JP5521800B2 - Radiation-sensitive resin composition, cured film, method for forming cured film, and display element - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition suitable as a material for forming a cured film such as an interlayer insulating film, a protective film or a spacer, a cured film formed from the composition, a method for forming the cured film, and the cured film. It is related with a display element provided with.

  Radiation-sensitive resin compositions are widely used as materials for forming interlayer insulating films, spacers, protective films, and the like. As this radiation-sensitive resin composition, for example, a composition containing a copolymer composed of an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound, or the like is disclosed (see JP 2001-354822 A). However, in order to increase the surface hardness to a level that is actually required commercially as a liquid crystal display element spacer, a baking process at a high temperature of 200 ° C. or more is required.

  On the other hand, in recent years, a color resist using a dye having excellent solubility for improving contrast has been widely used. In general, dyes have poor heat resistance compared to pigments, and phenomena such as fading are observed in a baking process at 200 ° C. or higher. Therefore, it is desired to lower the temperature in the baking process in the production of a display that normally requires 200 ° C. or higher.

  In view of the above circumstances, a technique of a coating liquid for a gate insulating film for a flexible display containing a polyimide precursor that can be cured even by low-temperature firing has been developed (see JP 2009-4394 A). However, since this coating solution does not have the ability to form a pattern by exposure and development, it is impossible to form a fine pattern. Furthermore, due to insufficient progress of the curing reaction, the resulting cured film is satisfactory in terms of transmittance, flatness, voltage holding ratio, etc. in addition to heat resistance, light resistance, and chemical resistance. is not.

  In view of this, it is conceivable to add a amine compound used as a curing agent for epoxy-based materials to advance the crosslinking reaction even at low temperatures. However, the addition of a general amine compound may cause a reaction with time with an epoxy group present in the composition, resulting in a decrease in storage stability.

  Under such circumstances, a radiation-sensitive resin composition having both storage stability and low-temperature firing, sufficient resolution and radiation sensitivity, and heat resistance, light resistance, and chemical resistance, which are required characteristics of a cured film. Development of a cured film having excellent transmittance, flatness, voltage holding ratio and the like is desired.

JP 2001-354822 A JP 2009-4394 A

  The present invention has been made based on the circumstances as described above, and its purpose is to achieve both storage stability and low-temperature firing, and a radiation-sensitive resin composition having sufficient resolution and radiation sensitivity, and curing. To provide a cured film excellent in heat resistance, light resistance, chemical resistance, transmittance, flatness, voltage holding ratio, and the like, which are required characteristics of the film, a method for forming the cured film, and a display element including the cured film. It is.

（式（１）中、Ｒ^１〜Ｒ^６はそれぞれ独立して、水素原子、電子吸引性基又はアミノ基である。但し、Ｒ^１〜Ｒ^６のうち少なくとも１つは電子吸引性基であり、Ｒ^１〜Ｒ^６のうち少なくとも１つはアミノ基であり、上記アミノ基は水素原子の全部又は一部が炭素数１〜６のアルキル基で置換されていてもよい。
式（２）中、Ｒ^７〜Ｒ^１６はそれぞれ独立して、水素原子、電子吸引性基又はアミノ基である。但し、Ｒ^７〜Ｒ^１６のうち少なくとも１つはアミノ基である。また、上記アミノ基は水素原子の全部又は一部が炭素数２〜６のアルキレン基で置換されていてもよい。Ａは単結合、カルボニル基、カルボニルオキシ基、カルボニルメチレン基、スルフィニル基、スルホニル基、メチレン基又は炭素数２〜６のアルキレン基である。但し、上記メチレン基及びアルキレン基はシアノ基、ハロゲン原子又はフルオロアルキル基で置換されていてもよい。） The invention made to solve the above problems is
[A] a compound having an epoxy group (hereinafter sometimes referred to as “[A] compound”),
[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter sometimes referred to as “[B] polymerizable compound”),
[C] Radiation sensitive polymerization initiator (hereinafter sometimes referred to as “[C] polymerization initiator”), and [D] selected from the group consisting of compounds represented by the following formulas (1) and (2) At least one kind (hereinafter sometimes referred to as “[D] compound”)
Is a radiation-sensitive resin composition.

(In formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group, provided that at least one of R ^{1 to} R ⁶ is an electron withdrawing group. , At least one of R ^{1 to} R ⁶ is an amino group, and in the amino group, all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms.
In formula (2), R ^{7 to} R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group, or an amino group. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with an alkylene group having 2 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, the methylene group and alkylene group may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. )

  The radiation sensitive resin composition contains a [A] compound, a [B] polymerizable compound, a [C] polymerization initiator, and a [D] compound. The radiation-sensitive resin composition, which is a photosensitive material, can easily form a fine and elaborate pattern by exposure and development utilizing radiation sensitivity, and has sufficient resolution and radiation sensitivity. Moreover, the said radiation sensitive resin composition can improve the required characteristics of cured films, such as heat resistance, even if it is a case of a low exposure amount by containing a [C] polymerization initiator. Furthermore, by containing the [D] compound having an amino group and an electron-withdrawing group, both the storage stability of the radiation-sensitive resin composition and the acceleration of curing of the cured film in low-temperature firing can be achieved at a high level, Further, the voltage holding ratio of the obtained display element having a cured film such as a protective film, an interlayer insulating film, or a spacer can be maintained at a high level.

  [A] The compound is preferably a polymer, more preferably a polymer further having a carboxyl group. When the [A] compound has such a structure, the radiation-sensitive resin composition can form a cured film having excellent heat resistance, light resistance, chemical resistance, transmittance, flatness, and the like.

  The said radiation sensitive resin composition is suitable for forming the cured film as an interlayer insulation film, a protective film, or a spacer.

