TWI343510B - Radiation-sensitive resin composition, display panel separator and displayer panel - Google Patents

Description

[Technical Field] The present invention relates to a radiation sensitive resin composition, a spacer for a display panel, and a display panel, and more particularly, the present invention relates to a suitable A radiation-sensitive resin composition for forming a material of a spacer used in a display panel such as a liquid crystal display panel or a touch panel, a spacer for a display panel formed of the composition, and a display panel having the spacer . [Prior Art] Conventionally, in order to keep the interval between the two substrates constant, spacer particles such as glass beads or plastic beads having a predetermined particle diameter are used in the liquid crystal display panel. However, since these spacer particles are Since it is randomly spread on a transparent substrate such as a glass substrate, when spacer particles are present in the pixel formation region, the spacer particles are written, or the incident light is scattered, and the contrast of the liquid crystal panel is lowered. In order to solve these problems, people use lithography to form spacers. In this method, a photosensitive resin composition or a radiation-sensitive resin composition (hereinafter, these compositions are collectively referred to as "radiation-sensitive resin composition®, etc.") are applied onto a substrate, and radiation such as ultraviolet rays is irradiated through a predetermined mask. Exposure, and then development, to form a dot-like or stripe-shaped spacer, basically solves the above problem since spacers can be formed only at predetermined portions other than the pixel formation region. However, in the case where a spacer is actually formed, for example, when a spacer is formed on a substrate used for a color filter or the like by lithography, a proximity exposure machine is often used. When performing such proximity exposure, it is preferable to perform exposure after a certain unit cell interval is set between the photomask and the substrate on which the film such as the radiation-sensitive resin composition is formed, and the exposure is performed according to the mask. Pattern exposure. The cell spacing is filled with air or nitrogen, and the radiation that has passed through the opening (transparent portion) of the mask spreads in the gap and widens, so that the actual exposure is wider than the design size of the mask pattern. In order to solve this problem, the inventors have found and pointed out in Patent Document 1 that by using 1,2-octanedione phenylthio)phenyl]-2-(0-benzylidene fluorene) as a photosensitive The photopolymerization initiator of the resin composition can faithfully reproduce the design size of the mask pattern even in the case of the proximity exposure, and can form a spacer for a display panel excellent in strength and heat resistance. In addition, as the size of the display panel increases, it is required to control the interval more accurately, but the radiation-sensitive resin composition for the spacer is used. When the adhesion between the formed film and the substrate is insufficient, the formed spacer moves from the substrate to deviate from the original position, and as a result, the interval cannot be accurately maintained. Further, the display panel is developed in a direction toward the high aperture of the pixel, and as a result, the area of the black matrix region in which the spacer can be formed is also gradually reduced. Therefore, the spacer is required to have higher transparency, so that even if the spacer ^ enters the pixel region to a certain extent, the hue of the pixel is not impaired. However, the radiation-sensitive resin composition or the like conventionally used for forming a spacer described in Patent Document 1 is still not very satisfactory in terms of adhesion to a substrate and transparency, and there is an urgent need for both tanning and development. A sensory radiation-sensitive resin composition or the like. In recent years, the mother glass substrate has been gradually increased in size due to the increase in the area of the display panel and the improvement in productivity. In the case of the conventional substrate size (about 680 x 880 mm), the size of the substrate 1343510 is smaller than that of the mask size, and thus it is possible to adopt a one-time exposure method, but on a large substrate (for example, l, 5〇〇xl, 8) In the case of 00 mm or so, it is almost impossible to make a mask size of the same size as such a substrate, and thus it is difficult to adopt a sub-exposure operation mode. As an exposure method that can accommodate a large substrate, a stepwise exposure method has been proposed. However, when the stepwise exposure method is used, it is necessary to perform multiple exposures for one substrate at a time, and each exposure requires time for the mating position or the step movement, and thus the throughput may be reduced as compared with the one-time exposure method. In addition, when using the one-time exposure method, the exposure sensitivity of about 3,00 OJ/m2 can be allowed, while in the step exposure mode, the exposure sensitivity is required to be 1,500 (U/m2 or less). When a radiation sensitive linear resin composition or the like of the spacer is formed, it is difficult to sufficiently form the shape and thickness of the spacer at an exposure amount of 1,500 J/m 2 or less. SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation sensitive resin composition. The design size of the reticle pattern can be faithfully reproduced with high sensitivity, and has good adhesion to the substrate, and the shape and film thickness of the spacer can be sufficiently formed even at an exposure amount of 1,50 OJ/m 2 or less. Further, a spacer for a display panel which is excellent in compressive strength and abrasion resistance can be formed. The first aspect of the present invention is a radiation sensitive resin composition (hereinafter referred to as "radiation-sensitive resin composition"), which is characterized in that The composition contains: [A] (al) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound, and (a3) a copolymer of an ethylenically unsaturated compound; Η 1343510 [B] a polymerizable compound having an ethylenically unsaturated bond; and [C] a compound represented by the following formula (1) or (2) as an essential component Radiation-sensitive linear polymerization initiator.

