms in R1 is preferably a group represented by the following formula (4). -8- 200949442 -CH- (4) As γ in the above formula (1), _〇_c〇_* is preferable (wherein the connection key with "*" is connected to R1). The η in the above formula (1) is preferably an integer of 2 to 8, more preferably an integer of 2 to 6, or 8, more preferably 2, 3, 4, 6, or 8. In the above formula (1), as '! ! The X at the time of 2 is preferably a linear or branched alkylene group having 2 to 10 carbon atoms, a divalent group represented by the following formula:

(In the formula (5), each of them is a hydrogen atom or a methyl group, and ml is an integer of from 1 to 20', and "*" is each a bond;), and X is preferably, for example, the above. a trivalent group represented by the formula (2), a trivalent group represented by the following formula (6) φ, or the like;

(In the formula (6), "*" is each represented by a linkage bond); and X as η is 4, 6 or 8 is preferably a 4, 6 or 8 valence group represented by the following formula (7). Mission, etc., -9- (7) 200949442 ch2 I *—CH2 - f ch2

(In the formula (7), m2 is an integer of 0 to 2, and "*" is each represented as a connection key). The polymer [A] may further have a polymerizable unsaturated bond in the side chain in addition to at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and the η-valent group represented by the above formula (1). . The content ratio of at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group in the polymer [Α] is preferably 0.1 to 1 mmol/g, more preferably 0.5 to 5 mmol/g. The content of the η-valent group represented by the above formula (1) in the polymer [A] is preferably 0.005 to 1 mmol/g, more preferably 0.01 to 0.5 mmol/g. When the polymer [A] has a polymerizable unsaturated bond in its side chain, the content ratio of the polymerizable unsaturated bond in the polymer [A] is preferably 20 mmol/g or less, more preferably 0.1 to 15 mmol/g. More preferably, it is 0.5 to 1 Ommo Ι/g ° The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the polymer [A] is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000. When the Mw is less than 2,000, the developability of the obtained film, the residual film ratio, and the like are not sufficiently good, and the pattern shape, heat resistance, and the like of the produced spacer may be impaired. On the other hand, if Mw exceeds 100,000. 'There will be insufficient resolution and the pattern shape of the manufactured spacer will be damaged. The molecular weight distribution (hereinafter referred to as "Mw/Mn") of the polymer [A] defined by the enthalpy of Mw divided by Mn (the number average molecular molecule - 10 200949442 in terms of polystyrene) is 1.0 to 2.8, preferably 1.0 to 2.5, more preferably 1.0 to 2.3. When Mw/Mn exceeds 2.8, when the high-speed coating by the slit die coating method is employed as the 'coating method, unevenness may occur on the formed film. The polymer [A], as long as it is a polymer as described above, may be obtained by any method, preferably at least (a1) contains a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. The at least one selected unsaturated compound (hereinafter referred to as "compound (al)") is a polymer obtained by a radical polymerization step in the presence of a compound represented by the following formula (8), X~~(-Y- R1—SH ) (8) ' 7 η (In the formula (8), X, Y, R1 and η are each the same as defined for X, Υ, R1 and η in the above formula (1)). The polymer may be the polymer itself obtained by the above steps, or may be a polymer which introduces a polymerizable unsaturated bond to the side chain of the polymer. As a result of intensive studies, the present inventors have found that the obtained polymer can be controlled by radical polymerization in the presence of a compound having two or more mercapto groups in one molecule represented by the above formula (8). The molecular weight distribution, which can increase the conversion rate of the unsaturated compound to the polymer which is supplied to the radical polymerization, and it is found that by including the polymer [Α] obtained by this method in the radiation sensitive resin composition, The amount of the volatile component generated at the time of formation of the spacer is very small, and it can be applied to the radiation-sensitive resin composition of the high-speed coating of the slit die coating method. As the polymer [Α] of the present invention, the following polymers [Α1], -11-200949442 polymer [A2-1] or polymer [a.2-2] are preferred. Polymer [A 1]: at least one selected from the group consisting of compound (ai) and an unsaturated compound selected from the group consisting of an unsaturated compound having an epoxy group and an unsaturated compound having an oxetanyl group (hereinafter referred to as "a compound" (a2 - 1)"), an unsaturated compound having a hydroxyl group (hereinafter referred to as "compound (a2-2)"), and a compound other than the above compound (al), compound (a2-1), and compound (a2-2) Copolymer obtained by radical polymerization of an unsaturated compound having at least one composition of a saturated compound (hereinafter referred to as "compound (a2-3)") in the presence of 0 of the compound represented by the above formula (8) Things. Polymer [A2-1]: an unsaturated compound of at least one selected from the group consisting of the compound (al) and the compound (a2-2) and the compound (a22-3) is represented by the above formula (8) A reaction product polymer obtained by reacting a copolymer obtained by radical polymerization in the presence of a compound (hereinafter referred to as "precursor polymer [A2_1]") with a compound (a2 - 1). Polymer [A2-2]: an unsaturated compound composed of at least one selected from the group consisting of compound (al), compound (a2-2), and group consisting of compound (a2-1) and compound (a2-3) a reaction product polymer obtained by reacting a copolymer obtained by radical polymerization in the presence of the compound represented by the above formula (8) (hereinafter referred to as "precursor [A2-2]") with an unsaturated isocyanate compound . Further, in the following, the compound (a2-l), the compound (a2-2) and the compound (a2-3) are also collectively referred to as "compound (a2)". As a specific example of the above compound (al), an unsaturated carboxylic acid For example, acrylic acid, methacrylic acid, crotonic acid, 2-propenyloxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, 2-methyl propylene oxime-12-200949442 ethyl A monocarboxylic acid such as hexahydrophthalic acid or a dicarboxylic acid such as maleic acid or fumaric acid; and examples of the unsaturated carboxylic acid anhydride include an acid anhydride of the above-exemplified dicarboxylic acid. Among these compounds ui), acrylic acid, methacrylic acid, and horse are preferred from the viewpoints of copolymerization reactivity, a coating film formed of the obtained radiation sensitive resin composition, and a solubility in an alkali developing solution. The acid anhydride or 2-methacryloxyethyl hexahydrophthalic acid. As a specific example of the above compound (a2_1), as the unsaturated compound having an epoxy group, a 4-methyl group is exemplified. Propylene methoxymethyl-2·cyclohexyl-1,3-dioxolan acrylate glycidyl ester, 2-methyl glycidyl acrylate, 3,4-epoxy butyl acrylate, acrylic acid 6 , an epoxycycloalkyl acrylate such as 7-epoxyheptyl ester, 3,4-epoxycyclohexyl acrylate or 3,4-epoxycyclohexylmethyl acrylate; glycidyl methacrylate Ester, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-cyclomethacrylate Oxycyclohexyl ester, methyl propylene glycol 3,4-epoxy Q cyclohexyl methyl ester, etc. Ester; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl ester of α-ethyl acrylate An α-alkyl acrylate alkyl acrylate; a homo-glycidyl glycidyl ether, a m-vinylbenzyl glycidyl acid, a glycidyl ether such as a bivalent glycidyl ether, or the like. Examples of the unsaturated compound having an oxetanyl group include 3-(methacryloxymethyl) oxetane, 3-(methylpropionyloxy-13-200949442 methyl) 3-ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-2-benzene Oxycyclobutane, 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-3.ethyloxetane, 2- Ethyl 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2-phenyloxetane, etc. having oxetanyl Methacrylate; 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(propyleneoxyloxy) Methyl)-2.methyloxocyclo@butane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(acryloxyethyl)oxetane Alkanes, 3-(acryloxyethyl)-3-ethyloxetane, 2-ethyl-3-(propyleneoxyethyl)oxetane, 3-(propylene oxide) Base ethyl)-2- An oxocyclic acrylate such as phenyloxetane or 2,2-difluoro-3-(acryloxyethyl)oxetane. Specific examples of the above compound (a2-2) include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, and methacrylic acid 3- Hydroxypropyl ester, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexyl methyl acrylate, 4-hydroxymethyl-cyclohexyl methyl methacrylate, 2,3-di acrylate Hydroxypropyl ester, 2,3-dihydroxypropyl methacrylate, 2-(6-hydroxyhexyloxy)ethyl acrylate, 2-(6-hydroxyhexyloxy)ethyl methacrylate, and the like. Specific examples of the compound (a2 - 3) include alkyl acrylates such as methyl acrylate and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and methyl group. Dibutyl acrylate, butyl methacrylate, etc. methyl propyl-14· 200949442 alkyl enoate: cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1. 02 '6] decane-8-yl ester, acrylate alicyclic ester such as 2-(tricyclo[5.2.1. 〇2'6]decane-8-yloxy)ethyl acrylate or isobornyl acrylate ; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.02,6]decane-8-yl methacrylate, 2-(tricyclic [5.2. 