JP2013200431A - Radiation-sensitive resin composition, cured film and formation method of cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having both storage stability and low-temperature curability and sufficient pattern forming capability; a cured film being formed using such a radiation-sensitive resin composition and being excellent in demand characteristics such as heat resistance and compression characteristics; and a formation method of such a cured film.SOLUTION: A radiation-sensitive resin composition contains [A] an alkali-soluble resin, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator and [D] a compound represented by the formula (1), where the [A] alkali-soluble resin has an epoxy group or further contains [E] an epoxy compound.

Description

  The present invention relates to a radiation-sensitive resin composition, a cured film formed from the composition, and a method for forming the cured film.

  Flexible displays such as electronic paper are widely used. As a substrate for this flexible display, a plastic substrate such as polyethylene terephthalate has been studied. This substrate stretches / shrinks when heated, and has a disadvantage of hindering the function as a display, and therefore, it is necessary to lower the temperature of the cured film baking process.

  On the other hand, as a cured film forming material having pattern forming ability, for example, a radiation sensitive resin composition containing an epoxy copolymer composed of an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound or the like is widely used. (See JP 2001-354822 A). However, when these radiation-sensitive resin compositions are used, a baking step at a high temperature of 200 ° C. or higher is required to increase the surface hardness to a level that is actually required as a cured film.

  In view of this, a method of proceeding the crosslinking reaction even at low temperatures by adding amine compounds such as primary amines, secondary amines, and imidazoles, which are used as curing agents for epoxy materials, has been studied. However, since a conventional amine compound causes a reaction with time with an epoxy group present in the composition, the composition containing such a conventional amine compound has insufficient storage stability. In addition, imidazoles have excellent storage stability, but their low-temperature curability is insufficient.

  In addition, the technique of the coating liquid for gate insulating films of the flexible display containing the polyimide precursor excellent in the low temperature curability which can be hardened even if it is low-temperature baking is developed (refer Unexamined-Japanese-Patent No. 2009-4394). 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, the cured film obtained is not at a satisfactory level in heat resistance, compression characteristics, solvent resistance, strength, voltage holding ratio, etc., due to insufficient progress of the curing reaction.

JP 2001-354822 A JP 2009-4394 A

  The present invention has been made on the basis of the circumstances as described above, and the object thereof is a radiation-sensitive resin composition having both sufficient storage stability and low-temperature curability and sufficient pattern forming ability, such as It is an object of the present invention to provide a cured film formed using a radiation-sensitive resin composition and excellent in required characteristics such as heat resistance and compression characteristics, and a method for forming such a cured film.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、炭素数１〜２０のアルキル基、炭素数６〜１８のアリール基又は炭素数７〜３０のアラルキル基である。但し、上記アルキル基、アリール基及びアラルキル基が有する水素原子の一部又は全部は、アミノ基及び水酸基からなる群より選択される少なくとも１種で置換されていてもよい。また、Ｒ^１及びＲ^２は、互いに結合して、それらが結合する窒素原子と共に環状構造を形成していてもよい。Ｒ^３は、炭素数４〜２０の窒素含有複素環基である。Ｗは、単結合又は炭素数１〜１２のアルカンジイル基である。） The invention made to solve the above problems is
[A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter also referred to as “[B] polymerizable compound”),
[C] a radiation sensitive polymerization initiator, and [D] a compound represented by the following formula (1) (hereinafter also referred to as “(D) compound”):
Containing
[A] A radiation-sensitive resin composition in which the alkali-soluble resin has an epoxy group or further contains an [E] epoxy compound.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. However, some or all of the hydrogen atoms of the alkyl group, aryl group and aralkyl group may be substituted with at least one selected from the group consisting of an amino group and a hydroxyl group, and R ¹ and R ² may be bonded to each other to form a cyclic structure together with the nitrogen atom to which they are bonded, R ³ is a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, W is a single bond or (It is an alkanediyl group having 1 to 12 carbon atoms.)

  The said radiation sensitive resin composition can form a fine and elaborate pattern easily by exposure and image development using radiation sensitivity. Moreover, the said radiation sensitive resin composition can improve the required characteristics of cured films, such as solvent resistance, even if it is a case of a low exposure amount by containing a [C] radiation sensitive polymerization initiator. Furthermore, since the radiation-sensitive resin composition has [A] the alkali-soluble resin has an epoxy group or further contains an [E] epoxy compound, the epoxy group and the [D] having the above specific structure having an amino group. The compound reacts to accelerate the curing reaction. In particular, since the [D] compound has an amino group on the heterocyclic ring, the curing reaction does not proceed during storage even if it coexists with a component having an epoxy group, and the radiation-sensitive resin composition is stored. Excellent stability. As a result, the radiation sensitive resin composition can achieve both low temperature curability and storage stability at a high level.

  [A] The alkali-soluble resin comprises (A1) one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter also referred to as “(A1) compounds”), and (A2 ) A copolymer obtained by copolymerizing an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”) is preferable.