[In the formulae (1) and (2), each R1 independently represents a linear, branched or cyclic alkyl group or a phenyl group having 1 to 12 carbon atoms, and each R2 independently represents a hydrogen atom, A linear, branched or cyclic alkyl group having a carbon number of -12 or a radical of each of R 3 independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and each R 4 ' Each of R5 and each R6 independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having a carbon number. However, the alkyl groups of R1, R2, R3, R4, R5 and R6 may also be respectively selected from a linear, branched or cyclic alkoxy group having from 1 to 6 carbon atoms, a substituent in a phenyl group and a halogen atom. The phenyl group substituted with R2 and R2 may also be selected from a linear, branched or cyclic alkyl group having a carbon number of 1-6, and a carbon atom number 66 to 1343510. The linear chain and the branch of «··· Substituted by a chain or a cyclic alkoxy group, a phenyl group, and a substituent in a halogen atom. A second aspect of the invention is a spacer for a display panel formed of the above-described radiation sensitive resin composition. A third aspect of the invention is a display panel having the above-described spacer for a display panel. [Embodiment] Hereinafter, the present invention will be described in detail. I <Rain-sensitive linear resin composition> Copolymer 丨A 1 The [A] component in the radiation-sensitive resin composition is composed of (a 1) ethylenically unsaturated carboxylic acid and/or ethylenically unsaturated carboxylic anhydride. (hereinafter referred to as "unsaturated carboxylic acid compound (al)"), (a2) an epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as "epoxy group-containing unsaturated compound (a2)") and (a3) other A copolymer of an ethylenically unsaturated compound (hereinafter referred to as "another unsaturated compound (a;?)") (hereinafter referred to as "copolymer [A]"). Among the components constituting the copolymer [A], the unsaturated carboxylic acid compound (a1) may, for example, be acrylic acid, methacrylic acid, citric acid or succinic acid mono(2-propenyloxyethyl ester). ), succinic acid-1 (2-methylpropenyloxyethyl ester), phthalic acid mono (2-propyleneoxyethyl ester), phthalic acid mono (2-methylpropenyloxyethyl ester) A monocarboxylic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; or an anhydride of the above dicarboxylic acid. In these unsaturated carboxylic acid compounds (al), acrylic acid, A is preferred from the viewpoints of copolymerization reactivity, solubility of the obtained copolymer [A] to an aqueous alkaline solution, and easily available -10- 1343510 - In the copolymer [Α], the unsaturated carboxylic acid compound (a 1) may be used singly or in combination of two or more kinds. In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid compound (a 1) is preferably from 5 to 50% by weight, preferably from 1 to 4% by weight, particularly preferably 1 5 . -30% by weight. In this case, when the content of the repeating unit derived from the unsaturated carboxylic acid compound (a1) is less than 5% by weight, the solubility in the alkaline aqueous solution tends to decrease, and when it exceeds 40% by weight. | The solubility of the resulting copolymer in an aqueous alkaline solution may be excessive. Further, examples of the epoxy group-containing unsaturated compound U2) include glycidyl acrylate '2-methyl glycidyl acrylate' 3,4-epoxybutyl acrylate, acrylic acid 6,7- Epoxyheptyl heptyl ester, 3,4-epoxycyclohexyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, A 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl methacrylate, etc. (methyl>acrylic acid epoxy alkyl esters; glycidyl ethacrylate, α-ethyl 2-methylglycidyl acrylate, 3,4-cyclobutyloxybutyl α-ethyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate, 3,4-cyclo-α-ethyl acrylate Cyclohexyl acrylate, 〇:-glycidyl propyl acrylate, α-alkyl acrylate epoxy group such as α-n-butyl acrylate, o-vinyl benzyl glycidyl ether, An unsaturated glycidyl ether such as vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether, etc. In these unsaturated compounds containing an epoxy group In a2), from the viewpoint of copolymerization reactivity and spacer strength, glycidyl methacrylate, 2-methyl glycidyl methacrylate, and methacrylic acid 6,7· -11- 1343510 I are preferred. ' ► ' ♦ 4 'μ ·. Epoxyheptyl heptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. In the copolymer [Α] The epoxy group-containing unsaturated compound (a2) may be used singly or in combination of two or more kinds. • In the copolymer [A], it is derived from a repeating unit of the epoxy group-containing unsaturated compound (a2). The content is preferably from 10 to 70% by weight, preferably from 20 to 60% by weight, particularly preferably from 30 to 50% by weight. In this case, a repeating unit derived from an epoxy group-containing unsaturated compound (a2) When the content is less than 10% by weight, the compressive strength of the obtained spacer tends to decrease. On the other hand, when 1 ^ exceeds 70% by weight, the storage stability of the obtained copolymer tends to be lowered. The other unsaturated monomer U3) may, for example, be methyl acrylate or propyl acrylate. Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, 2·methylcyclohexyl acrylate, methacrylic acid Ester, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, second butyl methacrylate, third butyl methacrylate, methacrylic acid ring Ethyl (meth) acrylate such as ester, 2-methylcyclohexyl methacrylate; tricyclo[5.2.1. 02'6] 癸-8-yl acrylate, 2-(tricyclic [ 5.2.1.02'6]decane-8-yloxy)ethyl ester, isobornyl acrylate, tricyclo[5.2.1.0''6]non-8-yl methacrylate, 2-methacrylic acid 2-( Tricyclo[5.2.1.02'6]decane-8-yloxy)ethyl ester, isobornyl methacrylate, and other (meth) acrylate alicyclic esters: phenyl acrylate, benzyl acrylate An aryl or aralkyl ester of (meth)acrylic acid such as phenyl methacrylate or benzyl methacrylate; 2-hydroxyethyl-12- 1343510 acrylate, propylene Hydroxyalkyl (meth) acrylate such as 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl acrylate, acrylic acid (tetrahydropyridyl) An oxygen atom-containing (meth)acrylic acid such as methyl-2-methyl)methyl methacrylate, tetrahydrofurfuryl methacrylate or tetrahydropyran-2-yl methacrylate Pentacyclic or heterohexacyclic ester; unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate; styrene, α-methylstyrene , vinyl aromatic compounds such as m-methylstyrene, p-methylstyrene, p-methoxystyrene; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 a conjugated diene compound such as butadiene; and examples thereof include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate. Among these other unsaturated compounds (a3), from the viewpoint of copolymerization reactivity and solubility of the obtained copolymer [A] for an aqueous alkaline solution, it is preferred that 2-methylcyclohexyl acrylate and methacrylic acid are preferred. Tributyl ester, tricyclo[5.2.1.0''6]non-8-yl methacrylate, tetrahydrofurfuryl methacrylate, styrene, p-methoxystyrene, 1,3-butadiene, and the like. In the copolymer [A], the other unsaturated compound (a3) may be used singly or in combination of two or more kinds. In the copolymer [A], the content of the repeating unit derived from the other unsaturated compound (a3) is preferably from 10 to 70% by weight, preferably from 20 to 50% by weight, more preferably from 30 to 50% by weight. %. In this case, when the content of the repeating unit derived from the other unsaturated compound (a3) is less than 10% by weight, the storage stability of the obtained copolymer tends to be low, and when it exceeds 70% by weight, the obtained copolymer The solubility in alkaline aqueous solutions tends to be low. -13- 1343510 - Diethylene glycol alkyl ether such as diethylene glycol diethyl ether or diethylene glycol ethyl methyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Propylene glycol monoalkyl ether such as butyl ether; propylene glycol monomethyl ether acrylate, propylene glycol monoethyl acrylate, propylene glycol mono-n-propyl ether acrylate, propylene glycol Propylene glycol monoalkyl ether acrylate such as n-butyl ether acrylate: propylene glycol monomethyl propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether Ethyl ester, propylene glycol mono-n-butyl ether propionate, etc., propylene glycol monoalkyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, 2-pentanone a ketone such as 3-pentanone, cyclohexanone or 4-hydroxy-4-methyl-2-pentanone; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2·A N-propyl oxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-propyl 2-propoxypropionate Base ester, n-butyl 2-ethoxypropionate, 2-n-propoxy Methyl propionate, ethyl 2-n-propoxypropionate, ® 2-n-propoxy propionate n-propyl ester, 2-n-propoxy propionate n-butyl ester, 2-n-butoxypropane Methyl ester, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid n-propyl ester, 3-methoxypropionic acid n-butyl ester, 3-ethoxypropionate methyl ester, 3-ethoxy group Ethyl propionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate , n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, -15- 1343510 * 3_n-butoxy Alkyl alkoxypropionates such as ethyl acetate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate: methyl acetate, ethyl acetate, acetic acid Propyl ester, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl glycolate, n-butyl glycolate, methyl lactate, ethyl lactate, n-propyl lactate, N-butyl acrylate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxyl N-propyl propionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl acetate & ethyl oxyacetate, n-propyl methoxyacetate Ester, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, n-propyl Ethyl oxyacetate, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, positive Other esters such as n-butyl butoxyacetate" Among these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether propionates, and alkyl alkoxypropionates are preferred. Wait. These solvents may be used alone or in combination of two or more. Further, the radical polymerization initiator to be used in the above polymerization is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethyl group). Valeronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl -2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds: An organic peroxide such as benzamidine oxide, laurel, butyl peroxypivalate, 1,1-di(t-butylperoxy)cyclohexane, or hydrogen peroxide. In the use of peroxide as a free radical polymerization lead -16- ttml-. S agent 2 hair bow or type seed original 1 also used to make oxygen alone as a single agent can be used to 'reagents with hair and bow to combine with the group can also be used to make some of this. ο. The hair 5·3 - -34 is used to dissolve the solution in the liquid phase to dissolve it from straight to cocoa. ]*, object [A compound into a group of poly-fat co-fat tree. The tree-like sex line is used to make the line-shot-shot-mixing and sensation-sensing to prepare a polystyrene-equivalent weight average molecular weight of the copolymer [A] measured by gel permeation chromatography (GPC) (below) The abbreviation "Mw" is usually 2,000-100,000, preferably 5,000-50,000. In this case, when the Mw of the copolymer [A] is less than 2,000, the film formation and residual film ratio of the obtained film are lowered, and the pattern is The shape and the heat resistance may be impaired. On the other hand, when the image is more than 10,000, the image resolution is lowered, or the shape of the pattern may be impaired. In the present invention, the copolymer [A] may be used alone or in combination of two or more. Polymer component 丨B 1 The component [B] in the radiation sensitive resin composition is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as "polymerizable compound [B]"). Polymerizable compound [B] There is no particular limitation, and monofunctional, difunctional or trifunctional or higher (meth) acrylates have good polymerizability, and these compounds are preferred from the viewpoint of improving the strength of the obtained spacer. Examples of the (meth) acrylates include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, diethylene glycol monoethyl methacrylate, and acrylic acid. Isobornyl ester, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, phthalic acid (2-propenyloxyethyl) (2-hydroxypropyl) Ester, -17- 1343510. (2-methylpropenyloxyethyl) (2-hydroxypropyl) ester, etc. Further, as a monofunctional (meth) acrylate, a commercially available product, for example It can be mentioned: Aronikkusu-10 1' Aronikkusu-1 1 1 , 8 1"〇11丨1^11311-114 (The above products are manufactured by East Asia Synthetic Co., Ltd.); 1<:People ¥11 TC-110S KAYARAD TC-120S (the above products are manufactured by Nippon Kayaku Co., Ltd.); Viscoat 158, Viscoat 2311 (the above products are manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. The above bifunctional (meth) acrylates can be, for example, For example: ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, B Diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol 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. Commercial products of difunctional (meth) acrylates include, for example, Aronikkusu-210, Aronikkusu-240, and Aronikkusu-6200 (the above products are manufactured by East Asia Synthetic Co., Ltd.): KAYARAD HDD A, KAYARAD • HDDAHX- 220, KAYARAD HDDA R-604 (the above products are manufactured by Nippon Kayaku Co., Ltd.); Viscoat 260, Viscoat 312, Viscoat 3 3 5HP (the above products are manufactured by Osaka Organic Chemical Industry Co., Ltd.). Examples of the above-mentioned trifunctional or higher (meth) acrylates include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and isoamyl alcohol. Trimethacrylate, isopentanol tetraacrylate, pentaerythritol tetramethacrylate, diisopentaerythritol pentaacrylate, diisopentaerythritol pentamethacrylate, diisopentatetra-18 - 1343510 » " · . Alcohol hexaacrylate, diisopentaerythritol hexamethacrylate, tris(2-propenyloxyethyl)phosphonate, tris(2-methylpropenyloxyethyl) Phosphonate. Examples of the hexa-functional or higher (meth) acrylates include a compound having an alkylene chain structure and an alicyclic structure and having two or more isocyanate groups, and a trifunctional group having one or more hydroxyl groups in the molecule. A squalane acrylate compound obtained by reacting a functional or 5-functional (meth) acryl compound. Commercial products of the trifunctional or higher (meth) acrylates include, for example, Aronikkusu M-309, Aronikkusu-400, Aronikkusu-405, Arοnikkusu-45 Ο, Aronikkusu-7 00,