1.02,6]decane-8-yloxy)ethyl ester, isobornyl methacrylate, etc.; methacrylate aryl ester such as phenyl acrylate or benzyl acrylate; Alkyl ester; aryl methacrylate such as phenyl methacrylate or benzyl methacrylate; and aralkyl methacrylate; maleic acid Dialkyl dicarboxylate such as ethyl ester, diethyl fumarate or diethyl itaconate; tetrahydrofurfuryl methacrylate, tetrahydrofuranyl methacrylate, tetrahydropyran-2, methacrylate a methyl acrylate or the like having a saturated five-membered heterocyclic ring or a six-membered heterocyclic ring containing one oxygen atom; φ 4-propenyloxymethyl-2-methyl-2-ethyl-1,3 - Dioxolane, 4· Propenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolan, 4-propenyloxymethyl-2-cyclohexyl-1 , 3-dioxolan, 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2 -Acetyl ester having a saturated five-membered heterocyclic ring containing two oxygen atoms, such as methyl-2-isobutyl-1,3-dioxolane; 4-propenyloxymethyl-2,2-dimethyl -1,3-dioxolane, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolan, 4-propenyloxymethyl-15- 200949442 Base-2,2-diethyl-1,3-dioxolane, 4-propanoid oxime oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4 - propylene methoxymethyl-2-cyclopentyl-1,3-dioxolane, 4-propane醯oxymethyl-2-cyclohexyl-1,3-dioxolane, 4·propenyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Propylene methoxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxybutyl-2 -methyl-2·ethyl-1,3 - an acrylate having a saturated five-membered heterocyclic ring containing two oxygen atoms, such as dioxolane; styrene, α-methylstyrene, m-methylstyrene, p-methylphenyrene, p-methoxy Vinyl aromatic compound such as styrene; fluorene-phenylmaleimide, fluorene-cyclohexylmaleimide, hydrazine-pre-maleimide, hydrazine-succinimide-3.醯imino benzoate, Ν-amber quinone imido-4-maleimido butyrate, Ν-amber quinone imido-6-maleimido hexanoate, Ν-Amber quinone imino-3-maleimidopropionate, Ν-(9-acridinyl)maleimide, and the like, a substituted-substituted maleimide; A conjugated diene such as butadiene, isoprene or 2,3-dimethyl-1,3-butadiene. In addition, a polar unsaturated compound such as acrylonitrile, methacrylonitrile, propylene Q decylamine or methacrylamide may be mentioned, and the compound (a2) used in the production of the polymer [Α1] is improved. From the viewpoints of copolymerization reactivity, developability of the film, and compression properties of the resulting spacer, it is preferred to use trimethyl [5.2.1.02'6]nonane-8-yl (methacrylate) of styrene and methacrylic acid. Tricyclodecyl ester), glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxy methacrylate Cyclohexylmethyl ester, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methyl-16- 200949442 Acryloxymethyloxane Butane, tetrahydrofurfuryl methacrylate, 1,3-butadiene, 2-hydroxyethyl acrylate, 2-(6-hydroxyethylhexyloxy)ethyl methacrylate and 4- At least one selected from the group consisting of acryloxymethyl-2-methyl-2-ethyl-1,3-dioxolane. The content ratio of the repeating unit derived from the compound (a1) in the polymer [A1] is preferably from 5 to 50% by weight, more preferably from 5 to 40% by weight, particularly preferably 10, based on the total of all repeating units. ~30% by weight. If the content ratio of the repeating unit derived from the compound (a1) is less than 5% by weight, the solubility of 0 in the alkali developing solution tends to be insufficient, and on the other hand, if it exceeds 50% by weight, it may occur. The solubility of the developing solution is too large. The content ratio of the repeating unit derived from the compound (a 1) in the precursor polymer [A2 - 1] is preferably 10 to 60% by weight, more preferably 15 to 50% by weight based on the total amount of all the repeating units. . The proportion of the repeating unit derived from the compound (a 1) in the precursor polymer [A2-2] is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, based on the total of all the repeating units. The content ratio of the repeating unit derived from the φ compound (a2-2) in the precursor polymer [A2-2] is preferably 5 to 60% by weight based on the total amount of all repeating units, and more preferably 1 to 50% by weight. %. The content ratio of the repeating unit of at least one selected from the group consisting of the free-derived compound (a2 - 1) and the compound (a2 - 3) in the precursor polymer [A2-2] is preferably based on the total amount of all repeating units. It is 2 〇 to 80% by weight, more preferably 25 to 70% by weight. The polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2] may be via a compound in which the unsaturated compound as described above is not in the above formula (8), Tables 17 to 200949442 (hereinafter In the presence of a "polythiol compound", it is preferably prepared by radical polymerization in the presence of a polymerization initiator in a suitable solvent. The above polythiol compound is in the polymer [A1], precursor polymerization. A component which acts as a chain transfer agent when the product [A2 -1] and the precursor polymer [A2 - 2] are synthesized. As the polyvalent thiol compound, for example, an esterified product of a mercaptocarboxylic acid and a polyhydric alcohol can be used, and Q is used as the above mercaptocarboxylic acid, and examples thereof include mercaptoacetic acid, 3-mercaptopropionic acid, and 3-mercaptobutyric acid. And 3-mercaptoic acid or the like; examples of the polyhydric alcohol include ethylene glycol, tetraethylene glycol, butylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-tri ( 2-hydroxyethyl) urethane, sorbitol, and the like. Specific examples of the preferred polyvalent thiol compound used in the present invention include, for example, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and tetraethylene glycol. Bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(mercaptoacetate), 1,4-bis(3-mercaptobutyrate) Butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione and the like. The above polythiol compounds may be used singly or in combination of two or more. The ratio of use of the polythiol compound in the synthesis of the polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2] is preferably 〇 with respect to 1 Å of all unsaturated compounds. 5 to 30 parts by weight, more preferably 1 to 20 -18 to 200949442 parts by weight, particularly preferably 1.5 to 10 parts by weight. When the ratio of use of the polythiol compound is less than 0.5 part by weight, there is a case where the desired molecular weight distribution cannot be obtained. On the other hand, when it exceeds 30 parts by weight, there is a case where a high polymerization conversion ratio is not easily obtained. Examples of the solvent which can be used in the synthesis of the polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2] include, for example, ethylene glycol alkyl ether acetate, diethylene glycol, and Propylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, ketones, esters, and the like. Λ As the diethylene glycol, for example, diethylene glycol monomethyl ether 'diethylene glycol oxime monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether And the dipropylene glycol may, for example, be dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol ethyl methyl ether or the like; as the propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; φ as propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; as the propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether Propionate, propylene glycol butyl ether propionate or the like; examples of the ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; -19- 200949442 Examples of the esters include methyl acetate Ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, ethoxylate, ethyl ethoxyacetate, propoxyacetic acid Methyl ester, methyl propoxy ethoxybutoxyacetate, ethyl butoxylate, methyl 3-methoxy 2-methoxypropionate, ethyl 2-methoxypropionate, 2-ethoxy Ester, ethyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butylethyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- 0 methyl ester, ethyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate Preferred is ethylene glycol alkyl ether acetate, diethylene glycol alcohol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, which is diethylene glycol dimethyl ether, diethylene glycol ethyl methyl Ether, dipropyl diether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, malonate or 3-methoxybutyl acetate. The above solvents may be used singly or in combination of two or more. The radical polymerization initiator which can be used in the production of the polymer [A1], the precursor polymer [A2-1], and the former [A2-2] is particularly limited, and examples thereof include 2,2'-azo Isobutyronitrile, bis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2-pentanenitrile), 4,4'-azobis(4- Cyanovalerate, dimethyl 2,2'-methylpropionate, 2,2'-azobis(4-methoxy-2,4-dimethyl nitrogen compound. These free radical polymerizations The initiator may be used singly or in combination. Esters, acetates, ethyl lactate, butyl acrylate, methoxypropionic acid ethoxypropyl 3-propoxy and the like. In the second, the special alcohol dimethyl alcohol methyl ether drive polymer does not have 2,2'-azo, 4 · dimethyl azobis(2-pentanenitrile) and other kinds of mixed -20- 200949442 By carrying out the polymerization as described above, the molecular weight distribution of the obtained polymer can be controlled 'at the same time, the unreacted unsaturated compound can be reduced. As a result, the supplied polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2] can be supplied. - 2] Free radical polymerization of insufficient And the conversion ratio of the compound to the polymer (hereinafter referred to as "conversion") is more than 95% by weight. Here, the polymerization conversion ratio may be the actual addition weight of each component supplied to the radical polymerization and the solid of the polymer solution after polymerization. The content concentration (the ratio of the total weight of all the components other than the solvent contained in the radiation sensitive resin composition to the total weight of the composition (% by weight). The same applies hereinafter. The solid content concentration is determined. The obtained polymer solution was weighed and placed in an aluminum dish and heated on a hot plate at 175 ° C for 1 hour, and the weight before and after heating was measured to calculate (weight after heating x 00 / weight before heating). (% by weight) = solid content concentration (% by weight) of the polymer solution after polymerization >< Actual addition total weight of all components/actual total weight of components other than solvent. In the preparation of the polymer [A2-1], the reaction of the precursor copolymer [A2-1] with the compound φ (a2 - 1) can be carried out by a known method. The compound (a2-1) used herein is preferably used from the viewpoint of improving the storage stability of the resulting radiation sensitive resin composition and further improving the heat resistance and chemical resistance of the spacer thus obtained. At least one selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. The ratio of the compound (a2_ used in the synthesis of the polymer [A2 - 1], preferably from 21 to 200949442, is selected from the group consisting of a carboxyl group and a carboxylic anhydride group contained in the precursor copolymer [A2 - oxime]. The residual amount of the group (unreacted group) which is not used for the reaction with the compound (a2-1) in at least one group is at a level suitable for alkali solubility of the obtained polymer [A2-1]. The ratio of the content of the repeating unit having the above-mentioned unreacted group in the polymer (polymer [A2 - 1]) after the reaction is 5 to 30% by weight based on the total amount of all the repeating units, and more preferably 1〇~20% by weight. In the synthesis of the polymer [A2-2], the reaction of the precursor copolymer [A2-2] with the non-φ saturated isocyanate compound can be carried out by a known method. As the unsaturated isocyanate compound, The unsaturated compound having an isocyanate group is not particularly limited, and examples thereof include 2-propenyloxyethyl isocyanate, 3-propenyloxypropyl isocyanate, and 4-propenyloxybutyl isocyanate. 