The method for forming the cured film of the present invention is as follows.
(1) The process of forming the coating film of the said radiation sensitive resin composition on a board | substrate (2) The process of irradiating at least one part of the coating film formed at the process (1),
(3) a step of developing the coating film irradiated with radiation in the step (2); and (4) a step of baking the coating film developed in the step (3).

  By the forming method of the present invention using the radiation-sensitive resin composition, a cured film satisfying the required characteristics such as heat resistance, light resistance, chemical resistance, transmittance, flatness, voltage holding ratio and the like in a balanced manner can be formed.

  It is preferable that the calcination temperature of the said process (4) is 200 degrees C or less. Since the radiation-sensitive resin composition contains the [D] compound as described above, it achieves low-temperature firing in this way and achieves both storage stability and sufficient resolution and radiation sensitivity. Therefore, the radiation-sensitive resin composition is suitably used as a material for forming a cured film such as a colored resist using a dye that is desired to be fired at a low temperature, an interlayer insulating film used in flexible displays, a protective film, and a spacer. .

  A cured film as an interlayer insulating film, protective film or spacer formed from the radiation sensitive resin composition is also suitably included in the present invention. Moreover, a display element provided with this cured film is also suitably included in the present invention.

  Note that “baking” in the present specification means heating until a surface hardness required for a cured film such as an interlayer insulating film, a protective film, and a spacer is obtained. The “radiation” of the “radiation sensitive resin composition” is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  As described above, the radiation-sensitive resin composition of the present invention can easily form a fine and elaborate pattern, achieves both storage stability and low-temperature firing, and has sufficient resolution and radiation sensitivity. Moreover, the cured film formed from the said radiation sensitive resin composition is excellent in the required characteristics, such as heat resistance, light resistance, chemical resistance, transmittance, flatness, and voltage holding ratio. Therefore, the radiation-sensitive resin composition is suitably used as a material for forming a cured film such as an interlayer insulating film, a protective film, or a spacer used in a colored resist or a flexible display using a dye that is desired to be fired at a low temperature.

  Hereinafter, embodiments of the present invention will be described in detail.

<Radiation sensitive resin composition>
The radiation-sensitive resin composition used for forming the cured film of the present invention contains [A] compound, [B] polymerizable compound, [C] polymerization initiator and [D] compound, and further contains optional components. May be. The radiation-sensitive resin composition, which is a photosensitive material, can easily form fine and elaborate patterns by exposure / development utilizing radiation sensitivity, achieves both storage stability and low-temperature firing, and has sufficient resolution. And having radiation sensitivity. Hereinafter, each component will be described in detail.

<[A] Compound>
The [A] compound contained in the radiation sensitive resin composition has an epoxy group. Examples of the compound [A] include compounds having two or more 3,4-epoxycyclohexyl groups in one molecule.

  Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-ethylene glycol) (Epoxycyclohexylmethyl) ether , Ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

Examples of other [A] compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl. Diglycidyl ethers of bisphenol compounds such as ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

Examples of these commercially available products include, as bisphenol A type epoxy resins, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (above, Japan Epoxy Resin Co., Ltd.);
As bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolak type epoxy resin, Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.), etc .;
As cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd.) and the like;
As polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (above, U C.C), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat 871, 872 (above, Japan Epoxy Resin), ED-5661, 5562 (Above, Celanese coating company) etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (Kyoeisha Chemical Co., Ltd.) and Epiol TMP (Nippon Yushi Co., Ltd.).
Of these, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  When the [A] compound as exemplified above and the [A] compound which is a copolymer having a carboxyl group described later are both contained in the radiation-sensitive composition, as exemplified above [ A] The amount of the compound used is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 2 parts by mass to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group described later. 15 parts by mass is particularly preferred.

  [A] The compound is preferably a polymer, and more preferably the polymer further has a carboxyl group. When the compound [A] has such a structure, the radiation-sensitive resin composition can form a cured film that is superior in heat resistance, light resistance, chemical resistance, transmittance, flatness, and the like.

  Examples of such a polymer of the [A] compound having a carboxyl group may be referred to as (a1) a radical polymerizable compound having an epoxy group that gives an epoxy group-containing structural unit (hereinafter referred to as “compound (i)”). ) And (a2) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (hereinafter referred to as “compound (ii)”) which gives a carboxyl group-containing structural unit (the carboxyl group also includes an acid anhydride group). ). Further, as necessary, as (a3), a radically polymerizable compound such as (meth) acrylic acid alkyl ester (hereinafter sometimes referred to as “compound (iii)”) is converted to the above compound (i) or compound (ii). In addition, a copolymer may be used.

Examples of the compound (i) include radical polymerizable compounds having an epoxy group (oxiranyl group, oxetanyl group) and the like. Examples of the radical polymerizable compound having an oxiranyl group include glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, Acrylic acid epoxy alkyl esters such as acrylic acid-3,4-epoxycyclohexylmethyl;
Such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate Methacrylic acid epoxy alkyl ester;
α-alkylacrylic acid epoxy alkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl;
Examples thereof include glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

  Examples of the radical polymerizable compound having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- ( Methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3 -Ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyl) Oxyethyl) oxetane, 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- (methacryloyloxymethyl) Oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxyethyl) -2-methyloxetane, 2- (methacryloyloxy) Ethyl) -4-methyloxetane, 2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- ( Acrylo Ruoxymethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyloxetane, 2- ( And methacrylic acid oxetanyl alkyl esters such as acryloyloxyethyl) -4-methyloxetane.

  Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl)- 3-ethyloxetane and 2- (methacryloyloxymethyl) oxetane have high adhesion to substrates of cured films such as interlayer insulating films, protective films, and spacers obtained, have high heat resistance, and reliability in display elements It is preferable from the point which raises.

Examples of the compound (ii) include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydro. Monocarboxylic acids such as phthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid;
Examples thereof include dicarboxylic acid anhydrides such as maleic anhydride.

  Of these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, maleic anhydride, from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkaline developer Is preferred.

  In the compound [A], structural units derived from the compound (i) can be used alone or in admixture of two or more. [A] In a compound, as content rate of compound (i), 10 mass%-70 mass% are preferable, and 15 mass%-65 mass% are more preferable. By controlling the content of the compound (i) from 10% by mass to 70% by mass, the molecular weight of the copolymer can be easily controlled, and the radiation sensitive resin composition is optimized at a higher level of developability and sensitivity. Things are obtained.

  In the compound [A], structural units derived from the compound (ii) can be used alone or in admixture of two or more. [A] In the compound, the content of the compound (ii) is preferably 1% by mass to 40% by mass, more preferably 7% by mass to 30% by mass, and particularly preferably 8% by mass to 25% by mass. By setting the content of compound (ii) to 1% by mass to 40% by mass, a radiation-sensitive resin composition optimized at a higher level of radiation sensitivity, developability, storage stability, and the like is obtained.

  Compound (iii) includes (meth) acrylic acid alkyl ester, (meth) acrylic acid alicyclic ester, unsaturated hetero five-membered ring containing oxygen atom and six-membered ring (meth) acrylic ester, and hydroxyl group (meta ) Acrylic acid ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, maleimide compound, styrene, α-methylstyrene, 1,3-butadiene.

  Examples of the (meth) acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t- Examples include butyl acrylate and n-lauryl methacrylate.

Examples of (meth) acrylic acid alicyclic alkyl esters include cyclopentyl methacrylate, cyclohexyl methacrylate, methacrylic acid-2-methylcyclohexyl, methacrylic acid tricyclodicyclopentani, methacrylic acid-2-dicyclopentanyloxyethyl, Isobornyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclodicyclopentani acrylate, 2-acrylate Examples include dicyclopentanyloxyethyl and isobornyl acrylate.

Examples of unsaturated heterocyclic 5-membered and 6-membered methacrylic acid esters containing an oxygen atom include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran- Unsaturated compounds containing a tetrahydrofuran skeleton such as 2-one;
2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan-2-butyl- 3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-en-3-one, Unsaturated compounds containing a furan skeleton such as acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one;
(Tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, Unsaturated compounds containing a tetrahydropyran skeleton such as 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one;
4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo-7-octenyl) -6-methyl-2- Examples thereof include unsaturated compounds containing a pyran skeleton such as pyran.

  Examples of (meth) acrylic acid ester having a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, and (meth) acrylic acid. -2,3-dihydroxypropyl and the like.

  Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate and benzyl (meth) acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  [A] In a compound, as content rate of the structural unit derived from a compound (iii), 10 mass%-70 mass% are preferable, and 15 mass%-65 mass% are more preferable. By controlling the copolymerization ratio of the compound (iii) to 10% by mass to 70% by mass, it becomes easy to control the molecular weight of the copolymer, and the development, sensitivity, adhesion, etc. are optimized at a higher level. A radiation resin composition is obtained.

<[A] Compound Synthesis Method>
The compound [A] can be synthesized, for example, by polymerizing the compound (i), the compound (ii) and, if necessary, the compound (iii) in a solvent using a radical polymerization initiator.

  [A] Examples of the solvent used in the polymerization reaction for producing the compound include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. , Propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

  Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

  Examples of ethers include cyclic ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate and the like.

  Examples of the cyclic ether include tetrahydrofuran and the like.

  Examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .

  Examples of aromatic hydrocarbons include toluene and xylene.

  Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl ropoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl xylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 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 the like. Of these, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferable.

  A radical polymerization initiator can be used individually or in mixture of 2 or more types. As a usage-amount of a radical polymerization initiator, 0.1 mass%-50 mass% are preferable normally with respect to a total of 100 mass% of a compound (i), a compound (ii), and a compound (iii). The mass% to 20 mass% is more preferable.

In the polymerization reaction, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

  As a usage-amount of a molecular weight modifier, it is 0.1 mass%-50 mass% normally, and 0.2 mass%-16 with respect to the total 100 mass% of a compound (i), a compound (ii), and a compound (iii). % By mass is preferable, and 0.4% by mass to 8% by mass is more preferable. As polymerization temperature, 0 degreeC-150 degreeC and 50 degreeC-120 degreeC are preferable normally. The polymerization time is usually preferably 10 minutes to 20 hours and 30 minutes to 6 hours.

[A] As a polystyrene conversion weight average molecular weight (Mw) of a compound, 2 * 10 < ³ > -1 * 10 < ⁵ > is preferable and 5 * 10 < ³ > -5 * 10 < ⁴ > is more preferable. [A] When the Mw of the compound is 2 × 10 ³ or more, a sufficient development margin of the radiation-sensitive resin composition is obtained, and the remaining film ratio of the coating film to be formed (the ratio in which the patterned thin film remains properly) ) Can be prevented, and the pattern shape and heat resistance of the resulting insulating film can be kept good. On the other hand, when the Mw of the [A] compound is 1 × 10 ⁵ or less, high radiation sensitivity is maintained and a good pattern shape can be obtained. Further, the molecular weight distribution (Mw / Mn) of the [A] compound is preferably 5.0 or less, and more preferably 3.0 or less. By making Mw / Mn of the compound [A] 5.0 or less, the pattern shape of the obtained insulating film can be kept good. Moreover, since the radiation sensitive resin composition containing the [A] compound having Mw and Mw / Mn in the preferred ranges as described above has high developability, it is easily generated without developing residue in the development process. A predetermined pattern shape can be formed.