Arοn ikku su - 8 0 3 0, Aron i kkusu- 8 0 6 0,

AronikkusuTO- 14 50 (The above products are manufactured by East Asia Synthetic Co., Ltd.): KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (The above products are 曰本化药( () manufacturing); Viscoat 29 5, Vi s co at 300, Viscoat 360, Viscoat GPT,

Vi scoat 3 PA, Vi sco at 400 (the above products are manufactured by Osaka Organic Chemical Industry Co., Ltd.), and are commercially available as urethane acrylate compounds. NEW FRONTIER R· 1150 (First Industrial Pharmaceutical Co., Ltd.) (manufacturing), KAYARAD DPHA-40H (manufactured by Sakamoto Chemical Co., Ltd.), etc. Among these monofunctional, difunctional or trifunctional or higher (meth) acrylates, a trifunctional or higher (meth) acrylate is preferable, and trimethylolpropane triacrylate is particularly preferable. Pentaerythritol triacrylate, pentaerythritol tetraacrylate, diisopentaerythritol pentaacrylate, and diisopentaerythritol hexaacrylate. In the present invention, the 'polymerizable compound [B] can be used alone! Species or -19- 1343510 * · , · • Two or more types are used in combination. In the radiation sensitive resin composition, the polymerizable compound [B] is preferably used in an amount of from 50 to 1 40 parts by weight, preferably from 60 to 1 20 parts by weight, per 100 parts by weight of the copolymer [A]. . In this case, when the amount of the polymerizable compound [B] is less than 50 parts by weight, when a developing solution composed of an alkaline aqueous solution is used for development, development residue may occur, and conversely, the amount thereof may be used. When it exceeds 140 parts by weight, the hardness of the resulting spacer tends to be relatively low. The polymerization initiator "C1 φ The radiation-sensitive linear resin composition of the composition [C] is a 0-fluorenyl oxazole compound represented by the above formula (1) or (2) (hereinafter referred to as "咔When the azole compound (C 1 )”) is used as an essential component, radiation-induced polymerization of an active species capable of initiating polymerization of the polymerizable compound [B] is generated by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, or X-ray. Agent (hereinafter referred to as "polymerization initiator [C]"). In the formulae (1) and (2), the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R1, R2 and R3 may, for example, be a methyl group, an ethyl group or a n-propyl group. Isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, ^n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, positive Dodecyl, cyclopentyl, cyclohexyl and the like. Further, the linear, branched or cyclic alkyl group having a carbon number of R 4 , R 5 and R 6 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or a second butyl group. Base, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like. In the substituents of the respective alkyl groups relative to R1, R2, R3, R4, R5 and R6 and the substituents of the respective phenyl groups relative to R1 and R2, as carbon atoms -20-1343510