6·Acrylonitrile Hexyl isocyanate, 8-propenyloxyoctyl isocyanate, 10-propenyloxydecyl isocyanate, 1,1-(dipropenyloxymethyl)ethyl isocyanate, 2-(2-isocyanate ethoxylate) Acrylic acid derivatives such as ethyl ester: ❹ 2 —methacryloxyethyl isocyanate, 3-methacryloxypropyl isocyanate, 4·methacryloxybutyl isocyanate, 6-methyl Propylene nonyloxyhexyl isocyanate, 8-methylpropenyloxyoctyl isocyanate, 10-methylpropenyloxydecyl isocyanate, hydrazine, dimethyl propylene methoxymethyl) ethyl isocyanate, A methacrylic acid derivative such as 2-(2-isocyanate ethoxy)ethyl acrylate; and the unsaturated isocyanate compound is preferably 2 _ from the viewpoint of reactivity with the precursor copolymer [A2 - 2]. Acryloxyethyl isocyanate-22-200949442 ester, 2-methylpropenyloxyethyl isocyanate, 2-(2-Isocyanate ethoxy) methacrylate, and the like. In the synthesis of the polymer [A2-2], the unsaturated isocyanate compounds may be used singly or in combination of two or more. The ratio of use of the unsaturated isocyanate compound when preparing the polymer [A2-2] is preferably 0.1 to 90 mol%, more preferably 1 to 80 mol%, based on the hydroxyl group of the precursor copolymer [A2-2]. % of ear, especially preferably 25 to 75 mol%. When the amount of the unsaturated isocyanate compound is less than 莫1 mol%, the sensitivity to the resulting radiation-sensitive resin composition and the improvement of the elastic properties of the spacer member produced therefrom are small. On the other hand, when it exceeds 90 mol%, an unreacted unsaturated isocyanate compound remains in the reaction liquid, and the storage stability of the obtained polymer solution and the radiation sensitive resin composition tends to be insufficient. [Polymerizable Compound [B]] The polymerizable compound [B] in the radiation sensitive resin composition of the present invention is a compound having a polymerizable unsaturated bond. The polymerizable compound [B] is not particularly limited, and a monofunctional, difunctional or trifunctional or higher (meth) group is preferably used from the viewpoint of good polymerizability and improvement in the strength of the obtained spacer. Acrylate. Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, and diethylene glycol monoethyl methacrylate. , isobornyl acrylate, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-propenyloxyethyl-2-hydroxypropane Phthalates, 2-methacryloxyethyl 2-hydroxypropyl orthophthalene-23-200949442 Dicarboxylate, ω-carboxypolycaprolactone monoacrylate, and the like. As the commercial product, for example, Aronix® 101, Aronix M-111, Aronix®-ΐ14, Aronix M-5300 (produced by East Asia Synthetic Co., Ltd.), KAYARAD TC-110S, KAYARAD TC-120S (by Nissan Chemical Co., Ltd.); Viscoat 158, Viscoat 2311 (produced by Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of the above difunctional (meth) acrylate include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, and tetraethylene glycol. Diacrylate, tetraethylene Φ alcohol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1 , 9-nonanediol dimethacrylate, bis(phenoxyethanol) ruthenium diacrylate, bis(phenoxyethanol) ruthenium dimethacrylate, and the like. As a commercial item, for example, Aronix® 210, Aronix® 240, Aronix M-6200 (produced by East Asia Synthetic Co., Ltd.), KAYARAD HDDA, KAYARAD® 220, KAYARAD R — 604 (by Japanese chemical) can be cited. (Stock) production); Viscoat 260, Viscoat 312, Viscoat 3 3 5 HP (produced by Osaka Organic Chemical Industry Co., Ltd.), etc. © The trifunctional or higher (meth) acrylate may, for example, be trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate or pentaerythritol. Tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propenyloxyethyl) a phosphonate, a tris(2-methylpropenyloxyethyl)phosphonate, an ethylene oxide-modified dipentaerythritol hexaacrylate, etc., in addition to the above, it can also be exemplified in the presence of -24-200949442 Aminic acid obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups with a (meth) acrylate compound having three or more functional groups having one or more hydroxyl groups in the molecule An ester (meth) acrylate compound or the like. The urethane (meth) acrylate compound is preferably a non-functional compound or more. As a commercially available product of the above trifunctional or higher (meth) acrylate, for example, Aronix M-309, Aronix® I-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, φ can be cited. Aronix Μ - 8060, Aronix TO — 1450 (produced by East Asia Synthetic Co., Ltd.); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA -20 > KAYARAD DPCA - 30, KAYARAD DPCA — 60, KAYARAD DPCA - 120, KAYARAD DPEA - 12 (produced by Nippon Kayaku Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (produced by Osaka Organic Chemical Industry Co., Ltd.), etc., especially as a non-functional urethane Examples of the (meth) acrylate compound include New Frontier R-1150 (above produced by First Industrial G Pharmaceutical Co., Ltd.), KAYARAD DPHA-40H (produced by Nippon Kayaku Co., Ltd.), and the like. As the polymerizable compound [B] in the present invention, among the above, a trifunctional or higher (meth) acrylate is preferably used, and particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethylene oxide-modified dipentaerythritol hexaacrylate. The above monofunctional, difunctional or trifunctional or higher (meth) acrylates -25 to 200949442 may be used singly or in combination of two or more. In the radiation sensitive resin composition of the present invention, the use ratio of the polymerizable compound [B] is preferably from 50 to 200 parts by weight, more preferably from 60 to 150 parts by weight, per 100 parts by weight of the polymer [A]. . When the amount of the polymerizable compound [B] is less than 50 parts by weight, there is a possibility that development residue may occur during development. On the other hand, if it exceeds 200 parts by weight, the adhesion of the resulting spacer to the substrate may not be sufficiently good. tendency. [[C] Radiation-Terminal Polymerization Initiator] The [C] radiation-sensitive polymerization initiator in the radiation sensitive resin composition of the present invention is irradiated with visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like. A component which produces an active seed capable of initiating polymerization of the polymerizable compound [B]. Examples of such a [C] radiation-sensitive polymerization initiator include a radiation-sensitive linear radical polymerization initiator and a radiation-sensitive linear cationic polymerization initiator. Examples of the radiation-sensitive radical polymerization initiator include a fluorenyl-fluorenyl hydrazine compound, an acetophenone compound, a diimidazole compound, a benzoin compound, a benzophenone compound, an α-diketonated compound, and a multinuclear compound. A ruthenium compound, a xanthone compound, a phosphine compound, a triple well compound, or the like. The radiation-sensitive linear cationic polymerization initiator may, for example, be a key salt or a metallocene compound. The above fluorene-fluorenyl hydrazine compound may, for example, be ethyl ketone, 1-[9-ethyl-6-(2-methylbenzomethyl)-9.Η.-carbazol-3-yl]-, 1-(0-ethylhydrazinium), 1-[9-butyl-6-(2-ethylbenzylidene)-9.Η.-carbazol-3-yl]-ethane-1- Ketooxime-indole-benzoate, ethyl ketone, 1-[9-ethyl-6-[2-methyl-4.(2,2-dimethyl-1,3-dioxolanyl) Methoxybenzylidene]-9.Η.-carbazole-3· -26- 200949442 base]-,l-(〇-acetamidoxime), 1,2-octanedione-l-[4 -(phenylthio)phenyl]-2·(0-benzylidenehydrazine), 1,2·butanedione-1-[4-(phenylthio)phenyl]-2-(0-benzene Mercaptopurine), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2·(0-acetamidopurine), 1,2-octanedione-1-[ 4-(methylthio)phenyl]-2-(0-benzylidenehydrazine), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0- (4-methylbenzimidoxime), etc. Among these 0-mercaptopurine compounds, particularly preferred is ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9 .Η.-carbazol-3-yl]-, 1-(0-ethylhydrazinium), ethyl ketone, 〇1-[9-ethyl-6-[2-methyl-4-(2,2 - dimethyl-1,3-dioxolanyl) methoxybenzimidazole Base]-9.Η.