  [A] Since the alkali-soluble resin is a copolymer of the compound (A1) and the compound (A2), it contains a carboxyl group and an epoxy group. Thus, the radiation-sensitive resin composition can make the curing acceleration effect of the [D] compound more effective because the [A] alkali-soluble resin has a carboxyl group and an epoxy group. Thus, the solvent resistance and the like of the obtained cured film can be improved.

In the above formula (1), the nitrogen-containing heterocyclic group represented by R ³ is preferably at least one group selected from the group consisting of a pyridyl group, a pyrazyl group, a pyrimidyl group, and a benzimidazole group. The said radiation sensitive resin composition can improve storage stability and low-temperature curability more because a [D] compound contains the said specific group.

  [D] Compounds include 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 2- (methyl Amino) pyridine, 3- (methylamino) pyridine, 4- (methylamino) pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine, 4- (4-aminopiperidino) pyridine, 2-aminopyrazine, 4-aminopyrimidine And at least one compound selected from the group consisting of 2-aminobenzimidazole is preferred. The radiation-sensitive resin composition can further improve storage stability and low-temperature curability by using the [D] compound as the specific compound.

  [A] The content of the [D] compound with respect to 100 parts by mass of the alkali-soluble resin is preferably 0.01 parts by mass or more and 10 parts by mass or less. The said radiation sensitive resin composition can make storage stability and low temperature curability highly compatible by making content of a [D] compound into the said range.

  The said radiation sensitive resin composition is suitable for the cured film formation as an interlayer insulation film, a protective film, or a spacer. Further, the present invention suitably includes a cured film as an interlayer insulating film, a protective film or a spacer. A cured film as an interlayer insulating film, protective film or spacer formed from the radiation-sensitive resin composition is excellent in heat resistance, solvent resistance, hardness, and the like.

The method for forming the cured film of the present invention is as follows.
(1) The process of forming a coating film using the radiation sensitive resin composition of this invention,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of baking the developed coating film.

  Since the said formation method uses the said radiation sensitive resin composition, the cured film in which characteristics, such as heat resistance, solvent resistance, and hardness, were improved with sufficient balance can be manufactured.

  As temperature in baking of the said process (4), 200 degrees C or less is preferable. Since the radiation sensitive resin composition contains the [D] compound as a curing accelerator as described above, firing at such a low temperature can be realized.

  Here, “baking” means heating until a surface hardness required for a cured film such as an interlayer insulating film, a protective film, or 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 is highly compatible with storage stability and low-temperature curability and has sufficient pattern forming ability. Moreover, the cured film formed using the said radiation sensitive resin composition has characteristics, such as outstanding heat resistance, a compression characteristic, solvent resistance, hardness, and voltage retention. Therefore, the radiation sensitive resin composition is suitably used as a material for forming an interlayer insulating film, a protective film, a spacer and the like used for a flexible display or the like where low temperature baking is desired.

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

<Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention contains [A] an alkali-soluble resin, [B] a polymerizable compound, [C] a radiation-sensitive polymerization initiator, and a [D] compound, and if necessary, [E]. Contains an epoxy compound. Furthermore, you may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] alkali-soluble resin>
[A] The alkali-soluble resin is not particularly limited as long as it is an alkali-soluble resin, but from the viewpoint of having sufficient alkali solubility, a polymer obtained by polymerizing a monomer compound containing at least the compound (A1) It is preferable that

  When the said radiation sensitive resin composition does not contain an [E] epoxy compound, [A] alkali-soluble resin needs to have an epoxy group, As such [A] alkali-soluble resin, A copolymer obtained by copolymerizing the compound (A1) and the compound (A2) is more preferable. Such a copolymer of the compound (A1) and the compound (A2) is obtained from the radiation-sensitive resin composition because the copolymer includes a structural unit having a carboxyl group and a structural unit having an epoxy group in the molecule. The cured film can improve characteristics such as solvent resistance and hardness. Furthermore, the low temperature curability of the radiation sensitive resin composition can be improved by the [D] compound acting on the epoxy group of the structural unit derived from the compound (A2). In the production of [A] alkali-soluble resin, together with the (A1) compound and the (A2) compound, an unsaturated compound other than the above (A1) and (A2) may be copolymerized as the (A3) compound.

  When the said radiation sensitive resin composition contains an [E] epoxy compound, as [A] alkali-soluble resin, the copolymer obtained by copolymerizing the said (A3) compound and (A1) compound More preferably, it is a coalescence. Moreover, even if the said radiation sensitive resin composition contains a [E] epoxy compound, you may use the alkali-soluble resin which has the above epoxy groups as [A] alkali-soluble resin. In addition, each compound may use 2 or more types together. Hereinafter, each compound will be described in detail.

[(A1) Compound]
The compound (A1) is at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. (A1) As the compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carboxylic acid, carboxyl group and hydroxyl group at both ends And mono (meth) acrylates of polymers having an unsaturated polycyclic compound having a carboxyl group and anhydrides thereof.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid, etc. are mentioned, for example. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like. . Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate. Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept. 2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy -6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2 .1] hept-2-ene anhydride and the like.

  Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.

  [A] The content ratio of the structural unit derived from the compound (A1) in the alkali-soluble resin is preferably 5 mol% to 30 mol%, more preferably 10 mol% to 30 mol%, based on all structural units. is there. (A1) Radiation sensitivity that optimizes the solubility of the alkali-soluble resin in an alkaline aqueous solution and has excellent sensitivity and developability by setting the content of the structural unit derived from the compound to 5 mol% to 30 mol%. A functional resin composition is obtained.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound and has radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid 3,4. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl Examples thereof include benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like.

Examples of unsaturated compounds having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (acryloyl). Oxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2 -Difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) ) Oxetane, 3- ( 2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyl) Oxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxy) Ethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane and other acrylic acid esters;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) -2- Pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2 , 4-trifluorooxetane, methacrylic acid esters such as 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, and the like.

  Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate are copolymerized. It is preferable from the viewpoint of improving the reactivity and curability of the resin composition.

  [A] The content ratio of the structural unit derived from the compound (A2) in the alkali-soluble resin is preferably 5% by mass to 35% by mass, and more preferably 10% by mass to 30% by mass with respect to all the structural units. is there. [A] By setting the proportion of the structural unit derived from the compound (A2) in the alkali-soluble resin to 5% by mass to 35% by mass, a cured product having excellent solvent resistance, hardness and the like can be formed.

[(A3) Compound]
The compound (A3) is not particularly limited as long as it is an unsaturated compound having radical polymerizability other than the compounds (A1) and (A2) described above. Examples of the compound (A3) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound having a skeleton represented by the following formula (2), the following formula (3 The phenolic hydroxyl group-containing unsaturated compound represented by) and other unsaturated compounds.

（式（２）中、Ｒ^４は水素原子又はメチル基である。ｍは１以上の整数である。）

(In Formula (2), R ⁴ is a hydrogen atom or a methyl group. M is an integer of 1 or more.)

（式（３）中、Ｒ^５は水素原子又は炭素数１〜４のアルキル基である。Ｒ^６〜Ｒ^１０はそれぞれ独立して、水素原子、ヒドロキシル基又は炭素数１〜４のアルキル基である。Ｙは単結合、−ＣＯＯ−又は−ＣＯＮＨ−である。ｐは０〜３の整数である。但し、Ｒ^６〜Ｒ^１０の少なくとも１つはヒドロキシル基である。）

(In the formula (3), ^{R 5} is ^.R 6 ^{to R 10} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms Y is a single bond, —COO— or —CONH—, p is an integer of 0 to 3, provided that at least one of R ^{6 to} R ¹⁰ is a hydroxyl group.

  Examples of the methacrylic acid chain alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n -Stearyl methacrylate etc. are mentioned.

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and tricyclo [5.2.1.0 ^2,6. ] Decan-8-yloxyethyl methacrylate, isobornyl methacrylate and the like.

  Examples of the methacrylic acid ester having a hydroxyl group include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, and 2-methacryloxyethylglycol. Side, 4-hydroxyphenyl methacrylate and the like.

Examples of acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2.1.0 ^2,6. ] Decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

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

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

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2 2.1] Hept- -Ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 ′ -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2. 2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 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.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene- 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, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc. Is mentioned.

  Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one , 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like.

  Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa-6-oxo. -7-octenyl) -6-methyl-2-pyran and the like.

  Examples of the unsaturated compound containing a skeleton represented by the above formula (2) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, and the like. Is mentioned.

（式（４）中、ｑは１〜３の整数である。Ｒ^５〜Ｒ^１０は上記式（３）と同義である。） Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3) include compounds represented by the following formulas (4) to (8) according to the definitions of Y and p.

(In the formula (4), q is ^.R 5 ^{to R 10} is an integer of 1 to 3 as defined in the above formula (3).)

（式（５）中、Ｒ^５〜Ｒ^１０は上記式（３）と同義である。）

(In the formula ^{(5), R} 5 ~R ¹⁰ has the same meaning as the above formula (3).)

（式（６）中、ｒは１〜３の整数である。Ｒ^５〜Ｒ^１０は上記式（３）と同義である。）

(In the formula (6), r is ^.R 5 ^{to R 10} is an integer of 1 to 3 as defined in the above formula (3).)

（式（７）中、Ｒ^５〜Ｒ^１０は上記式（３）と同義である。）

(In the formula ^{(7), R} 5 ~R ¹⁰ has the same meaning as the above formula (3).)

（式（８）中、Ｒ^５〜Ｒ^１０は上記式（３）と同義である。）

(In the formula ^{(8), R} 5 ~R ¹⁰ has the same meaning as the above formula (3).)

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A3) compounds, it has a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a skeleton represented by the above formula (2). An unsaturated compound, a phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3), an unsaturated aromatic compound, and an acrylic acid cyclic alkyl ester are preferred. Of these, styrene, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide , N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are more preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution.