> * II 4 - a linear, branched or cyclic alkoxy group of 1 to 6, and examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and the like. Further, among the substituents of the respective phenyl groups of R1 and R2, examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group and positive group. Propyl, isopropyl, n-butyl, tert-butyl, and the like. In each of the base groups and each of the phenyl groups, one or more of these substituents may be present. In the formulae (1) and (2), R1 is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a phenyl group or the like, and R2 is preferably a hydrogen atom, a methyl group or a methyl group. Base, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc., R3 is preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl The radicals, n-butyl and the like 'R4, R5 and R6 are preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group. Preferred examples of the carbazole compound (C 1) include 1 _ [ 9 · ethyl 6 -benzimidyl-9 · Η--oxazol-3-yl]-nonane-1,2-壬 肟 肟 肟 〇 〇 苯 苯 、 1-, 1-[9-ethyl-6-benzhydryl-9.Η.-Miso-3-yl]-壬院-1,2·壬院-2-2 -肟-0-acetate, 1-[9-ethyl-6-benzylidenyl- 9.Η.-oxazol-3-yl]·pentane-1,2-pentane- 2·肟-0·acetate, 1-[9-ethyl-6-benzhydryl-9.Η.-oxazol-3-yl]-octane-1-one oxime-indole acetic acid Ester, hydrazine-[9.ethyl_6_(2-methylbenzhydryl)-9-indole-oxazol-3-yl]-ethyl-1-one oxime-indole-benzoate, 1-[ 9-Ethyl-6-(2-methylbenzyl)-9.Η·-哩哩-3-yl]•Ethyl-1-ketone brick-0-acetic acid vinegar, 1-[9·ethyl -6-(1,3,5-trimethylbenzylidene)_9.Η·-Oxazol-3-yl]-ethyl-1-one oxime-0-benzoate, ΐ-[9- n-Butyl-6-(2-ethylbenzylidene)-9.H--oxazol-3-yl]-ethan-1-one oxime-indole-benzoate. -21 - 1343510 Among these carbazole compounds (Cl), particularly preferred is [[9-ethyl-6-(2-methylbenzhydryl)-9·Η·-carbazol-3-yl). ]-Ethyl-1-ketooxime-0-acetate. In the present invention, the carbazole compound (C1) may be used singly or in combination of two or more kinds. Further, in the photosensitive resin composition, other radiation-sensitive polymerization initiators (hereinafter referred to as "other polymerization initiators") may be used in combination with the carbazole compound (C1). The other polymerization initiator is preferably a 0-fluorenyl hydrazine type compound (hereinafter referred to as "other fluorene-fluorenyl hydrazine type polymerization initiator"). Examples of the other fluorene-fluorene-based polymerization initiator include 1,2-octanedione-1-[4-(phenylthio)phenyl]-2·(0-benzylidene).肟), 1,2-butanedione-1-[4-(phenylthio)phenyl]-2-(0-benzylidene fluorenyl), 1,2-butanedione-1-[4- (phenylthio)phenyl]-2-(0-acetamidofluorene), 1,2-octanedione-1-[4-(methylthio)phenyl]-2-(0-benzamide (肟), 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-(4-methylbenzhydrylhydrazine)) and the like. Among these other fluorene-fluorene type polymerization initiators, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(0-benzylidene fluorenyl) is particularly preferred.肟). The above-mentioned other fluorene-fluorene-based polymerization initiators may be used singly or in combination of two or more kinds. In the present invention, by using the carbazole compound (C1) or the carbazole compound (C1) and other 0-fluorenyl hydrazine type polymerization initiators, even at an exposure amount of 1,500 Å/m2 or less, A spacer for a display panel having high sensitivity and excellent adhesion to a substrate is formed. In the radiation sensitive resin composition, relative to 100 parts by weight of poly-22-1343510.

A. Mixed use of the above type In the present invention, by using a biimidazole compound as another polymerization initiator, the sensitivity, the image resolution, and the adhesion of the obtained spacer to the substrate can be further improved. In addition, when a biimidazole compound is used as another polymerization initiator, in order to sensitize it, an aromatic compound having a dialkylamine group (hereinafter referred to as "dialkylamino group-containing" may be used. Sensitizer"). Examples of the dialkylamine group-containing sensitizer include 4,4′·bis(dimethylamino)benzophenone and 4,4′-bis(diethylamino)benzophenone. P-dimethylamine 1 benzoic acid ethyl ester, p-diethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-diethylaminobenzoic acid isoamyl ester, and the like. Among these sensitizing agents containing a dialkylamine group, '4,4'-bis(diethylamino)benzophenone is preferred. The sensitizer containing a dialkylamine group may be used singly or in combination of two or more kinds. The amount of the sensitizer containing a dialkylamine group is preferably from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight, per part by weight of the copolymer [A]. In this case, when the amount of the sensitizer containing a dialkylamine group is less than 0.1 part by weight, the resulting spacer may have a film reduction or the shape of the pattern may be impaired, and if it exceeds 50 parts by weight, the spacer may be The shape of the pattern may be damaged. Further, as another polymerization initiator, a biimidazole compound and a dialkylamine group-containing sensitizer may be used, and a thiol compound may be added as a hydrogen supply compound. The biimidazole compound is sensitized by a sensitizer containing a dialkylamine group to generate an imidazole radical, but the desired effect of the high -25-1343510 may not be impaired at this time. Additives If necessary, a surfactant, a binder adjuvant, a storage stabilizer, a heat resistance enhancer, or the like may be added to the radiation sensitive resin composition, for example, within a range not impairing the effects of the present invention. The above surfactant is a component for improving coating properties, and preferred surfactants include a fluorine type surfactant and a decyl alkoxide surfactant. The fluorine-type surfactant described above is preferably a compound having a fluoroalkyl group and/or a fluorine alkyl group at at least one of a terminal group, a main chain and a side chain, for example, 1, 1, 2, 2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, octaethylene Alcohol bis(1,1,2,2-tetrafluoro-n-butyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl)ether, hexapropylene glycol di 1,1,2,2-tetrafluoro-n-butyl)ether, hexapropylene glycol bis(1,I,2,2,3,3-hexafluoro-n-pentyl)ether, perfluoro-n-dodecanesulfonic acid Sodium, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, 1,1,2,2,3,3-hexafluoro-n-decane, and halothane Sodium benzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylate, fluoroalkyl polyoxyethylene ether, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluorine Alkyl ammonium iodide, fluoroalkyl betaines, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyl alcohols, perfluoroalkyl alkoxylates, fluorine alkyl ethers, and the like. Further, examples of commercially available products of the fluorine-type surfactant include BM-1000 and BM-1100 (the above products are manufactured by BM CHEMIE Co., Ltd.), Megafusck F142D, Megafusck F172, Megafusck F173' Megafusck F183, and Megafusck F178. Megafusck F191, -27- 1343510

Megafusck F471, Megafusck F476 (the above products are manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluonlite FC-170C, Fluonlite FC-171 'Fluonlite FC-430, Fluonlite FC-431 (The above products are manufactured by Sumitomo 3M Co., Ltd.) , Safron S-112, Safron S-113, Safron S-1 3 1 ' Safron S-141, Safron S-145, Safron S-3 82, Safron SC-101, Safron SC-102, Safron SC-130 ' Safron SC-104, Safron SC-105, Safron SC-106 (the above products are manufactured by Asahi Glass Co., Ltd.), F-TOP EF30 1, F-TOP EF303, F-TOP EF3 52 (The above products are new Akita Chemicals Co., Ltd.) Manufacturing), Futajento FT-100, Futajento