-carbazol-3-yl]·, 1-(0-ethylindenyl), 1,2-octanedione-1-[4-(phenylthio)phenyl]- The above-mentioned 0-fluorenyl hydrazine compound may be used singly or in combination of two or more. Examples of the acetophenone compound include an α-hydroxyketone compound and an α-amino ketone compound. And other compounds other than these. Examples of the above α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4·isopropylphenyl)_2- Hydroxy-2-methylpropane-1-one-1-one, 4-(2·hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, etc.; The above α-amino ketone compound may, for example, be 2-methyl-1(4-methylthiophenyl)-2-morpholinylpropan-1-one or 2-benzyl-2-dimethylamine. Base-i-(4-morpholinylphenyl)-butan-1-one, 2-(4-methylbenzylidene)-2-(dimethylamino)-: 1-(4-) And phenyl phenylbutane-1-one; and other compounds other than these, for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-di Methoxy-2-phenylphenethyl-27- 20 0949442 Ketones, etc. Among these acetophenone compounds, 'extra is 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one or 2-(4-methylbenzene) Mercapto)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butane-one. These acetophenone compounds may be used singly or in combination of two or more. As the above diimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxyanthrylphenyl)·ι, 2'_ can be mentioned. Dimime, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)_1,2,-diimidazole, 2,2, - bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2,-bis(2,4-dichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2,-diimidazole, 2,2,-bis(2,4,6-trichlorophenyl)-4,4,,5,5' - Tetraphenyl-1,2'-diimidazole and the like. Among these diimidazole compounds, 2,2,-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2,- is preferred. Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2,-bis(2,4,6-trichlorobenzene 4-) 4,4',5,5'-tetraphenyl-1,2,-diimidazole, etc., particularly preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-diimidazole. © The above diimidazole compounds may be used singly or in combination of two or more. By using these diimidazole compounds, the sensitivity to radiation, the resolution, and the adhesion of the produced spacer to the substrate can be further improved. In the radiation sensitive resin composition of the present invention, when a diimidazole compound is used as the [C] radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamine group may be added (hereinafter, referred to as At least one selected from the group consisting of an "amine-based sensitizer" and a thiol compound. The above amine-based sensitizer is a compound having a function of increasing the sensitivity of the radiation of the diimidazole compound to -28-200949442 and improving the efficiency of production of the imidazole radical, and can improve the sensitivity and resolution of the radiation-sensitive resin composition and further improve The spacer or the protective film formed is added for the purpose of adhesion to the substrate. Examples of such an amine-based sensitizer include N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-di(diethylamino). Among these amine-based sensitizers, such as benzophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, etc., particularly preferred is 4,4'-di(diethylamino). ) benzophenone. These amine-based sensitizers may be used alone or in combination of two or more. The addition amount of the amine-based sensitizer is preferably 0.1 to 50 parts by weight, more preferably 1 to 1 part by weight per 100 parts by weight of the diimidazole compound. 20 parts by weight. When the amount of the amine-based sensitizer added is less than 1 part by weight, the improvement effect of sensitivity, resolution, and adhesion may be insufficient. On the other hand, if it exceeds 50 parts by weight, it may occur. The case of damaging the shape of the spacer formed. The above thiol compound is a compound having a function of supplying a hydrogen radical to an imidazole radical and, as a result, producing a component having a sulfur radical. The polymerization initiation energy of the diimidazolium chelating compound which is broken by radiation irradiation to generate an imidazole radical is moderately high, and is not very high. Therefore, if it is directly used for forming a spacer of a liquid crystal display element, spacers may occur. The case where the sectional shape is an undesired shape of an inverted cone shape. However, by adding a thiol compound thereto, a hydrogen radical is supplied from the thiol compound to the imidazole radical, and as a result, the imidazole radical is converted into a neutral imidazole, and at the same time, a component having a higher thiol radical having a higher polymerization initiation energy is produced. This ensures that the shape of the spacer becomes a better positive taper. As such a thiol compound, for example, 2-锍-29-200949442 benzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzene can be mentioned. An aromatic thiol compound such as thiazole or 2-mercapto-5-methoxybenzimidazole; 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 3- An aliphatic monothiol compound such as octyl propyl propionate; 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate) An aliphatic thiol compound or the like having two or more functional groups. Among these thiol compounds, particularly preferred is 2, mercaptobenzothiazole. The amount of the thiol compound to be added is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, per part by weight of the diimidazole φ compound. When the amount of the thiol compound added is less than 0.1 part by weight, the effect of improving the shape of the spacer may be insufficient. On the other hand, if it exceeds 50 parts by weight, the shape of the spacer formed may be impaired. . In the radiation sensitive resin composition of the present invention, when a diimidazole compound is used as the [C] radiation-sensitive polymerization initiator, it is preferred to add both the above-mentioned amine-based sensitizer and thiol compound. The onium salt in the above-mentioned radiation-sensitive cationic cationic polymerization initiator may, for example, be phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate or phenyldiazonium hexafluoroarsenate. Wait for the diazonium salt. Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, three Phenylhydrazine p-toluenesulfonate and the like. Examples of the metallocene compound include (l-6-η-cumene) (η·cyclopentadienyl) iron (1+) hexafluorophosphoric acid (1 Ί, etc.). The above-mentioned radiation-sensitive cationic cationic polymerization initiator may be used alone or The two are used in combination with -30-200949442. The ratio of use of the [C] radiation-sensitive polymerization initiator in the radiation-sensitive resin composition of the present invention is preferably 0.01 to 120 with respect to 100 parts by weight of the polymer [A]. The amount by weight is more preferably from 1 to 100 parts by weight. When the ratio of use of the [C] radiation-sensitive polymerization initiator is less than 0.01 part by weight, the residual film ratio tends to be insufficient at the time of development, and on the other hand, if it exceeds 120 parts by weight In the case where the portion which is not exposed during development is insufficient in solubility in the alkali developer, the radiation sensitive linear composition of the present invention preferably contains the [C] radiation-sensitive polymerization initiator. A ruthenium-indenyl ruthenium compound. In the radiation sensitive resin composition of the present invention, a highly sensitive radiation sensitive resin composition can be obtained by using a ruthenium-fluorenyl ruthenium compound, and good adhesion can be obtained. of In the radiation sensitive resin composition of the present invention, when a ruthenium-indenyl ruthenium compound is used as the [C] sensitizing radiation polymerization initiator, the use ratio of the oxime oxime compound is relative to 100 parts by weight. The polymer [A] is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight. When the amount of the polymerization initiator of the 0-fluorenyl type is less than 0.01 part by weight, development may occur. When the residual film ratio is insufficient, on the other hand, if it exceeds 30 parts by weight, the portion which is not exposed during development may be insufficiently soluble in the enamel developing solution. In the radiation sensitive resin composition of the present invention, [C] a radiation-sensitive polymerization initiator, which can be used in combination with one or more other radiation-sensitive polymerization initiators. As another radiation-sensitive polymerization initiator, an acetophenone compound is preferred. At least one selected from the group consisting of a diimidazole compound and a sensitization-31-200949442 radiation-based cationic polymerization initiator. In the radiation-sensitive resin composition of the present invention, when ruthenium-fluorenyl ruthenium is polymerized When used in combination with other radiation-sensitive polymerization initiators, the ratio of use of the other radiation-sensitive polymerization initiator is preferably 80% by weight or less, and more preferably 70% by weight, based on the total radiation polymerization initiator. In the invention, the shape, compression strength, and the like of the resulting spacer can be further improved by using at least one selected from the group consisting of an acetophenone compound and a diimidazole compound as the other polymerization initiator. <Other Additives> The radiation sensitive resin composition of the present invention contains the polymer [A], the polymerizable compound [B], and the [C] radiation-sensitive polymerization initiator as described above as essential components without impairing the present invention. Within the scope of the intended effects of the invention, other additives than the above may be contained as needed. Examples of such other additives include [D] surfactant, [E] binder, [F] storage stabilizer, [G] heat resistance improver, and the like. [[D] Surfactant] G The above [D] surfactant may be contained in the radiation sensitive resin composition of the present invention in order to improve coatability. As such a [D] surfactant, a fluorine-based surfactant, a siloxane-based surfactant, or another surfactant can be mentioned. As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group in at least any of a terminal, a main chain and a side chain is preferably used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether and 1,1,2,2-tetrafluorooctylhexyl ether. Octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol di(i,i,2,2,3,3-hexafluoropentyl)-32- 200949442 ether, Octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, fluoroalkyl polyoxyethylene ether , diglycerin tetra (fluoroalkyl polyoxyethylene ether), perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, fluoroalkyl ester, and the like.