<[B] Polymerizable compound>
[B] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. Examples of the [B] polymerizable compound contained in the radiation-sensitive resin composition include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tri Cyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) In addition to phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, etc., a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, And urethane (meth) acrylate compounds obtained by reacting with a compound having one or more hydroxyl groups and 3 to 5 (meth) acryloyloxy groups.

As a commercial item of the above-mentioned [B] polymerizable compound, for example, Aronix M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8100, M-8530, M-8560, M-9050, Aronix TO-1450, TO-1382 (above, Toagosei Co., Ltd.) ;
KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (above, Nippon Kayaku Co., Ltd.);
Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.);
As a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.);
KAYARAD DPHA-40H, UX-5000 (Nippon Kayaku Co., Ltd.);
UN-9000H (Negami Kogyo Co.);
Aronix M-5300, M-5600, M-5700, M-210, M-220, M-240, M-270, M-6200, M-305, M-309, M M-310, M-315 (above, Toagosei Co., Ltd.);
KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301 UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.);
Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (Negami Industrial Co., Ltd.);
SH-500B biscoat 260, 312 and 335HP (above, Osaka Organic Chemical Industry Co., Ltd.).

  [B] A polymeric compound can be used individually or in mixture of 2 or more types. As a content rate of the [B] polymeric compound in the said radiation sensitive resin composition, 20 mass parts-200 mass parts are preferable with respect to 100 mass parts of [A] compound which is a copolymer which has a carboxyl group, 40 mass parts-160 mass parts are more preferable. [B] By setting the content ratio of the polymerizable compound in the above range, the radiation-sensitive resin composition has excellent adhesion and sufficient hardness even at a low exposure amount, an interlayer insulating film, a protective film, a spacer, and the like A cured film is obtained.

<[C] Polymerization initiator>
[C] polymerization initiator contained in the said radiation sensitive resin composition is a component which produces the active seed | species which can start the superposition | polymerization of a [B] polymeric compound in response to a radiation. [C] Examples of the polymerization initiator include O-acyloxime compounds and acetophenone compounds.

  Examples of the O-acyloxime compound include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Of these, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 -Morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  Of these, α-aminoketone compounds are preferred, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-Morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are more preferred.

  [C] The polymerization initiators can be used alone or in admixture of two or more. As a content rate of the [C] polymerization initiator in the said radiation sensitive resin composition, 1-40 mass parts is preferable with respect to 100 mass parts of [A] compound which is a copolymer which has a carboxyl group, 5 mass parts-30 mass parts are more preferable. [C] By setting the content ratio of the polymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition has an interlayer insulating film and a protective film having high hardness and adhesion even in the case of a low exposure amount. In addition, a cured film such as a spacer can be formed.

<[D] Compound>
The radiation-sensitive resin composition contains a [D] compound having an amino group and an electron-withdrawing group, so that the storage stability of the radiation-sensitive resin composition and the acceleration of curing of the cured film in low-temperature firing are achieved. It is possible to achieve both at a high level, and it is possible to maintain the voltage holding ratio of the obtained display element having a cured film such as a protective film, an interlayer insulating film, and a spacer at a high level.

[D] A compound is at least 1 sort (s) chosen from the group which consists of a compound represented by the said Formula (1) and Formula (2). In said formula (1), R < ¹ > -R < ⁶ > is respectively independently a hydrogen atom, an electron withdrawing group, or an amino group. However, at least one of R ^{1 to} R ⁶ is an electron-withdrawing group, and at least one of R ^{1 to} R ⁶ is an amino group, and the amino group has all or part of the hydrogen atoms as a carbon number. It may be substituted with 1 to 6 alkyl groups.
In formula (2), R ^{7 to} R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group, or an amino group. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with an alkylene group having 2 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group, or an alkylene group having 2 to 6 carbon atoms. However, the methylene group and alkylene group may be substituted with a cyano group, a halogen atom or a fluoroalkyl group.

Examples of the electron withdrawing group represented by R ^{1 to} R ¹⁶ include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an acyl group, an alkylsulfonyl group, an alkylsulfonate group, a dicyanovinyl group, and a tricyano group. A vinyl group, a sulfonyl group, etc. are mentioned. Of these, a nitro group, an alkyl sulfonate group, and a trifluoromethyl group are preferable. The group represented by A is preferably a methylene group which may be substituted with a sulfonyl group or a fluoroalkyl group.

[D] As a compound,
2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4′-diaminobenzophenone, 4,4′-diaminophenylbenzoate, 4,4 '-Diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1, 4-diamino-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2′-dichlorobenzidine, 2,2′-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis (trifluoromethyl) benzidine , Ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, and 4,4′-diaminodiphenyl Sulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) benzidine, ethyl 3-aminobenzenesulfonate, 3,5-bistrifluoromethyl-1,2- Diaminobenzene, 4-aminonitrobenzene, and N, N-dimethyl-4-nitroaniline are more preferable.

  As a content rate of the [D] compound in the said radiation sensitive resin composition, 0.1-20 mass parts is preferable with respect to 100 mass parts of [A] compound which is a copolymer which has a carboxyl group, 0.2 mass part-10 mass parts are more preferable. [D] By setting the content ratio of the compound to 0.1 parts by mass to 10 parts by mass, the storage stability of the radiation-sensitive resin composition and the acceleration of curing of the cured film can be achieved at a high level and further obtained. In addition, the voltage holding ratio of the display element having a cured film such as a protective film, an interlayer insulating film, or a spacer can be maintained at a high level.

<Optional component>
In addition to the above [A] compound, [B] polymerizable compound, [C] polymerization initiator, and [D] compound, the radiation sensitive resin composition may be used as long as the desired effect is not impaired. [E] Adhesive aids, [F] surfactants, [G] storage stabilizers, and [H] heat resistance improvers. Each of these optional components may be used alone or in combination of two or more. Hereinafter, it explains in full detail in order.

[[E] Adhesive aid]
[E] The adhesion assistant can be used to further improve the adhesion between the obtained interlayer insulating film, a cured film such as a spacer or a protective film, and the substrate. As such [E] adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxiranyl group is preferable. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri And methoxysilane.

  [E] The amount of the adhesion assistant used is preferably 20 parts by mass or less and more preferably 15 parts by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. [E] When the amount of the adhesion aid used exceeds 20 parts by mass, there is a tendency that a development residue is likely to occur.

[[F] Surfactant]
[F] Surfactant can be used to further improve the film-forming property of the radiation-sensitive resin composition. [F] Surfactants include, for example, fluorine-based surfactants, silicone-based surfactants, and other surfactants. The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and 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, hexaethylene glycol di (1,1,2, 2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3, 3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether Sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n -Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoroalkylpolyoxy Examples thereof include ethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Commercially available fluorosurfactants include, for example, BM-1000, BM-1100 (above, BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, Sumitomo 3M), Surflon S-112, -113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, Asahi Glass), F-top EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), Footent FT-100, -110, -140A, -150, -250, and -25 , The -300, the -310, the -400S, Ftergent FTX-218, the -251 (or, Neos Co., Ltd.).

  Examples of commercially available silicone surfactants include Torresilicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) and the like.

  Examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n- Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymer polyflow No. 57, no. 95 (above, Kyoeisha Chemical Co., Ltd.).

  [F] The amount of the surfactant used is preferably 1.0 part by mass or less and more preferably 0.8 part by mass or less based on 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. . [F] When the amount of the surfactant used exceeds 1.0 part by mass, film unevenness tends to occur.

[[G] Storage stabilizer]
[G] Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxyl. Examples include amine aluminum.

  [G] The amount of the storage stabilizer used is preferably 3.0 parts by mass or less and more preferably 1.0 part by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. [G] When the compounding quantity of a storage stabilizer exceeds 3.0 mass parts, the sensitivity of the said radiation sensitive resin composition may fall and a pattern shape may deteriorate.

[[H] heat resistance improver]
Examples of the [H] heat resistance improver include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.

  Examples of N- (alkoxymethyl) glycoluril compounds include N, N ′, N ″, N ′ ″-tetra (methoxymethyl) glycoluril, N, N ′, N ″, N ′ ″-tetra (Ethoxymethyl) glycoluril, N, N ′, N ″, N ′ ″-tetra (n-propoxymethyl) glycoluril, N, N ′, N ″, N ′ ″-tetra (i-propoxy) Methyl) glycoluril, N, N ′, N ″, N ′ ″-tetra (n-butoxymethyl) glycoluril, N, N ′, N ″, N ′ ″-tetra (t-butoxymethyl) Examples include glycoluril. Of these, N, N ', N ", N" "-tetra (methoxymethyl) glycoluril is preferred.

  Examples of N- (alkoxymethyl) melamine compounds include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″. Hexa (ethoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (I-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (T-butoxymethyl) melamine and the like. Of these, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is preferred, and examples of commercially available products include Nicalac N-2702 and MW-30M (above, Sanwa Chemical). Company).

  [H] The amount of the heat resistance improver used is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. [H] When the compounding amount of the heat resistance improver exceeds 50 parts by mass, the sensitivity of the radiation-sensitive resin composition may be reduced, and the pattern shape may be deteriorated.

<Preparation of radiation-sensitive resin composition>
In addition to the [A] compound, the [B] polymerizable compound, the [C] polymerization initiator, and the [D] compound, the radiation-sensitive resin composition of the present invention can be used as long as the desired effect is not impaired. It is prepared by mixing arbitrary components at a predetermined ratio. This radiation-sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent.

  As a solvent used for the preparation of the radiation sensitive resin composition, [A] compound, [B] polymerizable compound, [C] polymerization initiator, [D] compound and optional components are uniformly dissolved or dispersed, Those that do not react with each component are used. As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to synthesize | combine the above-mentioned [A] compound is mentioned. A solvent can be used individually or in mixture of 2 or more types.

  Diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, etc. Acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol and 3-methoxybutanol are preferred.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent include N-methylpyrrolidone, N, N-dimethylacetamide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, malein Examples include diethyl acid, γ-butyrolactone, and propylene carbonate. Of these, N-methylpyrrolidone, γ-butyrolactone or N, N-dimethylacetamide is preferred.

  As a solvent for the radiation-sensitive resin composition, when a high-boiling solvent is used in combination, the amount used is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass with respect to the total amount of solvent. The following are particularly preferred: When the amount of the high-boiling solvent used is 50% by mass or less, the film thickness uniformity, sensitivity, and residual film rate are good.

  When the radiation-sensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) may be any concentration (for example, depending on the purpose of use, desired film thickness, etc. 5 mass% to 50 mass%). A more preferable solid content concentration varies depending on the method of forming a film on the substrate, which will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore size of about 0.5 μm.

<Method for forming cured film>
A cured film as an interlayer insulating film, protective film or spacer formed from the radiation sensitive resin composition is also suitably included in the present invention. Hereinafter, a method for forming a cured film using the radiation-sensitive resin composition will be described in detail.

The method for forming a cured film of the present invention includes at least the following steps (1) to (4) in the order described below.
(1) The process of forming the coating film of the said radiation sensitive resin composition on a board | substrate (2) The process of irradiating at least one part of the coating film formed at the process (1),
(3) Step of developing the coating film irradiated with radiation in step (2) and (4) Step of baking the coating film developed in step (3)

  By the forming method of the present invention using the radiation-sensitive resin composition, a cured film satisfying the required characteristics such as heat resistance, light resistance, chemical resistance, transmittance, flatness, voltage holding ratio and the like in a balanced manner can be formed. Hereinafter, each of these steps will be described in detail.

[(1) Step of forming a coating film of the radiation-sensitive resin composition on a substrate]
A transparent conductive film is formed on one side of the transparent substrate, and a film of the radiation sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and 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 (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Etc.

  In the case of forming a film by a coating method, the film can be formed preferably by heating (pre-baking) the coated surface after coating the solution of the radiation sensitive resin composition on the transparent conductive film. . As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the application method of the radiation sensitive resin composition solution include spraying, roll coating, spin coating (spin coating), slit coating (slit die coating), bar coating, and ink jet coating. An appropriate method can be adopted. Of these, spin coating or slit coating is preferred.

  The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are preferably 70 ° C. to 120 ° C. and about 1 to 15 minutes. The film thickness after pre-baking of the coating is preferably 0.5 μm to 10 μm, more preferably about 1.0 μm to 7.0 μm.

[(2) Step of irradiating at least a part of the coating film formed in step (1)]
Next, radiation is applied to at least a part of the formed film. At this time, when irradiating only a part of the film, for example, the irradiation can be performed through a photomask having a predetermined pattern.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. ^{Inc.), 100J / m 2 ~5,000J} / m 2 is Preferably, 200 J / m ^{2 to} 3,000 J / m ² is more preferable.

The radiation-sensitive resin composition has high radiation sensitivity as compared with conventionally known compositions, and a desired film even if the radiation dose is 700 J / m ² or less, and even 600 J / m ² or less. There is an advantage that a cured film such as an interlayer insulating film, a protective film or a spacer having a thickness, a good shape, excellent adhesion and high hardness can be obtained.

[(3) Step of developing the coating film irradiated with radiation in step (2)]
Next, by developing the film after irradiation, unnecessary portions are removed to form a predetermined pattern.

  As the developer used for development, for example, an inorganic alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate, or an aqueous solution of an alkaline compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide is used. it can. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.

  The developing method may be any of a liquid filling method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[(4) Step of baking the coating film developed in step (3)]
Next, the obtained patterned film is baked (post-baked) with a suitable heating device such as a hot plate or oven to obtain a cured film. As baking temperature, 100 to 200 degreeC is preferable and 150 to 180 degreeC is more preferable. The firing time is preferably, for example, 5 minutes to 30 minutes on a hot plate and 30 minutes to 180 minutes in an oven. Since the radiation-sensitive resin composition contains the [D] compound as described above, it achieves low-temperature firing in this way and achieves both storage stability and sufficient resolution and radiation sensitivity. Therefore, the radiation-sensitive resin composition is suitably used as a material for forming a cured film such as a colored resist using a dye that is desired to be fired at a low temperature, an interlayer insulating film used in flexible displays, a protective film, and a spacer. .

<Display element>
A display element provided with the cured film is also preferably included in the present invention. The display element of the present invention can be produced, for example, by the following method.

  First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is used on the transparent conductive film of one of the substrates according to the method described above. A spacer or a protective film or both are formed. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as described above. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly to this Example.

In the following synthesis examples, the weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Apparatus: GPC-101 (Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran

<Synthesis of [A] Compound>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 38 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and 20 parts by weight of glycidyl methacrylate were charged. After nitrogen substitution, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 4 hours to obtain a solution containing the copolymer (A-1) ( Solid content concentration = 34.4% by mass, Mw = 8,000, Mw / Mn = 2.3). In addition, solid content concentration means the ratio of the copolymer mass which occupies for the total mass of a copolymer solution.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by weight of methacrylic acid, 30 parts by weight of n-lauryl methacrylate, 20 parts by weight of glycidyl methacrylate and 30 parts by weight of styrene were charged, and after nitrogen substitution, the temperature of the solution was raised to 70 ° C. while gently stirring. By polymerizing while maintaining this temperature for 5 hours, a solution containing the copolymer (A-2) was obtained (solid content concentration = 31.9% by mass, Mw = 8,000, Mw / Mn = 2). .3).

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by mass of methacrylic acid, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decyl methacrylate, 5 parts by mass of styrene, and 50 parts by mass of glycidyl methacrylate were charged, purged with nitrogen, and then gently stirred. While the temperature of the solution was raised to 70 ° C. and polymerization was carried out while maintaining this temperature for 5 hours, a solution containing the copolymer (A-3) was obtained (solid content concentration = 32.3 mass%). Mw = 8,000, Mw / Mn = 2.3).

<Preparation of radiation-sensitive resin composition>
[Examples 1 to 17 and Comparative Examples 1 to 4]
The types and amounts of [A] compound, [B] polymerizable compound, [C] polymerization initiator, and [D] compound shown in Table 1 were mixed, and [E] γ-glycidoxypropyltri was added as an adhesion assistant. Mixing 5 parts by mass of methoxysilane, 0.5 parts by mass of [F] surfactant (FTX-218, Neos), and 0.5 parts by mass of 4-methoxyphenol as a storage stabilizer, the solid content concentration is After adding propylene glycol monomethyl ether acetate (S-1) so that it might become 30 mass%, the radiation sensitive resin composition was prepared by filtering with a Millipore filter with a hole diameter of 0.5 micrometer. In addition, “-” in the column represents that the corresponding component was not used.

  Details of the [B] polymerizable compound, the [C] polymerization initiator, and the [D] compound constituting the radiation sensitive resin composition are shown below.

[A] Compound (A-4) novolak type epoxy resin (Epicoat 152, Japan Epoxy Resin Co., Ltd.)
(A-5) Novolac type epoxy resin (Epicoat 157S65, Japan Epoxy Resin Co., Ltd.)

[B] Polymerizable compound (B-1) Dipentaerythritol hexaacrylate (B-2) Mixture of polyfunctional acrylate compound (KAYARAD DPHA-40H, Nippon Kayaku Co., Ltd.)
(B-3) 1,9-nonanediol diacrylate (B-4) Aronix M-5300 (Toagosei Co., Ltd.)

[C] Polymerization initiator (C-1) Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, Ciba Specialty Chemicals)
(C-2) 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE01, Ciba Specialty Chemicals)
(C-3) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, Ciba Specialty Chemicals)
(C-4) 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379, Ciba Specialty Chemicals) )

[D] Compound (D-1) 4,4′-Diaminodiphenylsulfone (D-2) 2,2-bis (4-aminophenyl) hexafluoropropane (D-3) 2,2′-bis (trifluoro Methyl) benzidine (D-4) 3-aminobenzenesulfonate ethyl (D-5) 3,5-bistrifluoromethyl-1,2-diaminobenzene (D-6) 4-aminonitrobenzene (D-7) N, N-dimethyl-4-nitroaniline (d-1) 3,3′-dimethoxybenzidine

<Evaluation>
The following evaluation was performed about the radiation sensitive resin composition of Examples 1-17 and Comparative Examples 1-4. The results are shown in Table 2.

[resolution]
A radiation-sensitive resin composition solution was applied onto an alkali-free glass substrate with a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 4.0 μm. Next, the obtained film was irradiated with radiation at a dose of 700 J / m ² using a high-pressure mercury lamp through a photomask having a plurality of circular residual patterns with different sizes in the range of 6 μm to 15 μm in diameter. . Thereafter, development was performed by a puddle method using a 0.40 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. with a development time as a variable, and then washing with pure water was performed for 1 minute. Further, a patterned cured film was formed by post-baking in the oven at the firing temperature and firing time shown in Table 1 (hereinafter sometimes referred to as “cured film forming step”). At this time, when a pattern was formed on a photomask of 9 μm or less, it was judged that the resolution was good.

[Sensitivity (J / m ² )]
A round residue pattern was formed on the substrate in the same manner as in the cured film formation step except that a photomask having a plurality of round residue patterns having a diameter of 15 μm was used and the exposure amount was varied.
The height of the circular residual pattern before and after development was measured using a laser microscope (VK-8500, Keyence Corporation). The residual film ratio (%) was determined from this value and the following formula.
Residual film ratio (%) = (height after development / height before development) × 100
The exposure amount at which the remaining film ratio was 90% or more was defined as sensitivity. When the exposure amount was 750 J / m ² or less, it was judged that the sensitivity was good.

[Storage stability (%)]
By operating in the same manner as the above-mentioned “resolution”, a cured film of the radiation-sensitive resin composition solution immediately after preparation was formed and the film thickness was measured (in the following formula, referred to as “film thickness immediately after preparation”). Moreover, the radiation sensitive resin composition solution was preserve | saved at 25 degreeC for 5 days, and the film thickness of the cured film formed similarly after 5 days was measured (in the following formula, it calls "the film thickness after 5 days"). The film thickness increase rate (%) was calculated from the following formula.
Film thickness increase rate (%) = (film thickness after 5 days−film thickness immediately after preparation) / (film thickness immediately after preparation) × 100
When the film thickness increase rate was 3% or less, it was judged that the storage stability was good.

[Light resistance (%)]
In the cured film forming step, the film obtained by exposing at a dose of 700 J / m ² without passing through a photomask and post-baking in an oven at 180 ° C. for 60 minutes is further applied to a UV irradiation device (UVX -02516S1JS01, Ushio Inc.) was irradiated with 800,000 J / m ² at an illuminance of 130 mW, and it was judged good if the film reduction amount was 2% or less.

[Heat-resistant(%)]
In the above cured film forming step, the film obtained by exposure at an exposure amount of 700 J / m ² without using a photomask and post-baking at 180 ° C. for 60 minutes in an oven, and further at 230 ° C. in an oven. The film thickness before and after heating for 20 minutes was measured with a stylus type film thickness measuring machine (Alpha step IQ, KLA Tencor), and the remaining film ratio (film thickness after treatment / film thickness before treatment × 100) was calculated, This remaining film rate was defined as heat resistance.

[chemical resistance(%)]
In the above-described cured film forming step, the film obtained by exposing with an exposure amount of 700 J / m ² without passing through a photomask and post-baking in an oven at 180 ° C. for 60 minutes, was heated to 60 ° C. It was immersed for 15 minutes in a membrane peeling solution Chemiclean TS-204 (Sanyo Kasei Kogyo Co., Ltd.), washed with water, and further dried in an oven at 120 ° C. for 15 minutes. The film thickness before and after this treatment was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor), and the remaining film ratio (film thickness after treatment / film thickness before treatment × 100) was calculated. The film rate was defined as chemical resistance.

[Transmissivity (%)]
In the above cured film forming step, exposure was performed at an exposure amount of 700 J / m ² without passing through a photomask, and the film obtained by post-baking at 180 ° C. for 60 minutes in an oven was obtained. The transmittance at 400 nm was measured using a spectrophotometer (150-20 type double beam, Hitachi, Ltd.). At this time, when the transmittance was less than 90%, the transparency was regarded as poor.

[Flatness (nm)]
Using a pigment-based color resist (JCR RED 689, JCR GREEN 706 and CR 8200B, JSR) on a SiO ₂ dip glass substrate, the following three stripe color filters of red, green and blue are used. Formed. Specifically, one color of the color resist was applied to a SiO ₂ dip glass substrate using a spinner, and pre-baked on a hot plate at 90 ° C. for 150 seconds to form a film. Thereafter, using an exposure machine (Canon PLA501F, Canon Inc.), the ghi line (intensity ratio of wavelengths 436 nm, 405 nm, 365 nm = 2.7: 2.5: 4.8) is passed through the predetermined pattern mask. Irradiation was performed at an exposure amount of 2,000 J / m ^{2 in} terms of conversion, followed by development using a 0.05 mass% aqueous potassium hydroxide solution and rinsing with ultrapure water for 60 seconds. Subsequently, a heat treatment was further performed in an oven at 230 ° C. for 30 minutes to form a single-color striped color filter. By repeating this operation for three colors, a striped color filter (stripe width 200 μm) of three colors of red, green and blue was formed.
Measurement length 2,000μm, measurement range 2,000μm square, measurement direction is red, green, blue stripe line minor axis direction and red / red, green / green, blue / blue same color stripe line major axis direction Measure unevenness on the surface of the color filter substrate with a contact-type film thickness measuring device (Alpha-Step, KLA-Tencor Corporation) with two directions and the number of measurement points n = 5 (total n number is 10) in each direction. As a result, it was 1.0 μm. Each thermosetting resin composition was applied to the substrate on which the color filter was formed with a spinner, then pre-baked on a hot plate at 90 ° C. for 5 minutes to form a cured film, and further in a clean oven. Then, a protective film having a thickness of about 2.0 μm from the upper surface of the color filter was formed by post-baking at the baking temperature and baking time shown in Table 1.
With respect to the substrate having the protective film on the color filter formed in this manner, the unevenness of the surface of the protective film was measured with a contact-type film thickness measuring device (Alpha-Step, KLA Tencor). This measurement has a measuring length of 2,000 μm, a measuring range of 2,000 μm square, measuring directions of red, green, blue stripe lines and minor axis directions, and red / red, green / green, blue / blue stripe lines of the same color. Two major axis directions are used, and the number of measurement points is n = 5 (total n number is 10) in each direction, and the average value of 10 times of the height difference (nm) between the highest part and the lowest part of each measurement is obtained. The planarization ability (flatness) of the protective film was evaluated. When this value was 210 nm or less, it was judged that the planarization ability of the protective film was good.

[Voltage holding ratio (%)]
After spin-coating the radiation-sensitive resin composition on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape And prebaking for 10 minutes in a clean oven at 90 ° C. to form a film having a thickness of 2.0 μm. Next, the film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 mass% aqueous potassium hydroxide solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and fired as shown in Table 1. Post-baking was performed at the temperature and the baking time, and the coating was cured to form a permanent cured film. Next, the substrate on which this pixel is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal (MLC6608) is injected. A liquid crystal cell was produced. Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (VHR-1A type, Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing “burn-in”.

  From the results of Table 2, it was found that the radiation sensitive resin compositions of Examples 1 to 17 had better resolution, storage stability and radiation sensitivity than the compositions of Comparative Examples 1 to 4. Moreover, although the cured film formed from the said radiation sensitive resin composition of Examples 1-17 was formed by low-temperature baking of 200 degrees C or less, light resistance, heat resistance, chemical resistance, transmittance | permeability, It was found that the flatness was excellent. Furthermore, the voltage holding ratio of the display element having the cured film was also good.

  The radiation-sensitive resin composition of the present invention can easily form a fine and elaborate pattern, achieves both storage stability and low-temperature firing, and has sufficient resolution and radiation sensitivity. Moreover, the cured film formed from the said radiation sensitive resin composition is excellent in the required characteristics, such as heat resistance, light resistance, chemical resistance, transmittance, flatness, and voltage holding ratio. Therefore, the radiation-sensitive resin composition is suitably used as a material for forming a cured film such as a colored resist using a dye desired to be fired at a low temperature, an interlayer insulating film used for a flexible display, a protective film, a spacer, and the like.

Claims (7)

[A] a compound having an epoxy group and a carboxyl group ,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] a radiation-sensitive polymerization initiator, and [D] a radiation-sensitive resin composition containing at least one selected from the group consisting of compounds represented by the following formulas (1) and (2).

(In formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group, provided that at least one of R ^{1 to} R ⁶ is an electron withdrawing group. , At least one of R ^{1 to} R ⁶ is an amino group, and in the amino group, all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms.
In formula (2), R ^{7 to} R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group, or an amino group. However, at least one of R ^{7 to} R ¹⁶ is an amino group. In the amino group, all or part of the hydrogen atoms may be substituted with an alkyl group having 2 to 6 carbon atoms. A is a single bond, mosquitoes Ruboniruokishi group, carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. However, the methylene group and alkylene group may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. )   The radiation sensitive resin composition according to claim 1, wherein the compound [A] is a polymer. The radiation sensitive resin composition of Claim 1 or Claim 2 used for formation of the cured film as an interlayer insulation film, a protective film, or a spacer. (1) The process of forming the coating film of the radiation sensitive resin composition of Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming a cured film, comprising: a step of developing the coating film irradiated with radiation in step (2); and (4) a step of baking the coating film developed in step (3). The method for forming a cured film according to claim 4 , wherein the firing temperature in the step (4) is 200 ° C. or lower. A cured film as an interlayer insulating film, protective film or spacer formed from the radiation-sensitive resin composition according to claim 3 . A display element provided with the cured film of Claim 6 .