FT-1 1 0 ' Futajento FT-140A, Futajento FT-150, Futajento FT- 2 5 0 ' Futajento FT-25 1 , Futajento FTX-251, Futajento FTX-2 1 8' Futaj ento FTX-3 00' Futaj ento FTX-3 1 0> Futaj ento FTX-400S (the above products are manufactured by Neos). The siloxane surfactant described above may, for example, be a product sold under the following trade names: Toray Polyoxygen DC3PA, Toray Polyoxygen DC7PA, Toray Polyoxyn SH11PA, Toray Polyoxo SH21PA , Dongli Polyoxo SH28PA, Toray Polyoxo SH29PA, Toray Polyoxo® SH30PA, Toray Polyoxo SH-190, Toray Polyoxyn SH-193, Toray Polyoxynium SZ-6032 Toray Polyoxyn SF-8428, Toray Polyoxygen DC-57, Toray Polyoxygen DC-190 (The above products are manufactured by TORAY'DOW CORNING · Silicone), TSF-4300, TSF-4440, TSF-4445 'TSF-4446, TSF-4452, TSF-4460 (The above products are manufactured by GE Toshiba Silicone). Further, examples of the surfactant other than the above include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oil -28-1343510. Polyoxyethylene alkyl groups such as alkyl ethers Polyoxyethylene aryl ethers such as polyoxyethylene n-octyl phenyl ether and polyoxyethylene n-decyl phenyl ether: polyoxyethylene dilaurate, polyoxyethylene distearate, etc. A nonionic surfactant such as an ethylene dialkyl ester; commercially available products include ΚΡ341 (manufactured by Shin-Etsu Chemical Co., Ltd.), P〇lyfl〇urn No. 57, and Polyfl〇urn No. 95 (a total of Wi products). Rongshe Chemical (share) manufacturing) and so on. These surfactants may be used alone or in combination of two or more. The blending amount B of the surfactant is preferably 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, when the amount of the surfactant is more than 5 parts by weight, the coating film is likely to be rough at the time of coating. The above-mentioned adhesion aid is a component for further improving the adhesion to the substrate, and a preferred binder aid is a functional decane coupling agent. The functional decane coupling agent described above may, for example, be a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl fluorenyl 'vinyl' isocyanate group or an epoxy group, and more specifically, Trimethoxy® decyl benzoic acid, T. methacryloxypropyltrimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, r-isocyanate propyl triethoxy Basear, τ-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These bonding aids may be used alone or in combination of two or more. The amount of the adhesion aid is preferably 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, if the amount of the bonding aid is more than 20 parts by weight, the use of a developing solution composed of an aqueous alkaline solution tends to cause developmental residue. Examples of the agent include sulfur, benzoquinones, hydroquinones, polyoxygen compounds, amines, nitronitroso compounds, and the like, and more specifically, 4·methoxyphenol and N-nitrous oxide The base-N-phenylhydroxylamine aluminum or the like may be used alone or in combination of two or more. B is preferably contained in an amount of 3.0 parts by weight or less, preferably 0.5 parts by weight or less based on 100 parts by weight of the copolymer [A]. In this case, when the compounding amount of the storage stability exceeds 3.0 parts by weight, the sensitivity is lowered, and the pattern shape of the obtained spacer may be impaired. The heat-resistant enhancer described above may, for example, be N-(alkoxy group A). A glycimamide compound, an N. (alkoxymethyl) melamine compound, a compound having two or more epoxy groups, and the like. The N-(alkoxymethyl)glycolide compound described above may, for example, be N,N,N,N-tetrakis(methoxymethyl)glycoluril, N,N,N,N-tetra (ethoxymethyl) glycoluril, N, N, N, N-tetrakis (n-propoxymethyl) glycoluril, N, N, N, N-tetrakis(isopropoxymethyl) glycoluril , Ν, Ν, Ν, Ν·tetra (n-butoxymethyl) glycoluril, hydrazine, hydrazine, hydrazine, hydrazine-tetrakis(t-butoxymethyl) glycoluril, etc., among which hail is preferred Ratio: ^-tetrakis (methoxymethyl) glycoluril. The Ν-(alkoxymethyl) tripolyfluoroamine compound described above may, for example, be ruthenium, osmium, iridium, osmium, iridium, osmium-hexa(methoxymethyl)melamine, 1^, 叱1^,MU1^,1^-hexa(ethoxymethyl)melamine, 虬1^,>1,>1, 叱1^hexa(n-propoxymethyl)melamine, hydrazine, hydrazine, Ν,Ν,Ν,Ν-hexa(isopropoxymethyl) -30- 1343510 , · · ^

V. Melamine, Yiyiyi > 4 Chuan, > 4-hexa(n-butoxymethyl)melamine 'N,N,N,N,N,N-hexa(t-butoxymethyl)melamine And, among them, preferred is 比1,1^,~hexa(methoxymethyl)melamine. In addition, as a commercial product of the N-(alkoxymethyl) melamine compound, for example, Nicarascu N-2702 and Nicarascu MW-30M (the above products are manufactured by Sanwa Chemical Co., Ltd.) may be mentioned. Examples of the compound having two or more epoxy groups as described above include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl alcohol. Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylol Propane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like. Further, as a commercially available product of a compound having two or more epoxy groups, for example, Epolide 40E, Epolide 100E, Epolide 200E, Epolide 70P, Epolide 200P, Epolide 400P, Epolide 1 500NP, Epolide 80MF, Epolide 100MF, Epolide 1 600, • Epolide 3002, Epolide 4000 (the above products are manufactured by Kyoeisha Chemical Co., Ltd.). These heat-resistant enhancers may be used alone or in combination of two or more. The composition solution radiation sensitive linear resin composition is usually dissolved in a suitable solvent by dissolving a component such as the copolymer [A], the polymerizable compound [B], and the polymerization initiator [C] in a practical solvent to prepare a composition solution. . -31- 1343510, " A solvent for preparing the above composition solution can be used as a solvent which can uniformly dissolve each component constituting the radiation sensitive resin composition, does not react with each component, and has moderate volatility. Examples of the solvent include the same solvents as those exemplified for the production of the polymerized portion of the copolymer [A]. Among these solvents, alcohols, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl groups are preferred from the viewpoints of the solubility of each component, the reactivity with each component, and the ease of forming a film. Ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, etc., particularly preferably benzyl alcohol, 2-phenylethyl alcohol, 3-phenylene -1-propanol, ethylene diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate and the like. These solvents may be used alone or in combination of two or more. Further, in the preparation of the composition solution, a high boiling point solvent may be used together with the above solvent. Examples of the high boiling point solvent include N-methylformamide, N,N-dimethylformamide, methylformamide, N-methylacetamide, N,N-dimethyl Ethyl amide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-indole Alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, etc. . These high-boiling solvents may be used singly or in combination of two or more kinds. -32- 1343510 The composition solution thus prepared can be used, for example, by filtration using a microporous sieve filter or the like having a pore diameter of 0.5 2-0.5 /zm, as needed. The composition of the preferred radiation sensitive resin composition of the present invention is more specifically, for example, the following (i) to (v). (i) The composition described below, that is, the unsaturated carboxylic acid compound (al) is one or more of acrylic acid, methacrylic acid, and maleic anhydride among the various components constituting the copolymer [A]. A mixture comprising an epoxy group-containing unsaturated compound (a2> from glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzene One or a mixture of two or more kinds of methyl glycidyl ether and p-vinylbenzyl glycidyl ether, and the other unsaturated compound (a3) is 2-methylcyclohexyl acrylate or methacrylic acid Butyl ester, 1,3-methacrylic acid tricyclo [5.2.1.0''6] fluoren-8-yl ester, tetrahydrofurfuryl acrylate, styrene, p-methoxystyrene and 1,3-butadiene or (ii) The composition of the above (i), in the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid compound (al) is 5 to 40% by weight. Preferably, the content of the repeating unit derived from the epoxy group-containing unsaturated compound (a2) is 10 to 30% by weight. 10-70% by weight, preferably 20-60% by weight, the content of the repeating unit derived from the other unsaturated compound (a3) is 10 to 70% by weight, preferably 20 to 50% by weight» (iii) The composition of the above (i) or (ii), wherein the polymerizable compound [B] is a monofunctional, difunctional or trifunctional or higher (meth) acrylate, preferably a trifunctional or higher (meth) acrylate. The esters are particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, isoamyltetraol tetrapropene-33-1343510, '· . . . acid ester, diisopentaerythritol pentaacrylic acid One or a mixture of two or more of the ester and diisopentaerythritol hexaacrylate. (iv) The composition according to any one of the above (i) to (iii), wherein the polymerization initiator [C] Further, a mixture of one or more than two kinds of other fluorene-fluorene-based polymerization initiators is contained. (v) The composition according to any one of the above (i) - (iv), wherein, relative to 100 weight The copolymer [A], the polymerizable compound [B] is used in an amount of 50 to 140 parts by weight, preferably 60 to 120 parts by weight, based on 100 parts by weight of the polymerizable compound. [B], the polymerization initiator [C] is used in an amount of 5 to 30 parts by weight, preferably 1 to 5 to 2. by weight. The radiation-sensitive resin composition is particularly suitable for use as a liquid crystal panel or a touch type. A spacer material for a display panel such as a panel. When a spacer for a display panel is formed using a radiation sensitive resin composition, the composition solution is applied onto the surface of the substrate, and then pre-baked to remove the solution to form a film. The coating method of the composition solution can be, for example, a spray coating method, a roll coating method, a spin coating method (centrifugal coating method), a slit die coating method, a wire bar coating method, an inkjet method, or the like, and the like. It is a spin coating method and a slit die coating method. The prebaking conditions vary depending on the type and ratio of each constituent component, and are usually baked at 70 to 901 for 1 to 15 minutes. Then, the prebaked film is exposed by a mask of a predetermined pattern, polymerized, developed with a developing liquid, and an unnecessary portion is removed to form a pattern. For the radiation used for exposure, visible light, ultraviolet light, -34-1343510 can be selected as appropriate. - - Radiation in the range of 1 0 0 · 4 5 0 n m from far ultraviolet rays, charged particle beams, xenon rays, etc. The method of developing may be, for example, any of the immersion methods of the fluid-flow method, and the development time is usually at a normal temperature, and the above-mentioned developing solution can be, for example, hydrogen hydroxide. Sodium carbonate, sodium citrate, sodium metasilicate, Primary amines such as ammonia and other inorganic amines; triethylamines such as diethylamine and di-n-propylamine; triolamines such as ethyldimethylamine and triethylamine; methyldiethanolamine, triethanolamine, etc. Acridine, N-methyl acridine, N-methylpyrrolidine, 1,8 - 0]-7--(--carbene, 1,5-diazabicyclo[4. 3. Tertiary amine a pyridine, a trimethylpyridine, a dimethyl tertiary amine; an aqueous solution of tetramethylammonium hydroxide or a tetraethylammonium hydroxide (alkaline aqueous solution).

Further, in the above aqueous alkaline solution, after the water-soluble organic solvent such as ethanol and/or the interface activity is developed, for example, the 3 0 -9 〇® portion is washed by running water, and then compressed air or compressed nitrogen is injected. pattern. Subsequently, the set temperature is heated using a hot plate or an oven, for example, heating at a temperature of 150-250 ° C, for example, heating for 5 - 30 minutes, and adding a desired spacer in an oven, for example, This addition _ [Effect of the invention] The radiation-sensitive resin composition of the present invention, preferably, has a wavelength of 30 - 180 seconds in a staining method, a shower method, etc. Sodium, potassium hydroxide, alkali Classes; ethylamine, n-propyl amines; trimethylamine, amines; dimethylethylalkanolamines; alicyclic groups such as pyrrole, diazabicyclo[5 . 4 . 〇]-5-decene Add an appropriate amount of methanol and hydrazine to a base such as a quaternary ammonium salt such as a pyridine or a quinoline to be an aromatic ammonium. In seconds, remove unnecessary lines to form a predetermined set, and the pattern is at the time J, on the hot plate i 30- 90 minutes, you can call it post-baking.) It is possible to faithfully reproduce the design size of the reticle pattern with high sensitivity -35- 1343510 - - and to have good adhesion to the substrate - the ideal spacer shape can be obtained with an exposure amount of 1,500 J/m 2 or less. In addition to the film thickness, it is possible to form a spacer for a display panel which is excellent in compressive strength and abrasion resistance. [Examples] Hereinafter, the embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Synthesis Example 1 _ In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and diethylene glycol methyl ethyl ether 200 were charged. Parts by weight, followed by 18 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 32 parts by weight of tricyclo [5.2.1.0''6] dec-8-yl methacrylate. After replacing with nitrogen, 5 parts by weight of 1,3-butadiene was charged, and the temperature of the solution was raised to 70 ° C while stirring slowly. This temperature was maintained for 5 hours and polymerized to obtain a copolymer [A. A solution (solid content concentration = 33.0% by weight). The Mw of the copolymer [A] was 11,000. Let the copolymer [A ] be "copolymer [A -1 ]". Lu Synthesis Example 2 A flask equipped with a cooling tube and a stirrer was charged with 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and diethylene glycol methyl ethyl ether 200. Parts by weight, followed by 18 parts by weight of methacrylic acid, 20 parts by weight of glycidol methacrylate, 5 parts by weight of phenylethyl, and trimethyl [5.2.1.02'6] 癸·8-yl ester of methyl propylene. 32 parts by weight and 25 parts by weight of tetrahydrofurfuryl methacrylate, after being replaced with nitrogen, the temperature of the solution was raised to 70 ◦C while stirring, and the temperature was maintained for 5 hours to obtain a copolymer [A]. Solution -36-1343510 (solids concentration = 33.4% by weight). The Mw of the copolymer [A] was 9,000. Let the copolymer [A] be "copolymer [a - 2 ]". Example 1 A composition solution was prepared as a copolymer of [A] component [A solution of octa-^ as an amount corresponding to the copolymer [Al] 10 parts by weight (solid content), and as a component [B] 80 parts by weight of pentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) and ι_[9_ethyl_6_(2-methylbenzoyl)-9 as component [c] ········································································· The solid content concentration was 35% by weight' and then filtered with a micropore filter having a pore size of 0.2 μm to prepare a composition solution (hereinafter referred to as "composition (S-1)"). Formation of spacer A composition solution (S-ι) was coated on an alkali-free glass substrate by a centrifugal coater and then prebaked on a hot plate at 90 ° C for 3 minutes to form a film having a film thickness of 6 · 0 /z m. Next, the obtained film was exposed by an ultraviolet ray having a wavelength of 3 6 5 nm and an exposure intensity of 3 〇 OW / m 2 at an exposure interval by a photomask having a residual 〇 / / m square pattern. Then, it was developed with 〇. 5% by weight potassium hydroxide aqueous solution at 25 ° C for 60 seconds, and washed with pure water for 1 minute. Then, it was placed in an oven and post-baked at 150 ° C for 120 minutes to form a spacer of a prescribed pattern. Then, the obtained spacers were subjected to various evaluations according to the following criteria, and the evaluation results are shown in Table 2-1. -37- 1343510 . ι,, ' w . (I) Evaluation of sensitivity For the obtained pattern, the residual film ratio after development (the film thickness after development XI 00 / initial film thickness is the same) 90%^±W Exposure® is used as sensitivity, and sensitivity is 1,500 J/m2 or less. (11) Evaluation of image resolution For the obtained pattern, the residual film ratio after imaging is 90% or more. The minimum pattern size of the exposure amount is evaluated. The smaller the pattern size is, the better the pattern resolution is. β (III) Evaluation of the pattern shape. The cross-sectional shape of the obtained pattern is observed by a scanning electron microscope, and the shape is equivalent to that shown in Fig. 1 according to the shape. One of the indicated A_c is evaluated. At this time, as shown in A, where the edge of the pattern is a forward taper, the image shape is good, as shown by B, where the edge of the pattern is vertical, the pattern shape is as shown in C, and the edge of the pattern is inverted. (In the case of the cross-sectional shape, the 'inverse triangle of the side of the film surface is longer than the side of the substrate side'.] The possibility of pattern peeling during the subsequent rubbing treatment is extremely high, and the pattern shape is poor. (IV) Evaluation of compressive strength The compressive strength of the obtained pattern was measured using a micro compression tester (trade name: MCTM-200, manufactured by Shimadzu Corporation). Specifically, 'the load of 1 OmN was applied using a flat indenter with a diameter of 50 μm at a temperature of 23 ° C', and the amount of deformation at this time was measured. When the crucible was below 55 °/m, the compressive strength was good. . (V) Evaluation of rubbing resistance AL3 046 (trade name, manufactured by JSR) was applied as a liquid crystal alignment agent to a substrate on which a spacer was formed by using a printer for coating a liquid crystal alignment film, and -38 - 1343510, 1 . After drying at l 8 (TC for 1 hour, a film thickness of 配5 μm of an alignment agent film was formed. Using a friction machine having a roll of a cloth made of polyamide, at a number of revolutions of 500 rpm, The coating film was subjected to rubbing treatment under the condition of a moving speed of the substrate of 1 cm/sec, and evaluated according to whether the pattern was cut or peeled off. (VI) Adhesive evaluation was performed except that the pattern mask was not used. In the case where a spacer is formed, a cured film for evaluating adhesion is formed in the same manner. Then, in the adhesion test of JIS K-5400 (l900) 8.5, a cross-hatch tape test of ^8.5' is performed according to The number of cells remaining in each of the cells was evaluated. Example 2 - I 8 [Α] component, [Β] component, and [C] component are shown in Table 11, except for Example 1. Operation, preparation of each composition solution, formation of spacers, various evaluations, evaluation results are shown in Table 2 - I" Example I 9 The same [Α] component, [Β] component and [C] component as in Example 3 were dissolved in Φ in diethylene glycol ethyl methyl ether to achieve a solid concentration concentration. 17.5% by weight, and then filtered with a microporous sieve filter having a pore size of 〇. 2 # m to prepare a composition solution (hereinafter referred to as "composition (S -1 9 )"). Composition (S - I 9 ) was used. A spacer was formed in the same manner as in Example 1 except that the composition (S-1) was used instead of the composition (S-1), and the results were shown in Table 2-1. Example 2 0 The same [A] component, [B] component, and [C] component as in Example 5 were dissolved - 39 - 1343510 Table 1-1 Composition of the composition [A credit (part) [B extinction ( [C) (Parts) Example 1 S-1 A-1 (100) B-1 (100) C-1 (8) - - Example 2 S-2 A-1 (100) B-1 (100) C-1 (5) r-2p〇) - Example 3 S-3 A-1 (100) B-1 (100) C-1 (10) 7-3(15) _ Example 4 S -4 A-1 (100) B-1 (100) C-1(3) 7-2/γ -3 (10/10) - Example 5 S-5 A-1 (100) B-1 (80) c- 1 (5) _ 7 -4/ γ -5/ 7 -6 (5/5/2.5) Example 6 S-6 A-1 (100) B-1 (80) C-1 (3) 7-2(25) 7 -4/ 7 -5/ γ -6 (5/5/2.5) Example 7 S-7 A-1 (100) B-1 (80) C-1 (5) r-3 (20) 7 -4/ γ -5/ 7 -6 (5/5/2.5) Example 8 S -8 A-1 (100) B-1 (100) C-1 (5) γ -2/ γ -3 (10/10) 7-4/7-5/7-6 (5/5/2, 5) Example 9 S-9 A-1 (100) B-1 (100) ci/ri (4/1) r-3 (20) γ -4/ 7 -5/ 7 ·6 (6/6/ 3) Example 10 S-10 A-1 (100) B-1/B-2 (90/10) C-1(7) - γ -4/ γ -5/ γ -6 (6/6/3) Example 11 S-11 A-1 (100) B-1/B-2 (90/10) C-1 (5) 7-2(10) 7 -4/ 7 -5/ 7 -6 (5/5/ 2.5) Example 12 S-12 A-1 (100) B-1/B-2 (90/10) C-1 (5) 7-3(15) 7 -4/ 7 -5/ 7 ·6 ( 5/5/2,5) Example 13 S-13 A-1 (100) B-1/B-2 (80/20) C-1(8) γ -2/ γ -3 (10/15) γ -4 / 7 -5/ τ -6 (5/5/2.5) Example 14 S-14 A-2 (100) B-1/B-2 (80/20) C-1 (5) _ 7 -4/ γ -5/ γ -6 (5/5/2.5) Example 15 S-15 A-2 (100) B-1/B-2 (60/40) C-1 (5) 7-2(25) 7 -4/- 7 -5/ r -6 (6/6/3) Example 16 S-16 A-2 (100) B-1/B-2 (80/20) C-1 (5) 7 -3(30) 7 -4/ 7 -5/ Τ -6 (6/6/3) Example Π S-17 A-2 (100) B-1/B-2 (90/10) C-1 (3) γ - 2/7-3 (10/10) 7 -4/ 7 -5/ 7 -6 (6/6/3) Example 18 S-18 A-2 (100) B-1/B-2 (90/ 10) ci/ri (3/2) 7-2/γ -3 (10/5) 7 -4/ r -5/ Τ *6 (6/6/3) Example 19 S-19 A-1 ( 100) B-1 (100) C-1 (10) 7-3(15) _ Example 20 S-20 A-1 (100) B-1 (80) c-1 (5) — 7 -4/ 7 -5/ 7 -6 (5/5/2.5) -42- 1343510

Table 1-2 Surface of the composition [A credit (parts) [B Cheng cent (parts) Polymerization initiator (parts) Comparative Example 1 s-1 A-1 (100) B-1 (100) A 7-2 (20) - Comparative Example 2 s-2 A-1 (100) B-1 (100) - r-3 (2 〇) - Comparative Example 3 s-3 A-1 (100) B-1 (100) 7-2/7-3 (10/10) - Comparative Example 4 s-4 A-1 (100) B-1 (100) One - 7 -4/ 7 -5/ 7 -6 (6/6/3 Comparative Example 5 s-5 A-1 (100) B-1 (80) A 7-2(15) γ -4/ 7 -5/ 7 *6 (6/6/3) Comparative Example 6 s-6 A-1 (100) B-1 (80) A 7-3(15) γ -4/ 7 -5/ Τ -6 (6/6/3) Comparative Example 7 s-7 A-1 (100) B -1 (80) A 7 -2/7 -3 (15/15) 7 -4/ 7 -5/ Τ -6 (5/5/2.5) Comparative Example 8 s-8 A-1 (100) B- 1 (80) ri(5) γ -2/γ -3 (10/10) 7 -4/ 7 -5/ 7 -6 (5/5/2,5) Comparative Example 9 s-9 A-1 ( 100) B-1/B-2 (80/20) - γ -2 / γ -3 (10/10) 7 -4/ 7 -5/ 7 -6 (5/5/2.5) Comparative Example 10 s- 10 A-2 (100) B-1/B-2 (90/10) 7-1(5) γ -2/γ -3 (10/10) 7 -4/ 7 -5/ 7 -6 (5 /5/2.5) -43- 1343510 Table 2-1

_ Sensitivity (J/m2) of the composition Image resolution ((4) Pattern shape compressive strength (μιη) Friction-resistant adhesion Example 1 S-1 1,500 10 B 0.51 Μ ί\\\ 100 Example 2 S- 2 1,3〇〇8 B 0.52 No 100 Example 3 S-3 1,300 10 A 0.32 No 100 Example 4 S-4 1,200 8 A 0.32 ΛττΤ. m 100 Example 5 S-5 1,000 10 B 0.48 4rrf. m 100 Example 6 S-6 800 8 B 0.52 frrr. m 100 Example 7 S-7 800 10 A 0.25 4rrf. m 100 Example 8 S-8 800 8 A 0.27 M 100 Example 9 S-9 700 8 A 0.28 4rrt. m 100 Example 10 S-10 800 12 A 0.28 4ττΤ. 100 Example 11 S-11 700 10 A 0.27 No 100 Example 12 S-12 700 12 A 0.25 Art No 100 Example 13 S-13 600 10 A 0.26 without 100 Example 14 S-14 900 8 A 0.28 fnf 100 Example 15 S-15 800 8 A 0.27 No 100 Example 16 S-16 800 8 A 0.25 inL M 100 Example 17 S-17 700 8 A 0.26 M 100 Example 18 S-18 600 8 A 0.26 AttT. m 100 Example 19 S-19 1,3〇〇10 A 0.33 M 100 Example 20 S-20 1,000 10 B 0.55 Ji\\ 100 -44 - 1343510 Table 2-2 Type sensitivity of composition (J/m 2) Image resolution (μηι) Pattern shape compressive strength (μιη) Friction resistance Adhesion Comparative Example 1 s-1 3,000 8 C 0.57 There are 80 Comparative Example 2 s-2 2,700 10 A 0.36 ΤΤΤΓ V»,, 100 Comparative Example 3 s-3 2,500 8 A 0.32 Arrr ι 100 Comparative Example 4 s-4 2,200 10 B 0.48 te y» nn 100 Comparative Example 5 s-5 2,000 8 B 0.56 fm*. τΤΓΓ j\w 100 Comparative Example 6 s -6 1,800 10 A 0.27 ^TTT. ittr 100 Comparative Example 7 s-7 1,600 8 A 0.29 M 100 Comparative Example 8 s-8 1,700 8 A 0.29 4ttT ΠΙΙ: w 100 Comparative Example 9 s-9 1,600 12 A 0.29 4fff 100 Comparative Example 10 s-10 1,700 8 A 0.27 fnT ittr 100 [Simple description of the drawing]

Fig. 1 is a view illustrating a cross-sectional shape of a pattern.

-45-

Claims (1)

1343510 _ ^ 丨ι哼 (Piece > Day Correction Replacement Page Revision No. 094 1 03 5 23 "Radiation Resin Composition, Display Panel Spacer and Display Panel" Patent Case (January 21, 2011) Amendment) X. Patent application scope: '1. A radiation sensitive linear resin composition characterized by: • [A] (al) ethylenically unsaturated carboxylic acid and/or ethylenically unsaturated carboxylic anhydride, (a2) a copolymer of an epoxy group-containing ethylenically unsaturated compound and (a3) another ethylenically unsaturated compound; φ [B] a polymerizable compound having an ethylenically unsaturated bond; and [C] the following formula (1) or The compound represented by the formula (2) is a radiation-sensitive polymerization initiator of an essential component, [In the formulae (1) and (2), each R1 independently represents a linear, branched or cyclic alkyl group or a phenyl group having 1 to 12 carbon atoms, and each of R2 is independently of the table 1343.510. I month > the next day correction replacement page '------- amend the hydrogen atom, a linear 'branched or cyclic alkyl group or a phenyl group having 1 to 12 carbon atoms, and each R3 is independent of each other. A linear or branched or cyclic group representing a hydrogen atom or a carbon number of 1 to 12, and each of R4, each R5 and each of R6 independently represents a hydrogen atom or a linear or branched chain having a carbon number of 丨-6. Or a cyclic alkyl group, but the alkyl groups of R1, R2, R3, R4, R5 and R6 may also be selected from a linear, branched or cyclic alkoxy group having from 1 to 6 carbon atoms, and a phenyl group. And a substituent in the halogen atom, the phenyl group of R1 and R2 may also be selected from a linear, branched or cyclic alkyl group having a carbon number of 1-6, and a linear chain having a carbon number of 1-6. a branched or cyclic alkoxy group, a phenyl group, and a substituent in a halogen atom are substituted.] 2. A spacer for a display panel, which is composed of a radiation sensitive resin as in the first item of the patent application. The object is formed. 3) A display panel having a spacer for a display panel according to item 2 of the patent application scope.