As the commercial product, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F178, Megafac F191, Megafac F471, Megafac F476 (above, produced by Di Aisheng Co., Ltd.), Ftergent FT-100, and Ftergent FT can be cited. 110, Ftergent FT

— 140A, Ftergent FT — 150, Ftergent FT — 250, Ftergent FT — 251' Ftergent FTX — 25 1. Ftergent FTX — 2 1 8. Ftergent FT — 300, Ftergent FT — 310, Ftergent FT — 400S (above, by Neos) (Production) and the like β as the above-mentioned polyoxyalkylene-based surfactant, and commercially available product names include, for example, Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA 'Toray Silicone SH29PA, Toray Silicone See SH30PA, Toray Silicone SH-190 'Toray Silicone SH — 193, Toray Silicone SZ — 6032, Toray Silicone SF — 8428, Toray Silicone DC — 57, Toray Silicone DC — 190 (above, produced by Toray Dowcornig Silicone) Wait. Examples of the other surfactants include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Commercially available products include KP 3 . 4 1 (Shin-Etsu Chemical Industry Co., Ltd.), Polyflow No. 57, 95 (Production of Kyoeisha Chemical Co., Ltd.) -33- 200949442, etc. These surfactants may be used alone or in combination of two or more. The amount of the [D] surfactant to be mixed is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 1 part by weight of the polymer [A] '. When the amount of the [D] surfactant is more than 5 parts by weight, film cracking tends to occur at the time of coating. [[E] Adhesive Aid] The radiation sensitive resin composition of the present invention may contain an [E] adhesion aid in order to improve the adhesion of the spacer having φ to the substrate. As such an [E] adhesion aid, a functional decane coupling agent is preferably used, and examples thereof include a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. . More specifically, for example, trimethoxydecyl benzoic acid, r-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, and r-isocyanate may be mentioned. Propyltriethoxydecane, τ·-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These adhesion aids may be used alone or in combination of two or more. The mixing ratio of the [E] binding aid in the radiation sensitive resin composition of the present invention is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the polymer [A]. If the compounding amount of the [E] binder is more than 20 parts by weight, development residue may easily occur. [[F] Storage Stabilizer] The radiation-sensitive resin composition of the present invention may contain [F] storage stability 1 ° as [F] storage stabilizer for the purpose of improving the stability of storage stability - 34 - 200949442, etc. For example, sulfur, a compound, a hydrogen compound, a polyoxy compound, an amine compound, a nitronitroso compound, and the like are listed. The radiation sensitive resin composition of the present invention is used in a proportion of preferably 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, per 100 parts by weight of the polymer [A], [F] storage stabilizer. When the cerium exceeds 3.0 parts by weight, a sufficiently high radiation sensitivity cannot be obtained, and a pattern shape may be deteriorated. φ [[G] heat resistance improver] In order to further improve the heat resistance of the produced spacer, an N-(alkoxymethyl)glycolide compound, N-( may be added to the radiation sensitive resin composition of the present invention. An alkoxymethyl) melamine compound or a compound having a difunctional or higher epoxy group in one molecule. Specific examples of the above N-(alkoxymethyl)glycoluric compound include N,N,N',N'-tetrakis(methoxymethyl)glycoluril, N,N,N',N'. - Tetrakis(ethoxymethyl) glycoluril and the like. Among them, N, N, N', N'-tetrakis(methoxymethyl) guanylurea is particularly preferred. Among the above N-(alkoxymethyl)melamine compounds, particularly preferred are 1^, :^, :^', :^',:^'', :^'-hexa(methoxymethyl)melamine. As the commercial product, Nikalac N-2702, MW-30M (the above is produced by Sanwa Chemical Co., Ltd.) and the like can be cited. Examples of the compound 'having a bifunctional or higher epoxy group in the above molecule include trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and bisphenol A diglycidyl ether. As a commercial example of -35-200949442, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1 500NP, Epolight 1 600, Epolight 80MF, Epolight 100 MF, Epolight 4000 can be cited. , Epolight3 0 02 (above produced by Gongrongshe Chemical Co., Ltd.), etc. They may be used singly or in combination of two or more. [The radiation sensitive resin composition] The radiation sensitive resin composition of the present invention preferably has a radiation sensitivity to the polymer [A], the polymerizable compound [B] and the [C]. The polymerization initiator and any other components selected for use in φ are dissolved in a suitable solvent to prepare a solution-like composition. As the solvent to be used in the preparation of the above-mentioned composition solution, a solvent which can uniformly dissolve the components constituting the radiation sensitive resin composition and does not react with each component is used. As such a solvent, the same solvent as exemplified as a solvent which can be used for the production of the above polymer [A1], precursor polymer [A2 - 1] and precursor polymer [A2 - 2] can be mentioned. © In such a solvent, it is preferable to use, for example, an alcohol, a glycol ether, or an ethylene glycol alkyl ether acetate from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like. Ester' esters and diethylene glycol. Among them, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, and the like can be used. Glycol ethyl methyl ether, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxypropionate, 3-methoxyl acetate Butyl ester. Further, in order to improve the in-plane uniformity of the film thickness of the formed film, a high boiling point solvent may be used in combination with the above solvent. Examples of the high-boiling solvent which can be used together include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N. _Dimethyl acetamide, N. methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, γ-butyrolactone, ethylene carbonate, Propylene carbonate, phenyl cellosolve acetate, and the like. Among them, preferred are Ν-methylpyrrolidone, γ-butyrolactone, hydrazine, hydrazine-dimethylacetamide. The composition solution thus prepared can also be filtered by using a micropore filter having a pore diameter of, for example, about 0·2 to 0.5 μηη, and then supplied. The radiation sensitive resin composition of the present invention is particularly suitably used as a material for forming a spacer for a display element such as a liquid crystal panel or a touch panel. <Method for Producing Spacer for Display Element> Next, a method of producing the spacer of the present invention using the radiation sensitive resin composition of the present invention will be described. The manufacture of the spacer of the present invention includes at least the steps in the following order. Ο (1) a step of forming a film of the radiation sensitive resin composition of the present invention, (2) a step of exposing at least a part of the film, (3) a step of developing the film after exposure, and ( 4) A step of heating the developed film. Hereinafter, each of these steps will be described in order. [(1) Step] A transparent conductive film is formed on one surface of a transparent substrate, and the radiation sensitive resin composition of the present invention is applied onto the transparent conductive film to form a film. -37-200949442 The transparent substrate used herein may, for example, be a glass substrate or a resin substrate, and more specifically, a glass substrate such as soda lime glass or samarium-free glass; polyethylene terephthalate or poly A plastic resin substrate such as butylene terephthalate, polyether mill, polycarbonate, or polyimide. As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (Sn 2), an ITO film made of indium tin oxide (In2〇3_SnO 2 ), or the like can be used. As a method of forming the film, a coating method or a dry film method can be employed. φ When the coating film is formed by a coating method, the radiation-sensitive resin composition of the present invention is applied onto the transparent conductive film, and then the solvent is removed by heating the coated surface (prebaking) to form a coating film. The solid content concentration of the radiation sensitive resin composition used in the coating method (the ratio of the total weight of all components except the solvent in the radiation sensitive resin composition to the total weight of the radiation sensitive resin composition (% by weight) The same is preferably from 5 to 50% by weight, more preferably from 1 to 40% by weight, still more preferably from 1 5 to 35% by weight. The coating method is not particularly limited, and may be, for example, a spray φ method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet coating method, or the like. The method is particularly preferably a spin coating method or a slit die coating method. The radiation sensitive resin composition of the present invention is particularly suitable for use in a slit die coating method, and even when the moving speed of the slit die is 150 mm/sec, uneven coating is not caused. Further, when the film is formed by the dry film method, the dry film to be used is formed by laminating a radiation sensitive layer composed of the radiation sensitive resin composition of the present invention on the base film, preferably on the plastic base film (hereinafter It is called "sensing -38- 200949442 ray dry film"). The radiation sensitive dry film can be formed by applying a radiation sensitive linear layer on the base film, preferably in the form of a solution composition, by applying the radiation sensitive resin composition of the present invention and removing the solvent. The solid content concentration of the composition solution for the radiation sensitive layer of the laminated radiation-sensitive dry film is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, still more preferably 20 to 50% by weight. , particularly preferably 30 to 50% by weight. As the base film of the radiation-sensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), φ polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the base film is preferably in the range of 15 to 125 μm. The thickness of the radiation sensitive layer is preferably from 1 to 30 μm. When the radiation-sensitive linear dry film is not used, the radiation-sensitive layer may be deposited on the radiation-sensitive layer. The film