  [A] The content ratio of the structural unit derived from the compound (A3) in the alkali-soluble resin is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass with respect to the total structural units. is there. [A] By setting the content of the structural unit derived from the compound (A3) in the alkali-soluble resin to 10% by mass to 80% by mass, the radiation-sensitive resin composition has developability and a cured product formed. Excellent solvent resistance.

[A] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2 × 10 ³ to 1 × 10 ^{5, and} more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . [A] By setting Mw of the alkali-soluble resin to 2 × 10 ³ to 1 × 10 ⁵ , the radiation sensitivity and developability of the radiation-sensitive resin composition can be improved. In addition, Mw and number average molecular weight (Mn) of the polymer in this specification were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Method for synthesizing alkali-soluble resin>
[A] The alkali-soluble resin can be produced, for example, by polymerizing monomers corresponding to predetermined respective structural units in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  [A] Solvents used in the polymerization reaction for producing the alkali-soluble resin include, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol mono Examples include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketones, and esters.

Examples of the alcohol include benzyl alcohol;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of the ethylene glycol alkyl ether acetate include ethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate;
Examples of the diethylene glycol monoalkyl ether include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Examples of the diethylene glycol dialkyl ether include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of the dipropylene glycol dialkyl ether include dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;
Examples of the propylene glycol monoalkyl ether include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether;
Examples of the propylene glycol alkyl ether acetate include propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate;
Examples of the propylene glycol monoalkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and the like;
Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone;
Examples of the ester include ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, butyl hydroxyacetate, methyl lactate, ethyl lactate, Propyl lactate, butyl lactate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2- Butyl propionate butyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate 3-ethoxy propionate propyl, 3-ethoxy propionate butyl, 3-propoxy-propionic acid methyl, and the like.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferred, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate is more preferred.

  [A] As the polymerization initiator used in the polymerization reaction for producing the alkali-soluble resin, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane and peroxides Examples include hydrogen oxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  [A] In the polymerization reaction for producing the alkali-soluble resin, 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, and thioglycolic acid; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

  Although the reaction temperature in the said polymerization should just be suitably determined according to the kind of radical polymerization initiator, it is 40 to 150 degreeC normally, and 50 to 120 degreeC is preferable. The reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.

<[B] Polymerizable compound>
[B] The polymerizable compound contained in the radiation-sensitive resin composition is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example, ω-carboxypolycaprolactone mono (meth) acrylate, Ethylene glycol (meth) acrylate, 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 tricyclodecane di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2′-vinylo) Ciethoxy) 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) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, and the like, and a linear alkylene group and an alicyclic structure, and Ureta obtained by reacting a compound having two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having 3 to 5 (meth) acryloyloxy groups (Meth) acrylate compounds, and the like.

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, KAYARAD DPEA-12, HUX-5000 (above, 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] alkali-soluble resin, and 40 mass parts-160 mass parts. Is more preferable. [B] By making the content rate of a polymeric compound into the said range, the said radiation sensitive resin composition is excellent in adhesiveness, and cured films, such as a spacer with sufficient hardness even in the low exposure amount, are obtained.

<[C] Radiation sensitive polymerization initiator>
The [C] radiation-sensitive polymerization initiator contained in the composition is a component that generates an active species capable of initiating polymerization of the [B] polymerizable compound in response to radiation. Examples of such [C] radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. In addition, [C] a radiation sensitive polymerization initiator may use 2 or more types together.

  Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9- Ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-oneoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- Ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1 -[9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 -(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Of these, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6 -(2-Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-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, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like can be mentioned.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl). ) -1- (4-Morpholin-4-yl-phenyl) -butan-1-one is more preferred.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′. -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi Examples include imidazole. Among these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred, and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is more preferred.

  [C] As the radiation-sensitive polymerization initiator, a commercially available product may be used. For example, 2-methyl-1- (4-methylthiophenyl))-2-morpholinopropan-1-one (Irgacure 907, 2 -(4-Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379), ethanone-1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02) (above, Ciba Specialty Chemicals).

  As a content rate of the [C] radiation sensitive polymerization initiator in the said radiation sensitive resin composition, 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 5 mass parts- 30 parts by mass is more preferable. [C] By making the content rate of a radiation sensitive polymerization initiator into 1 mass part-40 mass parts, the said composition can form the cured film which has high hardness etc., even in the case of a low exposure amount.

<[D] Compound>
The radiation-sensitive resin composition containing a component having an epoxy group can achieve both storage stability and curing acceleration (low-temperature curability) in low-temperature firing at a high level by containing the [D] compound. When a normal primary amine compound or secondary amine compound coexists with a component having an epoxy group, a curing reaction proceeds by nucleophilic attack on the epoxy group of the amine during storage of the composition solution, and the quality as a product is improved. There is a risk of damage. However, since the [D] compound used in the present invention has an amino group on the heterocyclic ring, the curing reaction does not proceed even if it coexists with a component having an epoxy group in the composition, and the storage stability is excellent. Only when the coating film made of the radiation-sensitive resin composition is heated can it sufficiently function as a curing catalyst.