preferably has a moderate release property so that it does not fall off when not in use (during storage), and can be easily peeled off during use. As the film which satisfies such a condition, for example, a polyoxyalkylene type release agent can be applied or sintered on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polyurethane film. Film. The thickness of the film is preferably 5 to 30 μm. These coatings may also be laminated coatings in which two or three layers are laminated. Such a dry film can be formed on a transparent conductive film of a transparent substrate by lamination by a suitable method such as hot pressing. The film thus formed is then preferably prebaked. The pre-baking conditions are different depending on the type of each component, the blending ratio, and the like, and it is preferably carried out at 70 to 120 ° C for about 1 to 15 minutes. -39- 200949442 The thickness after pre-baking of the film is preferably 0.5 to 10 μm, more preferably 1.0 to 7.0 μm. [(2) Step] Next, at least a part of the formed film is exposed. At this time, when a part of the film is exposed, exposure is performed via a photomask having a predetermined pattern. As the radiation to be used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength of from 190 Å to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable. The exposure amount is 値 measured by an illuminometer (Model OAI model 3 56, manufactured by OAI Optical Associates Inc.), which is preferably 100 to 10000 J/m2, more preferably 500 to 3,000. J/m2. [(3) Step] Next, by developing the exposed film, unnecessary portions are removed to form a predetermined pattern. The developing solution used for development is preferably an alkali developing solution, and examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia; An aqueous solution of a basic compound such as a quaternary ammonium salt such as a quaternary ammonium or tetraethylammonium hydroxide. Further, an aqueous solution of the above basic compound may be added with an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant. As the developing method, any one of the liquid-filling method, the dipping method, and the rinsing method may be -40-200949442, and the development time is preferably about 10 to 180 seconds. After the development, it is washed with running water for, for example, 30 to 90 seconds, and then air-dried by, for example, compressed air or compressed nitrogen to form a desired pattern. [(4) Step] Next, the obtained pattern is heated (post-baking) at a predetermined temperature, for example, 1 to 230 ° C by using a heating means such as a hot plate or an oven, to obtain a desired interval. Things. The heating time is preferably from 5 to 30 minutes when the heating is carried out on the hot plate, and preferably from 30 $ to 180 minutes when it is carried out in an oven. <Liquid Crystal Display Element> The liquid crystal display element of the present invention has a spacer manufactured from the radiation-sensitive resin composition of the present invention as described above. The liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b). (a) First, a pair of (two) transparent substrates having a transparent conductive film (electrode) on one side are prepared, and on the transparent conductive film of one of the substrates, the radiation-sensitive resin composition of the present invention is used. The method forms a spacer. Then, an alignment film having liquid crystal alignment energy was formed on the transparent conductive film and the spacer of these substrates. The one surface on which the alignment film is formed is used as the inner side, and these substrates are disposed to face each other with a certain gap (cassette gap) so that the liquid crystal alignment directions of the respective alignment films are perpendicular or antiparallel to each other, and the substrate surface (alignment film) and the spacer are provided. The cell gap enclosed by the object fills the liquid crystal, and the filling hole is closed to form a liquid crystal cell. Then, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarization direction thereof is the same as the liquid crystal alignment direction of the alignment film formed on one side of the substrate or the vertical direction of -41-200949442, and the liquid crystal display of the present invention can be obtained. element. (b) First, a pair of transparent substrates in which a transparent conductive film, a spacer, and an alignment film are formed in the same manner as in the above method (a) are prepared. Then, an ultraviolet curable sealant was applied by a dispenser along the end portion of one of the substrates, and then fine droplets of liquid crystal were dropped by a liquid crystal dispenser, and the two substrates were bonded under vacuum. Then, the above-mentioned sealant portion is irradiated with ultraviolet rays by a high-pressure mercury lamp to close the two substrates. Finally, a polarizing plate is bonded to both outer surfaces of the liquid crystal cell to obtain a liquid crystal display element of the present invention. φ The liquid crystal used in each of the above methods may, for example, be a nematic liquid crystal or a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a triple benzene liquid crystal, or a combination can be used. Phenylcyclohexane liquid crystal or the like. Further, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and the trade names "C-15" and "CB-15" (above by Merck) The chiral agent sold is produced by using a ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate. The polarizing plate used for the outer side of the liquid crystal cell is made of a polarizing plate or a ruthenium film which is obtained by sandwiching a polarizing film called a "ruthenium film" which is obtained by stretching and orienting polyvinyl alcohol and absorbing iodine. Polarizer and the like. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. -42- 200949442 In the following synthesis examples, the measurement of Mw and Μη of the copolymer was carried out by gel permeation chromatography (GpC) using the following apparatus and conditions. Device: GPC-101 (manufactured by Showa Denko Co., Ltd.) Column: QPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804. Mobile phase: tetrahydrofuran containing 0.5% by weight of phosphoric acid. Synthesis Example 1 In a flask equipped with a cooling tube and a stirrer, '8 parts by weight of 2,2'-φ azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added. ester. Continue to add 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo[5.2.1.02,6]decane-8-yl (tricyclodecyl methacrylate), 40 parts by weight Glycidyl methacrylate and 2 parts by weight of pentaerythritol tetrakis(3-mercaptopropionate), after replacement with nitrogen, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-1]. The conversion in the synthesis example was 98%, the solid content concentration of the obtained polymer solution was 30.0 wt%, the Mw of the polymer [A-_1] was 15,000, and the Mw/Mn was 2.1. Synthesis Example 2 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2,-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added. . Continue to add 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5.2.1.02'6]nonane-8-yl (tricyclodecyl methacrylate), 40 parts by weight Glycidyl methacrylate and 4 parts by weight of pentaerythritol tetrakis(3-mercaptopropionate), after replacement with nitrogen, began to stir slowly. -43- 200949442 The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the compound [A-2]. The conversion in the synthesis example was 99%, the solid content concentration of the polymer solution was 30.5 wt%, the Mw of the polymer 2] was 12,000, and the Mw/Mn was 1.9. Synthesis Example 3 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of azobis(isobutyronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added. Continuing 5 parts by weight of styrene, 10 parts by weight of methacrylic acid, 4 parts by weight of propylene 0 31 parts by weight of benzyl methacrylate, 45 parts by weight of methacrylate orthoester and 4 parts by weight of dipentaerythritol hexa(3-fluorenyl) Propionate), after stirring with nitrogen, began to stir slowly. The temperature of the solution was raised to 80 ° C and maintained for 4 hours to obtain a polymer solution containing the polymer [A-3]. The conversion of this synthesis example was 96%, the solid content concentration of the obtained polymer solution was 28% by mass, the Mw of the polymer was 12,000, and the Mw/Mn was 1.7. Synthesis Example 4 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of φ azobis(2,4-dimethylvaleronitrile), 250 parts by weight of 3-methoxybutyl acetate, and 5 parts by weight were added. Styrene, 12 parts by weight of methacrylic acid, 23 parts of tricyclo[5.2.1.0''6]decane-8-yl (tricyclodecylenoic acid ester), 30 parts by weight of glycidyl methacrylate Ester, 25-fold 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4 parts of pentaerythritol tetrakis(3-mercaptopropionate) after replacement with nitrogen , start to mix. The temperature of the solution was raised to 70 ° C to maintain the temperature for 4 hours to obtain a polymer solution of the polymer [A-4]. The conversion polymerization in this synthesis example, [A-2, 2, - was added to the acid, butyl substitution temperature of .7 heavy 2,2'-ester. Weight basis parts by weight Weight slowly stirred to a content of -44 - 200949442 96% 'The solid content concentration of the obtained polymer solution was 29.8% by weight, the Mw of the polymer was 12,000, and the Mw/Mn was 1.7. Synthesis Example 5 To a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2,-azobis(isobutyronitrile), 250 parts by weight of 3-methoxybutyl acetate were added, and 18 parts by weight were further added. Methacrylic acid, 30 parts by weight of tricyclomethyth[5.2.1.02,6]decane-8-yl ester, 5 parts by weight of styrene, 5 parts by weight of butadiene, 25 parts by weight of methacrylic acid 2- Hydroxyethyl ester, 17 parts by weight of tetrahydrofuranyl-2-yl methacrylate, and 2 parts by weight of trimethylolpropane tris(3-mercaptopropionate), after being replaced with nitrogen, slowly stirred. While raising the temperature of the solution to 80 ° C, the temperature was maintained for 4 hours, and then the temperature was raised to 100 ° C, and the temperature was maintained for 1 hour to carry out polymerization to obtain a polymer solution containing the precursor copolymer [a-5]. The conversion in the synthesis of the precursor copolymer [a-5] was 98%, and the solid content concentration of the obtained polymer solution was 29.5 wt%. Next, in the forward-copolymer [a-5] solution, 14 parts by weight of 2? formazan methoxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Electric Co., Ltd.) and 0.08 parts by weight of 4-A were added. After the oxyphenol, the reaction was carried out by stirring at 60 ° C for 2 hours to obtain a polymer solution containing the polymer [A - 5 ]. Here, the progress of the reaction of the isocyanate group derived from 2-methylpropenyloxyethyl isocyanate with the hydroxyl group derived from the precursor copolymer [a - 5] was confirmed by IR (infrared absorption) spectroscopy. At the same time as the reaction, the peak near 2270 cm·1 of the isocyanate group derived from 2-methacryloxyethyl isocyanate was confirmed to be in a reduced state. The obtained polymer [A-5] had an Mw of 12,000 and an Mw/Mn of 1.9. -45- 200949442 Synthesis Example 6 In Synthesis Example 5, 15 parts by weight of 2-(2-isocyanate ethoxy)ethyl methacrylate (trade name Karenz MOI) was added to the forward copolymer [a_5] solution. EG, produced by Showa Denko Electric Co., Ltd.) in place of 2-methylpropenyloxyethyl isocyanate, and after adding 0.1 part by weight of 4-methoxyphenol, stirring at 40 ° C for 1 hour, and then at 60 ° C The reaction was carried out by stirring for 2 hours to obtain a polymer solution containing the polymer [A-6]. Here, the reaction of the isocyanate group derived from 2-(2-isocyanateethoxy)ethyl methacrylate with the hydroxyl group derived from the precursor copolymer [a-5] was carried out, and IR was used in the same manner as in Synthesis Example 5. (Infrared absorption) spectrum was confirmed. The obtained polymer [A-6] had a Mw of 12,500 and a M w / Μη of 1.9. Synthesis Example 7 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added. . Continuing to add 5 parts by weight of styrene, 20 parts by weight of methacrylic acid, 38 parts by weight of tricyclo[5.2.1.0''6]nonane-8-yl(tricyclodecylmethylpropionate), 10 parts by weight of 3-(methacryloxymethyl)-3.ethyloxetane, 30 parts by weight of 4-propenyloxymethyl-2-methyl-2-ethyl-1, 3. Dioxolane and 4 parts by weight of pentaerythritol tetrakis(3-mercaptopropionate), after replacement with nitrogen, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the precursor copolymer (a-7). The conversion ratio in this synthesis example was 96%, the solid content concentration of the obtained polymer solution was 29.8% by weight, the Mw of the polymer was 12,000, and the Mw/Mn was 1.7. Next, to the forward copolymer (a-7) solution, 0.16 part by weight of -46-200949442 triphenylphosphine and 0.08 part by weight of 4-methoxyphenol were added, and the temperature was raised to 90 °C. Then, after adding 7 parts by weight of glycidyl methacrylate, the mixture was stirred at 90 ° C for 8 hours to obtain a polymer solution containing the polymer [A-7]. Here, the progress of the reaction of the glycidyl group derived from glycidyl methacrylate with the carboxyl group derived from the precursor copolymer (a-7) was confirmed by IR (infrared absorption) spectroscopy. While the reaction was being carried out, it was confirmed that the peak near the 800 cm·1 of the glycidyl group derived from glycidyl methacrylate was decreased. 0 The obtained polymer [A-7] had Mw of 13,000 and Mw/Mn of 2.0. Comparative Synthesis Example 1 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added. Ester continued to add 5 parts by weight of styrene '16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo[5.2.1.〇2'6]decane-8-yl (tricyclodecyl methacrylate) And 40 parts by weight of glycidyl methacrylate, after replacing with nitrogen, 'start slow stirring. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-7]. The conversion ratio in the synthesis example was 94%, the solid content concentration of the obtained polymer solution was 28.8% by weight, the polymer [man-7] was 15,000, and the range was 3.1. Comparative Synthesis Example 2 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2,-azobis(isobutyronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added to continue to add 5 weights. Parts styrene, 10 parts by weight of methacrylic acid, 4 parts by weight of acrylic acid, parts by weight of benzyl methacrylate, 45 parts by weight of n-47-.200949442 butyl methacrylate and 4 parts by weight of α-methylstyrene After the dimer was replaced with nitrogen, stirring was started slowly. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A - 8]. The conversion ratio in this synthesis example was 92%, and the solid content concentration of the obtained polymer solution was 27.5 wt%'. The Mw of [A-8] of the polymer was 12,000, and Mw/Mn was 2.8. Comparative Synthesis Example 3 To 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 3-methoxybutyl acetate were added to continue to add φ. 18 parts by weight of methacrylic acid, 30 parts by weight of tricyclo[5.2.1.0''6]nonane-8-yl methacrylate, 5 parts by weight of styrene, 5 parts by weight of butadiene, 25 parts by weight of methacrylic acid 2 -hydroxyethyl ester and 17 parts by weight of tetrahydrofuran-2-yl methacrylate, after replacing with nitrogen, while slowly stirring, the temperature of the solution was raised to 80 ° C, the temperature was maintained for 4 hours, and then the temperature was raised to 100 ° At ° C, the temperature was maintained for 1 hour to carry out polymerization to obtain a polymer solution containing the precursor copolymer [a - 9]. The conversion ratio in the synthesis of the precursor copolymer [a - 9] was 94%, and the solid content concentration of the obtained polymer solution was 29.0% by weight. /. . Gw (gel permeation chromatography) HLC-8020 (trade name, manufactured by Tosoh Co., Ltd.) was used to measure Mw of the obtained precursor copolymer [a-9], Mw was 14000, Mw/Mn = 2·5 〇, then, driving In the copolymer [a-9] solution, after adding 14 parts by weight of 2-methylpropenoloxyethyl isocyanate (trade name: Karenz® 01, manufactured by Showa Denko), and 0.08 parts by weight of 4-methoxyphenol The reaction was carried out by stirring at 60 ° C for 2 hours to obtain a polymer solution containing the polymer [A-9]. -48- 200949442 Here, in the same manner as in Synthesis Example 5, IR (infrared absorption) spectrum was used to confirm the isocyanate group derived from 2·methacryloxyethyl isocyanate and the hydroxyl group derived from the precursor copolymer [a-9]. The reaction proceeds. The obtained polymer [A-9] had Mw of 14,000 and Mw/Mn of 2.5. Comparative Synthesis Example 4 To a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate were added. ester. Continue to add 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo[5.2.1.02'6]nonane-8-yl (tricyclodecyl methacrylate), 40 weights The glycidyl methacrylate and 0.5 part by weight of pentaerythritol tetrakis(3-mercaptopropionate) were replaced with nitrogen and stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A - 10]. The conversion ratio in the synthesis example was 98%, the solid content concentration of the obtained polymer solution was 28.8% by weight, the Mw of the polymer [A-10] was 16,000, and the Mw/Mn was 2.9. Example 1 <Preparation of a radiation sensitive resin composition> The polymer solution containing the polymer [A-1] obtained in Synthesis Example 1 as the polymer [A] is converted into a polymer [A] equivalent to 100 The amount by weight, 100 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as the polymerizable compound [B], and acetamidine, 1-[9-B as a [C] sensitizing radiation polymerization initiator 5- 6-(2-methylbenzoic acid)-9·Η· -Oryt-3-yl]-, 1-(0-acetoxy) (Irgacure 0X02, manufactured by Ciba Specialty Chemicals) 5 parts by weight And 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-?-49-200949442 linyl-4-yl-phenyl)-butyl-1-one (Ciba Irgacure 3 79) 10 parts by weight of Specialty Chemicals, dissolved in propylene glycol monomethyl hydrazine acetate to a solids concentration of 21% by weight, and then filtered through a micropore filter with a pore size of 0.2 μη to prepare a radiosensitivity Resin composition (S-1). The radiation sensitive resin composition (S-1) was evaluated as follows. The evaluation results are shown in Table 2. <Evaluation of Radiation-Sensitive Resin Composition> (1) Evaluation of Sensitivity@ The radiation-sensitive resin composition (S-1) was applied onto an alkali-free glass substrate by a spin coater at 90 ° C. The hot plate was prebaked for 3 minutes to form a coating film having a film thickness of 3.0 μm. Then, the obtained coating film was exposed by using ultraviolet light having a circular pattern having a diameter of 15 μm as an opening portion, ultraviolet light having a strength of 250 W/m 2 at 365 nm, and exposure time as a variable. Then, after developing with a 0.05 wt% aqueous potassium hydroxide solution at 25 t for 60 seconds, it was washed with pure water for 1 minute, and then post-baked in an oven at 23 ° C for 20 minutes to form an interlayer spacer. At this time, the residual film rate after the post-baking (film thickness after post-baking Χίοο / film thickness after exposure) is a minimum exposure amount of 90% or more as sensitivity. (2) Evaluation of the amount of volatile components The radiation sensitive linear resin composition (S-1) was applied onto a ruthenium sheet by a spin coater, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film thickness. It is a coating film of 3. Ομιη. The substrate on which the coating film was formed was cut into short strip test pieces, and subjected to headspace gas chromatography/quality analysis (headspace sampler: -50-200949442 JHS-100A, manufactured by Nippon Analytical Industries Co., Ltd., gas chromatography/ Quality analysis device: JEOL JMS - Model AX505W Quality Analyzer) for analysis. The purge condition was 100 ° C / 10 min, and the peak area of the volatile component was determined. The standard substance is octane (specific gravity of octane: 0.701, injection amount of xinyuan: ΐ. 02 μΐ), and the amount of all volatile components converted to octane is determined by the following formula based on the peak area. Amount of the sexual component (μ8) = (peak area of the volatile component + peak area of octane) x 0.02 x 0.701 » (3) Evaluation of the coatability by the slit die coating method U using the slit die coating method The radiation sensitive resin composition (S-1) was coated on a 50 50 x 650 mm chromium film-forming glass. The slit die moving rate was 150 mm/sec, the solvent was removed to 0.5 Torr, and after drying, the film was prebaked in a clean box at 100 ° C for 3 minutes to form a coating film, and then exposed at an exposure of 20,000 J/m 2 . A film having a film thickness of 3 μm was formed from the upper surface of the chromium film-forming glass. The film surface was