The compound [D] is represented by the above formula (1). In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. . However, some or all of the hydrogen atoms of the alkyl group, aryl group and aralkyl group may be substituted with at least one selected from the group consisting of an amino group and a hydroxyl group. However, R ¹ and R ² may be bonded to each other to form a cyclic structure together with the nitrogen atom to which they are bonded. R ³ is a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms. W is a single bond or an alkanediyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include, for example, a linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and heptyl group. Octyl, nonyl, decyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

  Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group and a naphthyl group.

  Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group and a phenethyl group.

The nitrogen-containing heterocyclic group having 3 to 20 carbon atoms represented by R ³ is not particularly limited as long as it is a heterocyclic group having the above-mentioned carbon number containing a nitrogen atom as a hetero atom, but a pyridyl group, a pyrazyl group, and a pyrimidyl group. Groups and benzimidazole groups are preferred. When R ³ is the specific group, the radiation-sensitive resin composition can achieve both storage stability and low-temperature curability in hardness.

[D] As the compound, a compound in which R ³ in Formula (1) is a pyridyl group, a pyrazyl group, a pyrimidyl group or a benzimidazole group is preferable, and 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 3- Aminomethylpyridine, 4-aminomethylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 2- (methylamino) pyridine, 3- (methylamino) pyridine, 4- (methylamino) pyridine, 4-dimethylamino More preferably, it is pyridine, 4-pyrrolidylpyridine, 4- (4-aminopiperidino) pyridine, 2-aminopyrazine, 4-aminopyrimidine, 2-aminobenzimidazole, 4-aminopyridine, 4-dimethylaminopyridine, 2-aminobenzimidazole, 3-aminomethylpyri More preferred are gin and 4-aminomethylpyridine. In addition, a [D] compound can be used individually or in mixture of 2 or more types.

  Since the function of the above [D] compound as a curing accelerator varies depending on the firing temperature, the above [D] compound is appropriately selected according to the type of the cured film to be formed, and one type suitable for the purpose is used alone. Alternatively, it is possible to control the characteristics such as the molecular weight of the resin by using a mixture of two or more. From such a viewpoint, for example, the radiation-sensitive resin composition using 4-aminomethylpyridine as a [D] compound, which is excellent in curing accelerating capability at low temperatures but slightly decreases in accelerating curing capability at high temperatures, It is preferable to perform firing in combination because the properties such as hardness of the obtained cured film can be controlled. Moreover, the radiation sensitive resin composition which mixed 4-aminopyridine with high hardening acceleration ability at low temperature and high temperature, said 4-aminomethylpyridine, etc. and was used as a [D] compound is preferable from the same viewpoint.

  As a content rate of the [D] compound in the said radiation sensitive resin composition, 0.01 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, 0.05 mass part-8 Part by mass is more preferable. [D] By making the content rate of a compound into 0.01 mass part-10 mass parts, the storage stability and low-temperature curability of the said radiation sensitive resin composition can be made compatible at a higher level.

<[E] epoxy compound>
[A] When the monomer having an epoxy group is not used as a copolymerization component in the alkali-soluble resin, it is necessary to use the following [E] epoxy compound. The radiation-sensitive resin composition can cause a curing reaction to proceed under heating or radiation irradiation by nucleophilic attack of the [D] compound on the [E] epoxy compound. As a result, it becomes insoluble in an alkali developer, and exhibits a negative negative radiation sensitivity. In the present invention, the epoxy group has a cyclic ether structure, and examples thereof include an oxiranyl group and an oxetanyl group.

  Examples of the compound having one epoxy group in the molecule include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic. 3,4-epoxybutyl acid, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzylglycidyl ether , M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, phenyl glycidyl ether, γ -Glycidoxypropyltrimethoxysilane, β- 3,4-epoxycyclohexyl) ethyltrimethoxysilane, .gamma.-glycidoxypropyl diethoxy silane, and the like.

Examples of the compound having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, water Bisphenol-type diglycidyl ethers such as bisphenol AD 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 ethers;
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;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers;
Examples include epoxidized soybean oil and epoxidized linseed oil.

Commercially available compounds having two or more epoxy groups in the molecule include, for example, bisphenol A novolak type epoxy resins such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 ( Above, made of Japan Epoxy Resin) etc .;
As bisphenol F type epoxy resin, Epicoat 807 (manufactured by Japan Epoxy Resin) and the like;
As a phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 (above, made by Japan Epoxy Resin), EPPN201, 202 (above, made by Nippon Kayaku), etc .;
As cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Japan Epoxy Resin) and the like;
As a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (made by Japan Epoxy Resin) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by 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 (Celanese coating)
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and Epiol TMP (manufactured by NOF Corporation).

  [E] The amount of the epoxy compound 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 [A] alkali-soluble resin. When the usage-amount of an epoxy compound exceeds 50 mass parts, the sensitivity of the said radiation sensitive resin composition may fall and a pattern shape may deteriorate.

<Optional component>
In addition to the above [A] alkali-soluble resin, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, [D] compound and [E] epoxy compound, the radiation sensitive resin composition is the present invention. In the range which does not impair the effect, optional components such as an adhesion assistant, a surfactant and a storage stabilizer can be contained as necessary. Each of these optional components may be used alone or in combination of two or more. Hereinafter, it explains in full detail in order.

[Adhesion aid]
The adhesion assistant can be used to further improve the adhesion between the obtained spacer or the like and the substrate. As such an 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, or an oxiranyl group is preferable. For example, trimethoxysilylbenzoic acid, γ-methacrylic acid is used. Roxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Is mentioned.

  The amount of the adhesion aid 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 [A] alkali-soluble resin. When the amount of the adhesion aid used exceeds 20 parts by mass, there is a tendency that development residue tends to occur.

[Surfactant]
A surfactant can be used to further improve the film-forming property of the composition. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, 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.).

  As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.8 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it will become easy to produce a film | membrane nonuniformity.

[Storage stabilizer]
Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. Is mentioned.

  As a usage-amount of a storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1.0 mass part or less is more preferable. When the amount of the storage stabilizer exceeds 3.0 parts by mass, the sensitivity of the radiation-sensitive resin composition may decrease and the pattern shape may deteriorate.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is added to [A] alkali-soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator and [D] compound, and [E] epoxy compound added as necessary. It is prepared by mixing other optional components at a predetermined ratio. This radiation-sensitive resin composition is preferably used in a solution state after being dissolved in an appropriate solvent.

  Solvents used for the preparation of the radiation sensitive resin composition include [A] alkali-soluble resin, [B] polymerizable compound, [C] radiation sensitive polymerization initiator, [D] compound, and [E] epoxy compound. In addition, an arbitrary component that is uniformly dissolved or dispersed and does not react with each component is 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] alkali-soluble resin 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 mono, from the viewpoint of solubility of each component, reactivity with each component, ease of coating formation, etc. Butyl ether 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 above 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 ratio of the resulting coating film are good.

  When preparing the said radiation sensitive resin composition in a solution state, solid content concentration (components other than the solvent which occupies in a composition solution) is 5 mass%, for example according to the intended purpose or the value of desired film thickness. It can be set to any concentration such as ˜50 mass%. A more preferable solid content concentration varies depending on a method of forming a coating film on a substrate, but this 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>
The said radiation sensitive resin composition is used suitably for formation of the cured film as an interlayer insulation film, a protective film, or a spacer. Further, the present invention suitably includes a cured film as an interlayer insulating film, a protective film or a spacer formed using the radiation sensitive resin composition. These interlayer insulating films, cured films as protective films or spacers are excellent in heat resistance, compression characteristics, solvent resistance, voltage holding ratio and hardness.

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

  According to the forming method of the present invention, it is possible to form a cured film such as a spacer having improved properties such as heat resistance, solvent resistance, and voltage holding ratio in a well-balanced manner. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a coating 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.

  When a coating film is formed by a coating method, the coating film is preferably formed by heating (pre-baking) the coated surface after coating the solution of the radiation sensitive resin composition on the transparent conductive film. Can do. 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 further more preferable. As a coating method of the radiation sensitive resin composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, an ink jet coating method, etc. This 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 film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.

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

  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 thickness, good shape, and high hardness even when the radiation dose is 850 J / m ² or less. The cured film can be obtained.

[Step (3)]
In this step, the coated film after irradiation is developed to remove unnecessary portions and form a predetermined pattern. Examples of the developer used for development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. It is done. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may 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.

[Step (4)]
In this step, the cured film is obtained by baking (post-baking) the obtained patterned coating film with a suitable heating device such as a hot plate or oven. As baking temperature, 60 to 200 degreeC is preferable, 80 to 190 degreeC is more preferable, and 100 to 180 degreeC is further more preferable. The firing time is preferably, for example, 2 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 can realize low-temperature baking for such a short time, and therefore, as a forming material for spacers used in flexible displays and the like where low-temperature baking is desired. Is preferred.

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

<[A] Synthesis of alkali-soluble resin>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate, and then 18 parts by mass of methacrylic acid as the compound (A1). As other copolymerizable monomer (A3), 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 5 parts by mass of styrene, 2-hydroxyethyl methacrylate 30 parts by mass and 22 parts by mass of benzyl methacrylate were charged and substituted with nitrogen. Next, while gently stirring, the temperature of the solution is raised to 70 ° C., and this temperature is maintained for 5 hours for polymerization to obtain a copolymer (A-1) solution having a solid content concentration of 28.8%. It was. Mw of the obtained copolymer (A-1) was 13,000.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by mass of methacrylic acid as (A1), 20 parts by mass of glycidyl methacrylate as (A2), and tricyclomethacrylate [5.2.1.0 ^2,6 ] decane-8 as other copolymerizable monomers -After charging 16 parts by weight of yl, 38 parts by weight of methyl methacrylate, and 10 parts by weight of styrene and purging with nitrogen, the temperature of the solution was raised to 70 ° C while gently stirring, and this temperature was maintained for 4 hours for polymerization. Thus, a solution containing the copolymer (A-2) was obtained (solid content concentration = 28.4% by mass, Mw = 8,000).

<Preparation of radiation-sensitive resin composition>
[Examples 1 to 5 and Comparative Examples 1 to 3]
The types and amounts of [A] alkali-soluble resin, [B] polymerizable compound, and [C] radiation sensitive polymerization initiator, [D] compound, and [E] epoxy compound shown in Table 1 were mixed, and the solid content concentration was After being dissolved in propylene glycol monomethyl ether acetate so as to be 30% by mass, it is filtered through a Millipore filter having a pore size of 0.5 μm, whereby the radiation sensitive resin compositions (S-1) to (S-5) and ( s-1) to (s-3) were prepared. In Table 1, “-” indicates that the corresponding component was not used.

  The detail of each component used by the Example and the comparative example is shown below.

<[B] Polymerizable compound>
B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.)
B-2: Ethylene oxide-modified dipentaerythritol hexaacrylate (KAYARAD DPEA-12, Nippon Kayaku Co., Ltd.)

<[C] Radiation sensitive polymerization initiator>
C-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, Ciba Specialty Chemicals)
C-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, Ciba Specialty Chemicals) )

<[D] Compound>
D-1: 4-aminopyridine D-2: 4-dimethylaminopyridine D-3: 4-aminomethylpyridine d-1: imidazole

<[E] epoxy compound>
E-1: Phenol novolac type epoxy resin (Epicoat 152 manufactured by Japan Epoxy Resin)

<Formation of spacer>
[Examples 6 to 15 and Comparative Examples 4 to 6]
Using a spinner on an alkali-free glass substrate, each of the radiation-sensitive resin compositions shown in Table 2 was applied and then pre-baked on a hot plate at 85 ° C. for 2 minutes to form a coating film having a thickness of 3.5 μm. did. The obtained coating film was exposed through a dot pattern mask having a diameter of 13 μm with an exposure amount of 850 J / m ² and an exposure gap of 250 μm. Subsequently, after developing with a 0.05 mass% potassium hydroxide (1.5 wt% CD150CR) aqueous solution at 25 ° C., it was rinsed with pure water for 1 minute. Furthermore, a spacer was formed by post-baking (baking) for 30 minutes in the oven at the temperature shown in Table 2, and the following characteristics evaluation was performed. The evaluation results are shown in Table 2.

<Evaluation>
[Heat-resistant]
Each spacer was further heated in an oven at 180 ° C. for 30 minutes, and the change in film thickness before and after heating was measured. The rate of change (%) represented by the following formula was evaluated as heat resistance.
Rate of change (%) = (film thickness after additional heating / film thickness after post-baking) × 100

[Compression characteristics]
For each spacer, a load of up to 50 mN was applied using a micro compression tester (Fischer Scope HM2000Xyp, Fischer Instruments) with a flat indenter of 50 μm × 50 μm with a loading speed and an unloading speed of 2.5 mN / sec. After holding for 5 seconds, unloading was performed, and a load-deformation curve at load and a load-deformation curve at slow load were created. At this time, the difference between the deformation amount at the load of 50 mN at the load and the deformation amount at the unload is L1, and the difference between the deformation amount at the load of 50 mN and the deformation amount at the unload is L2. The elastic recovery rate was calculated by the following formula.
Elastic recovery rate (%) = (L2 / L1) × 100

<Formation of cured film as interlayer insulating film or protective film>
[Examples 16 to 25 and Comparative Examples 7 to 9]
Each of the radiation sensitive resin compositions shown in Table 3 was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Thereafter, the substrate is exposed at an exposure amount of 800 J / m ² without passing through a mask, and this substrate is post-baked (baked) at a temperature shown in Table 3 for 30 minutes in a clean oven to thereby provide interlayer insulation on the silicon substrate. A cured film applicable as a film or a protective film was formed, and the following characteristics evaluation was performed. In the evaluation of the voltage holding ratio, a cured film was formed by the following method and evaluated. The respective evaluation results are shown in Table 3.

<Characteristic evaluation as cured film>
[Evaluation of solvent resistance]
The thickness (T1) of each cured film was measured. Next, the silicon substrate on which this cured film was formed was immersed in dimethyl sulfoxide whose temperature was controlled at 70 ° C. for 20 minutes, and then the film thickness (t1) of the cured film was measured, and the rate of change in film thickness due to immersion. Was calculated from the following formula. A film thickness change rate of 5.0% or less was judged good.
Film thickness change rate (%) = {(t1−T1) / T1} × 100

[surface hardness〕
About the board | substrate which has each cured film, the surface hardness of the cured film was measured by the 8.4.1 pencil scratch test of JISK-5400-1990. When the result was 3H or more, the surface hardness was judged to be good.

[Voltage holding ratio]
Each radiation sensitive resin composition was spin-coated on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface, and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape. Then, prebaking was performed for 2 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an integrated dose of 1,000 J / m ² without using a photomask. Next, development by a dip method was performed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds. Further, post-baking was performed at the firing temperature and firing time shown in Table 2 to form a cured film. Next, after spraying a 5.5 μm diameter bead spacer on the substrate having the cured film, the liquid crystal injection port is placed in a state where this is opposed to a soda glass substrate on which the ITO electrode is deposited in a predetermined shape. The remaining four sides were bonded using a sealing agent mixed with 0.8 mm glass beads, and liquid crystal MLC6608 manufactured by Merck was injected, and then the liquid crystal injection port was sealed to prepare a liquid crystal cell. This liquid crystal cell was put 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 calculated from the following equation. The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility of causing a problem called “burn-in” when forming the liquid crystal panel. On the other hand, the lower the voltage holding ratio, the more the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, which means that the liquid crystal cannot be sufficiently aligned. There is a high risk of burning.
Voltage holding ratio (%) = (potential difference of liquid crystal cell after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds) × 100

[Thickness change rate]
About the radiation sensitive resin composition solution immediately after preparation, the film thickness of the cured film formed by operating in the same manner as in the above-mentioned “formation of cured film” was measured (in the following formula, “film thickness immediately after preparation” and Called). 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 "film thickness after 5 days"). The film thickness increase rate (%) was calculated from the following formula. When the film thickness increase rate was 3% or less, it was judged that the storage stability was good.
Film thickness increase rate (%) = (film thickness after 5 days−film thickness immediately after preparation) / (film thickness immediately after preparation) × 100

  From the results of Tables 2 and 3, it was found that the radiation-sensitive resin composition had high storage stability. Moreover, it has also confirmed that it had sufficient pattern formation ability. Furthermore, it has been found that the spacer formed from the radiation-sensitive resin composition has good heat resistance and compression characteristics even by low-temperature and short-time baking. On the other hand, it was found that a cured film as an interlayer insulating film or protective film formed from the radiation sensitive resin composition was excellent in solvent resistance, hardness and voltage holding ratio.

  The radiation-sensitive resin composition of the present invention has both storage stability and low-temperature curability and has sufficient pattern forming ability. Moreover, the cured film formed from the said radiation sensitive resin composition is excellent in the heat resistance which is the required characteristic, a compression characteristic, etc. Therefore, the said fat composition is suitable as forming materials, such as a spacer used for the flexible display etc. in which low temperature baking is desired.

Claims (9)

[A] alkali-soluble resin,
[B] a polymerizable compound having an ethylenically unsaturated bond,
[C] a radiation sensitive polymerization initiator, and [D] a compound represented by the following formula (1),
[A] A radiation-sensitive resin composition in which the alkali-soluble resin has an epoxy group or further contains an [E] epoxy compound.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. However, some or all of the hydrogen atoms of the alkyl group, aryl group and aralkyl group may be substituted with at least one selected from the group consisting of an amino group and a hydroxyl group, and R ¹ and R ² may be bonded to each other to form a cyclic structure together with the nitrogen atom to which they are bonded, R ³ is a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, W is a single bond or (It is an alkanediyl group having 1 to 12 carbon atoms.)   [A] The alkali-soluble resin is a copolymer of (A1) one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and (A2) an epoxy group-containing unsaturated compound. The radiation sensitive resin composition according to claim 1, wherein the radiation sensitive resin composition is a copolymer. The nitrogen-containing heterocyclic group represented by R ³ in the formula (1) is at least one group selected from the group consisting of a pyridyl group, a pyrazyl group, a pyrimidyl group, and a benzimidazole group. Item 3. The radiation-sensitive resin composition according to Item 2.   [D] Compound is 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 2- (methylamino) ) Pyridine, 3- (methylamino) pyridine, 4- (methylamino) pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine, 4- (4-aminopiperidino) pyridine, 2-aminopyrazine, 4-aminopyrimidine and The radiation-sensitive resin composition according to claim 3, which is at least one compound selected from the group consisting of 2-aminobenzimidazole.   [A] The radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the content of the [D] compound with respect to 100 parts by mass of the alkali-soluble resin is 0.01 parts by mass or more and 10 parts by mass or less. object.   The radiation-sensitive resin composition according to any one of claims 1 to 5, which is used for forming a cured film as an interlayer insulating film, a protective film, or a spacer.   A cured film as an interlayer insulating film, protective film or spacer formed from the radiation-sensitive resin composition according to claim 6. (1) The process of forming a coating film using the radiation sensitive resin composition of Claim 6,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) The process of developing the coating film irradiated with the said radiation, (4) The formation method of the cured film which has the process of baking the developed said coating film.   The method for forming a cured film according to claim 8, wherein the temperature in the firing in the step (4) is 200 ° C. or lower.