irradiated with a sodium lamp, and the coated film surface was visually identified. When it is identified that there is uneven streaks (one or more lines of unevenness that can be observed in the direction of the slit or in the direction intersecting with the slit), the evaluation is "X" (poor), and the confirmation is slightly At one point, the evaluation was "△" (slightly defective), and when it was not identified, the evaluation was "〇" (good). Examples 2 to 1 3 and 15 and Comparative Examples 1 to 4 In Example 1, except that the components contained in the radiation sensitive resin composition were respectively used in the types and amounts listed in Table 1, and Examples 1 Each composition solution was prepared in the same manner and evaluated. The polymer [Α] is used in the form of a polymer solution, and the amount (parts by weight) in Table 1 is converted to the weight of the polymer contained in the polymer solution used. In addition, [Β] Polymerization-51- The addition amount of the 200949442 compound and the [C] radiation-sensitive polymerization initiator was respectively relative to 100 parts by weight of the polymer [A]. Further, when the [C] radiation-sensitive polymerization initiator was used together with the amine-based sensitizer and the thiol compound, they were listed in the column of [C] sensitizing linear polymerization initiator in Table 1. The evaluation results are shown in Table 2. Example 14 and Comparative Example 5 <Preparation of Radiation-sensitive Resin Composition> As the polymer [A], [B] polymerizable compound, and [C] radiation-sensitive poly-Q initiator, the types and amounts listed in Table 1 were used, respectively. The radiation sensitive resin composition (S-14) and (s-5) were prepared in the same manner as in Example 1 except that the solid content concentration was 40% by weight in the propylene glycol monomethyl ether acetate. . <Evaluation of Radiation-Resistant Resin Composition> Using the above-described radiation-sensitive resin compositions (S - 14) and (s - 5), the dry film was produced as follows, and the transfer property to the glass substrate was carried out. Evaluation. The evaluation results are shown in Table 2. (4) Evaluation of transferability of dry film to glass substrate [Production of dry film] The above-mentioned radiation sensitive resin composition was applied to polyethylene terephthalate having a thickness of 38 μm by an applicator ( On the PET film, the obtained coating film was heated at 100 ° C for 5 minutes to remove the solvent, and a radiation-sensitive dry film having a radiation-sensitive layer having a thickness of 4 μm on PET was produced. [Evaluation of Transferability to Glass Substrate] Next, the surface of the glass substrate and the surface of the radiation-sensitive transfer layer were bonded to -52 to 200949442, and they were superposed on the above-mentioned radiation-sensitive transfer dry film, and were subjected to hot pressing. The radiation-sensitive dry film was transferred to a glass substrate. At this time, when the dry film can be uniformly transferred onto the glass substrate, the transfer property is evaluated as "〇" (good), and some dry film remains on the base film or the dry film on the glass substrate is not well adhered, etc. In the case where the film could not be uniformly transferred onto the glass substrate, it was evaluated as "X" (poor). In Table 1, the abbreviations of the respective components represent the following compounds. B-1: Dipentaerythritol hexaacrylate (trade name "KAYARAD DPHA", produced by Sakamoto Chemical Co., Ltd.). H B — 2: A polymerizable unsaturated compound containing a polyfunctional urethane acrylate compound (trade name "KAYARAD DPHA-40H", manufactured by Nippon Kayaku Co., Ltd.). B-3: Pentaerythritol tetraacrylate (trade name "Aronix Μ - 450", produced by East Asian Synthetic Co., Ltd.). Β-4: ω-carboxypolycaprolactone monoacrylate (trade name "Aronix Μ 1500", produced by East Asia Synthetic Co., Ltd.). Β - 5: 1,9-nonanediol diacrylate (trade name "Light-Acrylate φ 1,9-NDA", produced by Kyoeisha Chemical Co., Ltd.). C-1: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzomethyl)-9·Η·-carbazol-3-yl]-, 1-(0-ethenyl)肟) (trade name "Irgacure OX02", produced by Ciba Specialty Chemicals). C-2: Ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzidine Base]-9.Η·-carbazol-3-yl]-, 1-(0-ethenylhydrazine) (trade name “Ν — 1919”, produced by ADEKA). C — 3: 2-dimethylamino 2-(4-methyl-benzyl)-1-(4-morpholinyl-4- 4-53- 200949442 phenyl-phenyl)-butane-1- Ketone (trade name "Irgacure 379", manufactured by Ciba Specialty Chemicals). C - 4 : 2,2'·bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole. C-5: 4,4'-bis(diethylamino)benzophenone. C — 6 : 2-mercaptobenzothiazole. C-7: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one (trade name "Irgacure 369", manufactured by Ciba Specialty Chemicals 0) . C — 8 : 2 -Methyl-1-(4-methylthiophenyl)-2 - phenanthrene propyl-1-e (trade name "Irgacure 907", produced by Ciba Specialty Chemicals). D — 1 : Phenolic novolac epoxy resin (trade name “Epikote 152”, manufactured by Japan Epoxy Resin Co., Ltd.). In Table 1, the "_" symbol indicates that the component is not added. In Table 2, the "one" symbol indicates that the evaluation was not performed. ❹ -54- 200949442 Ϊ嗽Other components parts by weight 1 1 I 1 1 1 1 1 Ο 1 1 1 1 1 1 1 inch 1 I 1 Type 1 1 1 1 1 1 1 1 NJ 1 1 1 1 1 1 1 Dl 1 1 1 1 蘅m ΠΓ» Φ m 迤m parts by weight 5+10 5+2+2+1+5 5+2+2+1+5 5+10 5+10 5+10 5+2+2+1 +5 5+10 5+2+2+1+5 5+2+2+1+5 5+2+2+1+5 5+2+2+1+5 5+2+2+1+5 5+2+2+1+5 5+10 5+10 5+2+2+1+5 5+2+2+1+5 5+2+2+1+5 Sao Omn P C-l+C -3 C-1+C-4+C-5+C-6+C-8 C-2+C-4+C-5+C-6+C-8 C-l+C-3 C-l +C-3 C-l+C-3 C-1+C-4+C-5+C-6+C-8 C-l+C-3 C-1+C-4+C-5+C -6+C-8 C-1+C-4+C-5+C-6+C-8 C-1+C-4+C-5+C-6+C-8 C-1+C- 4+C-5+C-6+C-8 C-1+C-4+C-5+C-6+C-8 C-1+C-4+C-5+C-6+C- 8 C-l+C-3 C-l+C-3 C-7 C-1+C-4+C-5+C-6+C-8 C-1+C-4+C-5+C -6+C-8 C-1+C-4+C-5+C-6+C-8 m I1 <π m such as m parts by weight Ο Ο 80+60+5 80+60+5 |50+50 |100+10 Ο Ο |80+60+5 1 100+10 (80+60+5 1 |80+ 60+5 1 |80+60+5 1 80+60+5 80+60+5 1 Ο 50+50 Ο Ο Ο 80+60+5 80+60+5 Ο C4 骏^mn P ώ Β-1+ Β-2+Β-4 Β-1+Β-2+Β-4 Β-1+Β-3 Β-1+Β-5 PQ Β-1+Β-2+Β-4 B-l+B- 5 Β-1+Β-2+Β-4 Β-1+Β-2+Β-4 Β-1+Β-2+Β-4 Β-1+Β-2+Β-4 Β-1+Β -2+Β-4 CQ B-l+B-3 ώ m Β-1+Β-2+Β-4 Β-1+Β-2+Β-4 PQ parts by weight ο rH ο Ο Ο Ο ο ο Ο Ο Ο Ο Ο Ο ο ο ο Ο ο ο ο Ο Ο ο ο <Π Embedded step ^Γ\ lll^l P Al Α-1 Α-1 Α-1 Α-1 Α-2 Α-2 Α-2 Α-3 Α-3 Α-4 Α-5 Α-6 Α -5 Α-7 Α-7 1 Α-8 Α-9 I Α-10 Α-9 Composition Name (S-1) (S-2) (S-3) (S-4) (S-5) (S-6) (S-7) (S-8) 1 (S-9) 1 1 (S-10) ! 1 (S-ll) j 1 (S-12) 1 (S-13) 1 ( S-14) (S-15) (s-2) in' (s-4) (s-5) Embodiment 1 Embodiment 2 Embodiment 3 1 Embodiment 4 1 Embodiment 5 1 1 Embodiment 6 1 Implementation Example 7 Example 8 丨 Example 9 1 1 Example ίο 1 1 Example 11 I 1 Example 12 1 丨 Example 13 1 Example 14 丨 Example 15 I Comparative Example 1 1 Comparative Example 2 1 1 Comparative Example 3 1 1 Comparative Example 4 1 Comparative Example 5 _lns- 200949442 Table 2 Composition mm Sensitivity: J/cm2) Evaluation of the amount of volatile components (4)) Evaluation of the coatability of the slit die coating method Transferability Example 1 ( S-1) 1200 1.42 〇 - Example 2 (S-2) 1000 1.45 〇 - Example 3 (S-3) 1000 1.42 〇 - Example 4 (S-4) 1000 1.44 〇 - Example 5 (S- 5) 1000 1.46 〇 - Example 6 (S-6) 1200 1.54 〇 - Example 7 (S-7) 1000 1.55 〇 - Example 8 (S-8) 1000 1.51 〇 - Example 9 (S-9)1000 1.12 〇 - Example 10 (S-10) 1000 1.12 〇 - Example 11 (S-11) 1000 2.01 〇 - Example 12 (S-12) 800 2.05 〇 - Example 13 (S-13) 800 2.05 〇 - Example 14 (S-14) — — — 〇 Example 15 (S-15) 1000 1.44 〇 - Comparative Example 1 (s-1) 1800 6.01 X - Comparative Example 2 (s-2) 2000 5.15 X — Comparative Example 3 (s-3) 800 7.21 Δ - Comparative Example 4 (s-4) 1700 3.07 Δ - Comparative Example 5 (s-5) — — — 〇 [Simple description of the drawing] Μ 〇 [Description of main component symbols] 4^* 〇-56-

Claims (1)

200949442 VII. Patent application scope: 1. A radiation sensitive resin composition characterized by comprising: [A] at least one base selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and the following formula (1) The η-valent group represented by the ratio of the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography to the polystyrene-equivalent number average molecular weight (Mn) (Mw/Mn) is 1 〇 ~ 2.8 polymer; [B] polymerizable unsaturated compound; and _ [C] sensitizing radiation polymerization initiator, X-(-Υ-R1-S-+) (1) In formula (1), R1 is a methylene group or an alkylene group having 2 to 10 carbon atoms or an alkylmethylene group, and Y is a single bond, -CO-, -σ-CO-* or -NHCO-*, wherein "*" is present. The linkage is linked to R1, η is an integer from 2 to 10, and X is an η-valent hydrocarbon group having 2 to 70 carbon atoms optionally having one or more ether linkages, or η is 3 and X is a formula ( 2) indicates a trivalent group, and "+" indicates a connection key. In the formula (2), R11 is each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" is each represented by a linking bond. -57-200949442 2 - The radiation sensitive resin composition of claim 1, wherein the [A] polymer is at least (al) comprising a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride a polymer obtained by a radical polymerization step in the presence of at least one unsaturated compound in the presence of a compound represented by the following formula (8), X—fV—-R^SH ) 〇 (8) in the formula (8), X, Y, R1 and η are each the same as defined for X, Υ, U R1 and η in the above formula (1). 3. The radiation sensitive linear resin composition according to claim 1 or 2, wherein the enthalpy in the formula (1) is -0-C0-*, wherein a bond having a "*" is connected to R1. 4. The radiation sensitive resin composition according to any one of claims 1 to 3, which is used for producing a spacer for a display element. A method for producing a spacer for a display element, characterized by comprising the step of forming a film of a radiation-sensitive resin composition as in the fourth aspect of the patent application, at least in the following order, (φ) 2) a step of exposing at least a portion of the film, (3) a step of developing the exposed film, and (4) a step of heating the film after development. A spacer for a display element, which is produced by a radiation-sensitive resin composition as disclosed in claim 4 of the patent application. 7. A liquid crystal display element characterized in that it has a spacer for a display element as in item 6 of the patent application. -58- 200949442 IV. Designated representative diagram: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: No 0 ❹ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: