JP5736718B2 - Radiation-sensitive resin composition, cured film and method for forming the same - Google Patents

Description

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

  In recent years, flexible displays such as electronic paper have become widespread. As a substrate for this flexible display, a plastic substrate such as polyethylene terephthalate has been studied. Since this substrate expands or contracts when heated, there is a disadvantage in that the function as a display is hindered, and a reduction in the manufacturing process of the flexible display has been studied. One of the processes requiring the highest temperature in manufacturing a flexible display is a step of baking an interlayer insulating film by heating, and a reduction in the baking step is required.

  At present, as a material for forming a cured film such as an interlayer insulating film, a radiation sensitive resin composition that has a small number of steps for obtaining a required pattern shape and can obtain high surface hardness is widely used. As such a radiation sensitive resin composition, there is known a radiation sensitive resin composition containing a copolymer composed of an unsaturated carboxylic acid and / or an anhydride thereof, an epoxy group-containing unsaturated compound, and the like. The surface hardness of the cured film is obtained by the reaction between the epoxy group and the epoxy group (see JP-A-2001-354822). However, in order to increase the surface hardness to a level that is actually required commercially as an interlayer insulating film, a baking process at a high temperature exceeding 200 ° C. is required. Therefore, 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. This may cause a reaction with the group over time, resulting in a decrease in storage stability.

  In addition, a technique for a coating liquid for a gate insulating film of a flexible display containing a polyimide precursor that can be cured even by low-temperature firing has been developed (see Japanese Patent Application Laid-Open No. 2009-4394). However, since this coating solution does not have a pattern forming ability by exposure and development, a fine pattern cannot be formed. Furthermore, due to insufficient curing reactivity, the fired film has a time of 1 hour or longer, and the obtained cured film such as an interlayer insulating film is not at a satisfactory level in surface hardness. Further, in the flexible display manufacturing process, a laminate may be formed on the upper layer of the interlayer insulating film. In this case, the interlayer insulating film is required to have a high dielectric constant and a solvent resistance to the solvent used when forming the laminate.

  Under such circumstances, development of a radiation sensitive resin composition suitable for producing a cured film for a flexible display is strongly demanded.

JP 2001-354822 A JP 2009-4394 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is to achieve both low-temperature firing and storage stability, and has a high radiation sensitivity, and a flexible display. It is desirable to provide a cured film as an interlayer insulating film, a protective film or a spacer excellent in surface hardness, solvent resistance and relative dielectric constant.

（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、かつＲ^１〜Ｒ^６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１〜６のアルキル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、水素原子の全部又は一部がシアノ基、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] (A1) An alkali-soluble resin obtained by copolymerizing at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and (A2) an epoxy group-containing unsaturated compound , Sometimes referred to as “[A] alkali-soluble resin”),
[B] quinonediazide compound, and [C] a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, an amidine salt, an amide compound, a ketimine At least one curing agent selected from the group consisting of a compound, a blocked isocyanate compound, an imidazole ring-containing compound, and an inclusion compound (hereinafter sometimes referred to as “[C] curing agent”)
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. In addition, at least one of R ^{1 to} R ⁶ is an amino group, and 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 1 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, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. )

  In addition to [A] alkali-soluble resin and [B] quinonediazide compound, the radiation-sensitive resin composition has a high radiation sensitivity by containing a [C] curing agent selected from the above specific compounds, [A] It acts as an effective curing catalyst for the epoxy group or the like of the alkali-soluble resin, and as a result, both storage stability and low-temperature firing can be achieved. In addition, a cured film formed from the radiation-sensitive resin composition is excellent in surface hardness, solvent resistance, and relative dielectric constant, and thus is suitably used as a material for forming an interlayer insulating film, a protective film, or a spacer of a flexible display. .

  [C] The curing agent is preferably at least one selected from the group consisting of compounds represented by the above formulas (1) and (2). [C] By selecting the specific compound having an amino group and an electron-deficient group as a curing agent, the storage stability and low-temperature firing of the radiation-sensitive resin composition can be compatible at a higher level, and further obtained. The relative dielectric constant of the cured film can be further improved.

  The radiation-sensitive resin composition is suitable for forming a cured film as an interlayer insulating film, a protective film, or a spacer because of the effects described above.

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) 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.

  When a cured film is formed by the above process using the radiation-sensitive resin composition, a pattern is formed by exposure / development using radiation sensitivity, so that a fine and elaborate pattern can be easily formed. Can do. Moreover, the cured film formed using the said radiation sensitive resin composition has sufficient surface hardness etc. even if it is low-temperature baking.

  The firing temperature in step (4) in the forming method is preferably 200 ° C. or lower. In addition to the ability to form a fine pattern using radiation sensitivity, the formation method can form a cured film such as an interlayer insulating film on a plastic substrate of a flexible display by being capable of firing at such a low temperature. Is preferably used.

  The present invention also includes a cured film as an interlayer insulating film, protective film or spacer formed from the radiation-sensitive resin composition.

  In addition, "baking" as used in this specification means heating until the intensity | strength requested | required of a cured film is obtained. The “radiation” irradiated upon exposure is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

  According to the radiation-sensitive resin composition of the present invention, surface hardness and solvent resistance suitable for use in a radiation-sensitive resin composition having a low radiation rate and storage stability and having high radiation sensitivity, and for flexible displays. It is possible to provide a cured film as an interlayer insulating film, a protective film, or a spacer that is excellent in properties and relative dielectric constant.

<Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention contains [A] an alkali-soluble resin, [B] a quinonediazide compound, and [C] a curing agent. Moreover, you may contain arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.

<[A] alkali-soluble resin>
[A] The alkali-soluble resin may be referred to as (A1) at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “(A1) compound”). ) And (A2) an epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “(A2) compound”).

  [A] The alkali-soluble resin is obtained by, for example, copolymerizing a compound (A1) giving a carboxyl group-containing structural unit and a compound (A2) giving an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound giving a hydroxyl group-containing structural unit (hereinafter sometimes referred to as “(A3) compound”) may be further added to obtain a copolymer. Further, in the production of [A] the alkali-soluble resin, the compound (A4) (derived from the compounds (A1), (A2) and (A3)) together with the compound (A1), the compound (A2) and the compound (A3). An unsaturated compound that gives structural units other than the structural unit to be added) can be further added to form a copolymer.

[(A1) Compound]
(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 unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
Examples of anhydrides of unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the above dicarboxylic acids;
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, for example, 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 acids and dicarboxylic anhydrides are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These (A1) compounds may be used alone or in admixture of two or more.

  (A1) As a using ratio of a compound, 5-30 mass% is based on the sum total of (A1) compound and (A2) compound (arbitrary (A3) compound and (A4) compound as needed). Preferably, 10% by mass to 25% by mass is more preferable. (A1) By making the usage-amount of a compound into the said range, while optimizing the solubility with respect to the aqueous alkali solution of [A] alkali-soluble resin, the radiation sensitive resin composition excellent in a sensitivity is obtained.

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

  Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic-6,7-epoxyheptyl, o-Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl is preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the cured film.

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. These (A2) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the total of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound if necessary). 10 mass%-50 mass% are more preferable. (A2) By making the use ratio of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.

[(A3) Compound]
Examples of the (A3) compound include a (meth) acrylic acid ester having a hydroxyl group, a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (3), and the like.

In the above formula ^{(3), R 17} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{18 to} R ²² 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 0-3. However, at least one of R ^{18 to} R ²² is a hydroxyl group.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol. (N = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside and the like. .

  Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-5) according to the definitions of Y and p. .

In the above formula (3-1), q is an integer of 1 to 3. R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In the formula ^(3-2), R 17 ^{to R 22} is as defined in the above formula (3).

In the above formula (3-3), r is an integer of 1 to 3. R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In the formula ^(3-4), R 17 ^{to R 22} is as defined in the above formula (3).

In the above formula ^(3-5), R 17 ^{to R 22} is as defined in the above formula (3).

  Of these (A3) compounds, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.

  (A3) As a using ratio of a compound, 5-30 mass% is based on the sum total of (A1) compound, (A2) compound, and (A3) compound (arbitrary (A4) compound as needed). Preferably, 10% by mass to 25% by mass is more preferable. (A3) By making the use ratio of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.

[(A4) Compound]
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. As the (A4) compound, for example, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, 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 containing skeleton represented by the following formula (4), and other unsaturated compounds Compounds and the like.

In the formula ^{(4), R 23} is a hydrogen atom or a methyl group. s is an integer of 1 or more.

  Examples of the methacrylic acid chain alkyl ester include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate. Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.

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 tricyclomethacrylate [5.2.1]. .0 ^2,6] decan-8-yl oxy ethyl, and isobornyl methacrylate.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. Examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.

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, and p-methoxystyrene.

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

Among these (A4) 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 (4). Unsaturated compounds, unsaturated aromatic compounds and acrylic acid cyclic alkyl esters are preferred. Among these, styrene, methyl methacrylate, 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 From the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution, it is more preferable. These (A4) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A4) used is preferably 10% by mass to 70% by mass based on the sum of the compound (A1), the compound (A2) and the compound (A4) (and any (A3) compound). A mass% to 60 mass% is more preferable. (A4) By making the usage-amount of a compound into the said range, the cured film excellent in solvent resistance etc. can be formed.

<[A] Method for synthesizing alkali-soluble resin>
[A] The alkali-soluble resin is produced, for example, by copolymerizing the compound (A1) and the compound (A2) (arbitrary (A3) compound and (A4) compound) in the presence of a polymerization initiator in a solvent. it can.

  [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, ketone, ester and the like.

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 monoalkyl ether acetate include propylene glycol monomethyl ether acetate and propylene glycol monoethyl 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, 3-methoxybutyl 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, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Kishipuropion ethyl 3-ethoxy propionate propyl, 3-ethoxy propionate butyl, 3-propoxy-propionic acid methyl, and the like.

  Among these solvents, 3-methoxybutyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol Methyl ethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are more preferable.

  [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.

[A] As a weight average molecular weight (Mw) of alkali-soluble resin, 1,000-30,000 are preferable and 5,000-20,000 are more preferable. [A] By making Mw of alkali-soluble resin into the said range, the sensitivity and developability of the said 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

<[B] quinonediazide compound>
The [B] quinonediazide compound used in the radiation-sensitive resin composition of the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;
Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxy). Phenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-) 4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl) -4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like;
Examples of other mother nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4 -Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4 , 6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably.

  These [B] quinonediazide compounds can be used alone or in combination of two or more. As a use ratio of the [B] quinonediazide compound in the said radiation sensitive resin composition, 5 mass parts-100 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 10 mass parts-50 mass parts are. More preferred. [B] By setting the use ratio of the quinonediazide compound within the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained cured film The solvent resistance is improved.

<[C] Curing agent>
The [C] curing agent contained in the radiation sensitive resin composition is a compound represented by the above formula (1), a compound represented by the above formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, It is at least one selected from the group consisting of an amidine salt, an amide compound, a ketimine compound, a blocked isocyanate compound, an imidazole ring-containing compound and an inclusion compound. When the radiation sensitive resin composition contains a [C] curing agent selected from the above specific compounds, both storage stability and low temperature firing can be achieved. Hereinafter, each compound will be described in detail.

[Compounds Represented by Formula (1) and Formula (2)]
[C] The curing agent is preferably at least one selected from the group consisting of compounds represented by the above formulas (1) and (2). [C] By selecting the specific compound having an amino group and an electron-deficient group as a curing agent, the storage stability and low-temperature firing of the radiation-sensitive resin composition can be compatible at a higher level, and further obtained. The relative dielectric constant of the cured film can be further improved.

In said formula (1), R < ¹ > -R < ⁶ > is a hydrogen atom, an electron withdrawing group, or an amino group each independently. 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 includes all or part of hydrogen atoms. It may be substituted with an alkyl group having 1 to 6 carbon atoms.
In said formula (2), R < ⁷ > -R < ¹⁶ > is a hydrogen atom, an electron withdrawing group, or an amino group each independently. 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 1 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, in the methylene group and alkylene group, all or part of the hydrogen atoms 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 alkyloxysulfonyl group, a dicyanovinyl group, and a trisia. Novinyl group, sulfonyl group and the like can be mentioned. Of these, a nitro group, an alkyloxysulfonyl 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.

As the compounds represented by the above formulas (1) and (2),
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.

  The compounds represented by the above formulas (1) and (2) can be used alone or in admixture of two or more. As a content rate of the compound represented by the said Formula (1) and Formula (2), 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, 0.2 mass Part to 10 parts by mass is more preferable. By making the content rate of the compound represented by the said Formula (1) and Formula (2) into the said range, the storage stability of the said radiation sensitive resin composition and low temperature baking can be made compatible at a higher level.

[Tertiary amine compound]
When a highly reactive general primary amine compound or secondary amine compound coexists with an epoxy compound, a curing reaction proceeds due to a nucleophilic attack on the epoxy group of the amine during storage of the composition solution. There is a risk of quality loss. However, when a tertiary amine is used, the storage stability is good even if it is coexistent with an epoxy compound in the composition part due to its relatively low reactivity.

  As the tertiary amine compound, at least one selected from the group consisting of compounds represented by the following formula (5) can be used.

In the above formula ^{(5), R} 24 ~R ²⁶ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group, or a C7-30 aralkyl group having 6 to 18 carbon atoms. However, R ²⁴ and R ²⁵ may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. In the alkyl group, aryl group and aralkyl group, part or all of the hydrogen atoms may be substituted.

Examples of the alkyl group having 1 to 20 carbon atoms indicated by the R ²⁴ to R ^26, for example, linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl Group, nonyl group, decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ^{24 to} R ²⁶ include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ^{24 to} R ²⁶ include a benzyl group and a phenethyl group.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, N, N-dimethylbenzylamine, triphenylamine, tributylamine, trioctylamine, tridodecylamine, dibutylbenzylamine, trinaphthylamine, N-ethyl-N-methylaniline. N, N-diethylaniline, N-phenyl-N-methylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-4-bromoaniline, N, N-dimethyl-4-methoxyaniline, N -Phenylpiperidine, N- (4-methoxyphenyl) piperidine, N-phenyl-1,2,3,4-tetrahydroisoquinoline, 6-benzyloxy-N-phenyl-7-methoxy-1,2,3,4 Tetrahydroisoquinoline, N, N′-dimethylpiperazine, , N- dimethylcyclohexylamine, 2-dimethylaminomethyl phenol, 2,4,6-tris (dimethylaminomethyl) phenol, and the like.

  Of these tertiary amine compounds, trioctylamine and 2-dimethylaminomethylphenol are preferred. The tertiary amine compounds can be used alone or in admixture of two or more. As a content rate of the tertiary amine compound in the said radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, 0.2 mass part-5 Part by mass is more preferable. By making the content rate of a tertiary amine compound into the said specific range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

[Amine salts and phosphonium salts]
As amine salt and phosphonium salt, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (6) can be used.

In the above formula (6), ^{A 1} is a nitrogen atom or a phosphorus atom. R ²⁷ to R ³⁰ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a C7-30 aralkyl group having 6 to 18 carbon atoms having 1 to 20 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted. Q ⁻ is a monovalent anion.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{27 to} R ³⁰ include a linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl. Group, nonyl group, decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ^{27 to} R ³⁰ include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to ³⁰ carbon atoms represented by R ^{27 to} R ³⁰ include a benzyl group and a phenethyl group.

Examples of the monovalent anion represented by Q ⁻ include chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, hypochlorite ion, chlorite ion, and chlorate ion. Perchlorate ion, permanganate ion, bicarbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carboxylate ion, sulfonate ion, phenoxide ion, tetrafluoroborate ion, tetraarylborate ion, Examples include hexafluoroantimonate ions.

When A ¹ is a nitrogen atom, that is, as an ammonium salt, for example, tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyl chloride Trimethylammonium, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzalkonium chloride, benzalkonium bromide, didecyldimethylammonium chloride, distearyl chloride Examples include dimethylammonium.

When A ¹ is a phosphorus atom, that is, as a phosphonium salt, for example, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium tetra (p-ethylphenyl) borate, tetra Phenylphosphonium tetra (p-methoxyphenyl) borate, tetraphenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium tetra (p-tert-butoxyphenyl) borate, tetraphenylphosphonium tetra (m-tolyl) Borate, tetraphenylphosphonium tetra (m-methoxyphenyl) borate, tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate, tetra (p-tril) L) Phosphonium tetra (p-tolyl) borate, tri (p-methoxyphenyl) phenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltriphenylphosphonium thiocyanate, p-tolyl Triphenylphosphonium thiocyanate, benzyltriphenylphosphonium hexafluoroantimonate, p-chlorobenzyltriphenylphosphonium hexafluoroantimonate, p-methylbenzyltriphenylphosphonium hexafluoroantimonate, p-methoxybenzyltriphenylphosphonium hexafluoroantimonate, α-methylbenzyltriphenylphosphonium hexafluoroantimonate, Namyltriphenylphosphonium hexafluoroantimonate, 2-hydroxy-5-nitrobenzyltriphenylphosphonium hexafluoroantimonate, 1-naphthylmethyltriphenylphosphonium hexafluoroantimonate, 3-trimethylsilyl-4-trimethylsiloxybenzyltriphenylphosphonium hexa Fluoroantimonate, p-methoxybenzyltris (p-chlorophenyl) phosphonium hexafluoroantimonate, p-methoxybenzyltris (p-methylphenyl) phosphonium hexafluoroantimonate, cinnamyltris (p-chlorophenyl) phosphonium hexafluoroantimonate P-methoxybenzyltriphenylphosphonium hexafluorophosphate, 1-pyre Nylmethyl-triphenylphosphonium hexafluoroantimonate, 1-pyrenylmethyl-butyldiphenylphosphonium hexafluoroantimonate, 9-anthracenylmethyl-triphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium decanoate, tri (tert-butyl) phosphonium -Tetraphenylborate, di-tert-butylmethylphosphonium-tetraphenylborate, p-tolyltriphenylphosphonium-tetra (p-tolyl) borate, tetraphenylphosphonium-tetrafluoroborate and the like.

  Of these amine salts and phosphonium salts, tetramethylammonium chloride and butyltriphenylphosphonium thiocyanate are preferable. Amine salts and phosphonium salts can be used alone or in admixture of two or more. As a content rate of the amine salt and phosphonium salt in the said radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, 0.5 mass part- 5 parts by mass is more preferable. By making the content rate of an amine salt and a phosphonium salt into the said specific range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

[Amidine salt]
As the amidine salt, at least one selected from the group consisting of salts of compounds represented by the following formula (7) can be used.

In said formula (7), m is an integer of 2-6. However, some or all of the hydrogen atoms of the alkylene group may be substituted with organic groups. Note that the above-mentioned alkylene group refers to both alkylene groups represented by (CH 2) _m in the alkylene group and wherein in the tetrahydropyrimidine ring (7).

Examples of the organic group that the alkylene group may have as a substituent include those having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. An alkyl group;
Such as hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxyisopropyl group, 3-hydroxy-t-butyl group, 6-hydroxyhexyl group, etc. A hydroxyalkyl group having 1 to 6 carbon atoms;
Examples thereof include C2-C12 dialkylamino groups such as dimethylamino group, methylethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, t-butylmethylamino group, and di-n-hexylamino group.

  Examples of the compound represented by the above formula (7) include 1,5-diazabicyclo [4,3,0] -nonene-5 (DBN), 1,5-diazabicyclo [4,4,0] -decene-5, 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5,4,0] -undecene-7, 5-dibutylamino-1,8 -Diazabicyclo [5,4,0] -undecene-7 and the like. Of these, DBN and DBU are preferred.

  Examples of the acid for the compound represented by the above formula (7) to form a salt include organic acids and inorganic acids.

Examples of the organic acid include carboxylic acid, monoalkyl carbonic acid, aromatic hydroxy compound, sulfonic acid and the like.
Examples of the carboxylic acid include saturated fatty acids such as formic acid, acetic acid, 2-ethylhexanoic acid and isovaleric acid;
Acrylic acid, crotonic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, vaccenic acid, eleostearic acid, arachidonic acid, cinnamic acid , Unsaturated carboxylic acids such as naphthoic acid, benzoic acid and toluic acid;
Α-substituted acetic acid such as chloroacetic acid, cyanoacetic acid, dichloroacetic acid, trichloroacetic acid, trimethylacetic acid, fluoroacetic acid, bromoacetic acid, methoxyacetic acid, mercaptoacetic acid, iodoacetic acid, vinylacetic acid, oxaloacetic acid, phenylacetic acid, phenoxyacetic acid;
Dicarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, arazeic acid, suberic acid, sebacic acid;
Hydroxycarboxylic acids such as glycolic acid, lactic acid, citric acid, d-tartaric acid, mesotartaric acid, ascorbic acid, mandelic acid;
Ketocarboxylic acids such as pyruvic acid and levulinic acid;
Examples thereof include halocarboxylic acids such as 2-chloropropionic acid and 3-chloropropionic acid.

Examples of monoalkyl carbonic acid include methyl carbonic acid and ethyl carbonic acid.
Examples of the aromatic hydroxy compound include phenol, cresol, catechol, naphthol and the like.
Examples of the sulfonic acid include octylbenzenesulfonic acid, butylbenzenesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, and methanesulfonic acid.

Examples of inorganic acids include halogen acids such as hydrochloric acid, hydrofluoric acid, and bromic acid;
And carbonic acid; and perhalogenated acids such as perchloric acid and perbromic acid.

  Of these acids, carboxylic acids, aromatic hydroxy compounds and sulfonic acids are preferred, saturated fatty acids, aromatic hydroxy compounds and sulfonic acids are more preferred, sulfonic acids which are strong acids are particularly preferred, toluenesulfonic acid, methanesulfonic acid, Octylbenzenesulfonic acid is most preferred. The amidine salt is preferably a salt of DBU and toluenesulfonic acid, a salt of DBU and octylbenzenesulfonic acid, a salt of DBN and toluenesulfonic acid, or a salt of DBN and octylbenzenesulfonic acid.

  Amidine salts can be used alone or in admixture of two or more. As a content rate of the amidine salt in the said radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts. Is more preferable. By setting the content ratio of the amidine salt within the above specific range, the storage stability and low-temperature firing of the radiation-sensitive resin composition can be achieved at a higher level.

[Amide compound]
As the amide compound, at least one selected from the group consisting of compounds having an amide group represented by the following formulas (8) to (10) can be used.

In the formula ^{(8), R 31} and ^{R 32} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group, or a 2-pyridyl group. However, the alkyl group having 1 to 12 carbon atoms, the phenyl group, and the naphthyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, or an acetyl group.
In said formula (9), ^R33 and ^R34 are respectively independently a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group. A ² is a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, a naphthylene group, or a vinylene group. However, the methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group, and the naphthylene group may be substituted with an alkyl group having 1 to 6 carbon atoms and a halogen atom.
In said formula (10), ^R35 and ^R36 are respectively independently a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group. A ³ is a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, a naphthylene group, or a vinylene group. However, the methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group, and the naphthylene group may be substituted with an alkyl group having 1 to 6 carbon atoms and a halogen atom.

  The amide compound represented by the above formula (8) is a compound having one amide bond in the molecule. Specific examples thereof include acetamide, N-methylacetamide, N-ethylacetamide, Nn-propylacetamide, N-isopropylacetamide, Nn-butylacetamide, N-isobutylacetamide, Nt-butylacetamide, Nn-hexylacetamide, Nn-octylacetamide, Nn-dodecylacetamide, propionylamide, butyrylamide, valerylamide, isovalerylamide, octanoylamide, acetanilide, acetoacetanilide, o-acetamide benzoic acid, m- Acetamide benzoic acid, p-acetamidobenzoic acid, o-acetamidophenol, m-acetamidophenol, p-acetamidophenol, acetamidonaphthalene, phthalamidic acid, acrylic acid , Benzamide, naphthamide, nicotinamide, isonicotinamide, and the like.

  Of these, acetamide, N-methylacetamide, and phthalamic acid are preferred from the viewpoints of improving storage stability at room temperature, heat resistance of the resulting cured film, voltage holding ratio, and the like.

  The compounds represented by the above formulas (9) and (10) are compounds having two amide bonds in the molecule. Specific examples thereof include, for example, phthalamide, isophthalamide, terephthalamide, malonamide, succinamide, glutaramide, adipineamide, pimelinamide, suberinamide, azelainamide, sebacinamide, maleamide, fumaramide, N, N′-dimethyl-phthalamide, N, N′-dimethyl-isophthalamide, N, N′-dimethyl-terephthalamide, N, N′-diacetyl-o-phenylenediamine, N, N′-diacetyl-m-phenylenediamine, N, N′-diacetyl -P-phenylenediamine, N, N'-dipropionyl-o-phenylenediamine, N, N'-dipropionyl-m-phenylenediamine, N, N'-dipropionyl-p-phenylenediamine, N, N'- Diacetyl-ethylenediamine N, N′-diacetyl-propylenediamine, N, N′-diacetyl-butylenediamine, N, N′-diacetyl-hexamethylenediamine, N, N′-diacetyl-dodecylmethylenediamine, N, N′-dibenzoyl- Ethylenediamine, N, N'-dibenzoyl-propylenediamine, N, N'-dibenzoyl-butylenediamine, N, N'-dibenzoyl-hexamethylenediamine, N, N'-dibenzoyl-dodecylmethylenediamine, N, N'-dinaphthoyl -Ethylenediamine, N, N'-dinaphthoyl-propylenediamine, N, N'-dinaphthoyl-butylenediamine, N, N'-dinaphthoyl-hexamethylenediamine, N, N'-dinaphthoyl-dodecylmethylenediamine and the like.

  Of these, from the viewpoint that both storage stability and low-temperature firing can be achieved at a high level, isophthalamide, adipineamide, N, N′-diacetyl-p-phenylenediamine, and N, N′-diacetyl-hexamethylenediamine are used. preferable.

  An amide compound can be used individually or in mixture of 2 or more types. As a content rate of the amide compound in the said radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts. Is more preferable. By making the content rate of an amide compound into the said specific range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

[Ketimine compound]
Ketimine compounds can be obtained by reaction of ketones with amines.

  Examples of the ketone include ethyl methyl ketone, isoamyl methyl ketone, isobutyl methyl ketone, methyl t-butyl ketone, ethyl butyl ketone, ethyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone, 3-methyl-2-hexanone, 2-octanone, Examples include 3-octanone, 4-octanone, methyl cyclohexyl ketone, and methylcyclohexanone.

Examples of amines include 2,5-dimethyl-2,5-hexanediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and amino groups on propylene branched carbons at both ends of the molecule. Bonded polypropylene glycol, ethylenediamine, trimethylenediamine, propylenediamine, tetramethylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene hexamine, trimethylhexamethylenediamine, N- aminoethylpiperazine, iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 CH _{2) 2} polyether backbone of the diamine methylene group bonded to the amine nitrogen as NH _2, 1,5-diamino-2-methylpentane, polyamidoamine, isophorone diamine, 1,3-bis-aminomethyl cyclohexane (1 , 3BAC), 1-cyclohexylamino-3-aminopropane, norbornane skeleton dimethyleneamine (NBDA), compounds represented by the following formula, and the like.

  In addition, aminoalkoxysilane can be used as an amine. As an amino alkoxysilane, the compound represented, for example by following formula (11) is mentioned.

In the above ^{formula, R 37} is an alkyl group, an alkoxy group or a monovalent siloxane derivative group having 1 to 6 carbon atoms having 1 to 6 carbon atoms. ^R38 is an alkylene group which may contain a nitrogen atom. R ³⁹ is an alkoxy group. u is an integer of 0-3.

The alkyl group having 1 to 6 carbon atoms R ³⁷ represents a methyl group, an ethyl group, a propyl group. The alkoxy group having 1 to 6 carbon atoms which R ³⁷ represents a methoxy group, an ethoxy group, a propoxy group are preferable. The monovalent siloxane derivative group represented by R ³⁷ is preferably a silyloxy group. Of these, a methoxy group and an ethoxy group are more preferable.

The alkylene group of an alkylene group which may contain a nitrogen atom which R ³⁸ represents preferably an alkylene group having 1 to 6 carbon atoms. As the alkylene group not containing a nitrogen atom, a methylene group, an ethylene group, and a propylene group are preferable. The alkylene group containing a nitrogen atom is preferably a group having an imino group (—NH—) in a hydrocarbon group exemplified by the divalent hydrocarbon group not containing the nitrogen atom. Of these, a methylene group, a propylene _{group, -C 2 H 4 NHC 3 H} 6 - is preferable.

The alkoxy group R ³⁹ represents preferably an alkoxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group are more preferable.

  Examples of the silicon-containing ketimine obtained by the reaction of a ketone and aminoalkoxysilane include a compound represented by the following formula (12), a polycondensate having a structural unit represented by the following formula (13), and the like.

In the above formula (12), R ⁴⁰ and R ⁴¹ are each independently a monovalent hydrocarbon group in which part or all of the hydrogen atoms may be substituted. However, R ⁴⁰ and R ⁴¹ may form a ring structure together with the carbon atom to which each is bonded. They are a C1-C6 alkyl group and a C1-C6 alkoxy group. R ⁴³ is an alkylene group that may contain a nitrogen atom. R ⁴⁴ is an alkoxy group. v is an integer of 0-3.

In the above formula (13), R ⁴⁵ and R ⁴⁶ are each independently a monovalent hydrocarbon group in which some or all of the hydrogen atoms may be substituted. However, R ⁴⁵ and R ⁴⁶ may form a ring structure together with the carbon atom to which each is bonded. R ⁴⁷ is an alkylene group which may contain a nitrogen atom. R ⁴⁸ is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

  The terminal of the polycondensate having the structural unit represented by the formula (13) is, for example, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group or a propyl group; a methoxy group, an ethoxy group or a propoxy An alkoxy group having 1 to 6 carbon atoms such as a group can be bonded.

  Of these amines, diamines having an alicyclic structure or an aromatic ring structure are preferred. Suitable ketimines include compounds represented by the following formula (14).

In the formula (14), R ^{49 to} R ⁵² are each independently a monovalent hydrocarbon group in which part or all of the hydrogen atoms may be substituted. However, R ⁴⁹ and R ⁵⁰ may form a ring structure together with the carbon atom to which each is bonded. R ⁵¹ and R ⁵² may form a ring structure together with the carbon atom to which each is bonded. R ⁵³ is a divalent hydrocarbon group which may be substituted.

Examples of the monovalent hydrocarbon group represented by R ^{49 to} R ⁵² include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Examples of the monovalent aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. As monovalent alicyclic hydrocarbon, a C3-C20 cycloalkyl group is mentioned, for example. Examples of the monovalent aromatic hydrocarbon group include an aryl group having 6 to 20 carbon atoms.

  As said C1-C20 alkyl group, a C1-C12 alkyl group is preferable and a C1-C6 alkyl group is more preferable. Preferred examples include methyl group, ethyl group, i-propyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, 1,1-dimethylpropyl group, 1-methylbutyl. Group, 1,1-dimethylbutyl group, and hexyl group.

  As said C2-C20 alkenyl group, a C2-C10 alkenyl group is preferable and a C2-C6 alkenyl group is more preferable. Preferable specific examples include vinyl group, allyl group, butenyl group, and hexenyl group.

  As said C2-C20 alkynyl group, a C2-C10 alkynyl group is preferable and a C2-C6 alkynyl group is more preferable. Preferable specific examples include ethynyl group and propynyl group.

  As said C3-C20 cycloalkyl group, a C3-C12 cycloalkyl group is preferable and a C3-C8 cycloalkyl group is more preferable. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, and a cyclohexyl group.

  The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 14 carbon atoms. Preferable specific examples include a phenyl group, a naphthyl group, an indenyl group, and an anthryl group, a phenyl group and a 2-naphthyl group are more preferable, and a phenyl group is particularly preferable.

As the divalent hydrocarbon group represented by R ⁵³ , a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, an alkylene-cycloalkylene-alkylene group, cyclohexane Examples include an alkylene-alkylene-cycloalkylene group and an alkylene-arylene-alkylene group.

  Examples of the divalent aliphatic hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms. Examples of the divalent alicyclic hydrocarbon include a cycloalkylene group having 3 to 20 carbon atoms and a cycloalkenylene group having 3 to 20 carbon atoms. Examples of the divalent aromatic hydrocarbon group include an arylene group having 6 to 20 carbon atoms.

  As said C1-C20 alkylene group, a C1-C12 alkylene group is preferable and a C1-C6 alkylene group is more preferable. Preferable specific examples include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

  As said C3-C20 cycloalkylene group, a C3-C12 cycloalkylene group is preferable and a C3-C6 cycloalkylene group is more preferable. Preferable specific examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Moreover, as a C3-C20 cycloalkenylene group, a C3-C12 cycloalkenylene group is preferable and a C3-C6 cycloalkenylene group is more preferable. Preferable specific examples include a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include arylene groups such as a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

  The alkylene-cycloalkylene-alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, an cycloalkylene group having 3 to 12 carbon atoms, and an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 1 to 6 carbon atoms and 3 to 3 carbon atoms. 6 cycloalkylylene-C1-C6 alkylene groups are particularly preferred. The cycloalkylene-alkylene-cycloalkylene group is preferably a cycloalkylene group having 3 to 12 carbon atoms, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, and a cycloalkylene group having 3 to 6 carbon atoms. A C1-C6 alkylene-C3-C6 cycloalkylene group is particularly preferred.

  The alkylene-arylene-alkylene group is preferably an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 14 carbon atoms, or an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 6 to 10 carbon atoms. The arylene-alkylene group having 1 to 6 carbon atoms is particularly preferable.

  Although the manufacturing method of ketimine is not specifically limited, For example, it can obtain by stirring and dehydrating a ketone and amine at room temperature or under heating. The reaction temperature is preferably 20 ° C to 150 ° C, more preferably 50 ° C to 110 ° C. The reaction time is preferably 2 hours to 24 hours, and more preferably 2 hours to 5 hours.

  Ketimine can obtain a commercial item, for example, H-3, H-30 (above, Mitsubishi Chemical Corporation) is mentioned.

  A ketimine compound can be used individually or in mixture of 2 or more types. As a content rate of the ketimine compound in the said radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts. Is more preferable. By making the content rate of a ketimine compound into the said specific range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

[Block isocyanate compounds]
A block polyisocyanate compound is a compound in which an isocyanate group is reacted with an active hydrogen group-containing compound (blocking agent) to make it inert at room temperature, and when this is heated, the blocking agent dissociates and the isocyanate group is regenerated. It has something. When the radiation-sensitive resin composition contains a block polyisocyanate, an isocyanate-hydroxyl group crosslinking reaction proceeds as an effective crosslinking agent, and the storage stability and low-temperature firing of the radiation-sensitive resin composition are high. Can be compatible.

  The block polyisocyanate compound is obtained by a known reaction between a polyisocyanate derived from an aliphatic or alicyclic diisocyanate and a compound having an active hydrogen (blocking agent).

  Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, 2,4,4-trimethyl-1,6-diisocyanate. Natohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexylmethane diisocyanate, norbornene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5 -Naphthalene diisocyanate, tolidine diisocyanate, xylidine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate Over DOO, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate.

As a commercial item, for example, as an isocyanate group blocked with an oxime of methyl ethyl ketone, Duranate TPA-B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, MF-B80M (above, Asahi Kasei Chemicals);
As the isocyanate group blocked with active methylene, Duranate MF-K60X (Asahi Kasei Kogyo Co., Ltd.);
As a block body of an isocyanate compound having a (meth) acryloyl group, Karenz MOI-BP and Karenz MOI-BM (above, Showa Denko KK) can be mentioned. Among these, when Duranate E402-B80T and MF-K60X are used, high flexibility is expressed, and it is preferable to use it in a mixed system with others because its hardness can be freely controlled.

  Examples of the polyisocyanate derived from diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, and allophanate type polyisocyanate. From the viewpoint of curability, isocyanurate type polyisocyanate is preferable.

  Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, urea compounds, oxime compounds, amines. Compounds, imine compounds, pyridine compounds and the like.

Examples of alcohol compounds include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like;
Examples of phenolic compounds include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester and the like;
Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like;
Examples of mercaptan compounds include butyl mercaptan and dodecyl mercaptan;
Examples of the acid amide compound include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam and the like;
Examples of acid imide compounds include succinimide and maleic imide;
Examples of imidazole compounds include imidazole and 2-methylimidazole;
Examples of the pyrazole compound include 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-ethylpyrazole and the like;
Examples of urea compounds include urea, thiourea, and ethylene urea;
Examples of oxime compounds include formal oxime, acetal oxime, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime and the like;
Examples of amine compounds include diphenylamine, aniline, carbazole and the like;
Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline.

  A block polyisocyanate compound can be used individually or in mixture of 2 or more types. As a content rate of the block polyisocyanate compound 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 3 mass parts-20 mass parts are more. preferable. By making the content rate of a block polyisocyanate compound into the said range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

[Imidazole ring-containing compound]
As the imidazole ring-containing compound, at least one selected from the group consisting of compounds represented by the following formula (15) can be used.

In the above formula (15), A ⁵ , A ⁶ , A ⁷ and R ⁵⁴ each independently represent a hydrogen atom or a linear, branched or cyclic group having 1 to 20 carbon atoms which may have a substituent. It is a hydrocarbon group. A ⁶ and A ⁷ may be connected to each other to form a ring.

Examples of the linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms represented by A ⁵ , A ⁶ , A ⁷ and R ⁵⁴ include a methyl group, an ethyl group, an n-propyl group and an i-propyl group. , N-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group An alkyl group having 1 to 20 carbon atoms, such as
A cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
Aryl groups having 6 to 20 carbon atoms such as phenyl group, toluyl group, benzyl group, methylbenzyl group, xylyl group, mesityl group, naphthyl group, anthryl group;
Examples thereof include a bridged alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclododecyl group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group, and a butyladamantyl group.

The hydrocarbon group may be substituted. Specific examples of the substituent include
Hydroxyl group;
Carboxyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl A hydroxyalkyl group having 1 to 4 carbon atoms such as a 4-hydroxybutyl group;
C1-C4 alkoxyl such as methoxyl group, ethoxyl group, n-propoxyl group, i-propoxyl group, n-butoxyl group, 2-methylpropoxyl group, 1-methylpropoxyl group, t-butoxyl group, etc. Group;
A cyano group;
A cyanoalkyl group having 2 to 5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group;
An alkoxycarbonyl group having 2 to 5 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a t-butoxycarbonyl group;
An alkoxycarbonylalkoxyl group having 3 to 6 carbon atoms such as a methoxycarbonylmethoxyl group, an ethoxycarbonylmethoxyl group, a t-butoxycarbonylmethoxyl group;
Halogen atoms such as fluorine and chlorine;
Examples thereof include fluoroalkyl groups such as a fluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

Preferred examples of the ring formed by connecting A ⁶ and A ⁷ to each other include an aromatic ring and a saturated or unsaturated nitrogen-containing heterocyclic ring having 2 to 20 carbon atoms. Examples of the imidazole ring-containing compound in the case where the ring formed by connecting A ⁶ and A ⁷ to each other is a benzene ring include compounds represented by the following formula (16).

In the above formula ^{(16), R 54} and ^{A 5} is as defined in the above formula (15). R ⁵⁵ to R ⁵⁸ are each independently a straight chain having 1 to 20 carbon atoms that may have a substituent, a branched or cyclic hydrocarbon group. As the hydrocarbon group represented by R ⁵⁵ to R ^58, it may be the same as the hydrocarbon group in the above formula (15).

  As the imidazole ring-containing compound, 2-phenylbenzimidazole, 2-methylimidazole, and 2-methylbenzimidazole are preferable. An imidazole ring containing compound can be used individually or in mixture of 2 or more types. As a content rate of an imidazole ring containing compound, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.2 mass part-5 mass parts are more preferable. By making the content rate of an imidazole ring containing compound into the said specific range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

[Inclusion compound]
The “inclusion compound” referred to in this specification is an inclusion of an imidazole compound or a benzimidazole compound with a tetrakisphenol compound represented by the following formula (17) or a dicarboxylic acid compound represented by the formula (18). Compound.

In said formula (17), X is a single bond, a methylene group, or a C2-C6 alkylene group. R ^{59 to} R ⁶⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an optionally substituted phenyl group, a halogen atom, or an alkoxy group having 1 to 12 carbon atoms.
In the above formula ^{(18), R 67} represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a nitro group or a hydroxyl group.

  The tetrakisphenol compound represented by the above formula (17) is preferably a compound represented by the above formula (17-1). By using a tetrakisphenol compound represented by the above formula (17-1), the storage stability is further improved and curing at low temperatures can be promoted.

In the above formula (17-1), X and ^R 59 ^{to R 66} is as defined in the above formula (17).

  The tetrakisphenol compound is not particularly limited as long as it is a compound represented by the above formula (17-1). For example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2 , 2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3 -Chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-4-hydroxy) Phenyl) ethane, 1,1,2,2-tetrakis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-4-hydro) Loxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ) Ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1 , 2,2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2 , 2-tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane 1,1,2,2-tetrakis (3-tert-butyl-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxy) Phenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis [(4-hydroxy-3-phenyl) phenyl] Ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis ( 3,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5- Dichloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-4-hydroxyphenyl) ) Propane, 1,1,3,3-tetrakis (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1 , 3,3-tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-t-butyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) Propane, 1,1,4,4-tetrakis (4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis ( 3,5-dimethyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dichloro- 4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) butane 1,1,4,4-tetrakis (3-bromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dibromo-4-hydroxyphenyl) Butane, 1,1,4,4-tetrakis (3-t-butyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) Butane, tetrakis (4-carboxyphenyl) ethane, tetrakis (4-carboxyphenyl) ethanetetramethyl ester, tetrakis (4-carboxyphenyl) ethanetetraethyl ester, tetrakis (4-carboxyphenyl) ethanetetra n-propyl ester, tetrakis (4 -Carboxyphenyl) ethane tetrabenzyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane tetramethyl ester, tetrakis (3,5-dimethyl- 4-carboxyph Enyl) ethane tetraethyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethanetetra n-propyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane tetrabenzyl ester, tetrakis (4-carboxyphenyl) Ethanetetrasodium salt, tetrakis (4-carboxyphenyl) ethanetetrapotassium salt, tetrakis (3-carboxyphenyl) ethane, tetrakis (3-carboxyphenyl) ethanetetramethyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ) Ethane, tetrakis (3-carboxyphenyl) ethane tetraethyl ester, tetrakis (3-carboxyphenyl) ethane tetra n-propyl ester, tetrakis (3-carboxypheny) ) Ethane tetrabenzyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ethane, tetrakis (3-carboxy-4,5-dimethylphenyl) ethane tetramethyl ester, tetrakis (3-carboxy-4,5-dimethyl) Phenyl) ethane tetraethyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ethane tetra n-propyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane tetrabenzyl ester, tetrakis (3-carboxyphenyl) Examples include ethane tetrasodium salt and tetrakis (3-carboxyphenyl) ethane tetrapotassium salt.

  Among these, when an imidazole compound or a benzimidazole compound included by 1,1 ′, 2,2′-tetrakis (4-hydroxyphenyl) ethane is used, the radiation-sensitive resin composition is obtained at room temperature. It is preferable because it is excellent in storage stability and the curing accelerator is easily released upon heating.

  The dicarboxylic acid compound is not particularly limited as long as it is a compound represented by the above formula (2). For example, 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, 5-methylisophthalic acid, 5-methoxyisophthalic acid, Examples include 4-nitroisophthalic acid, 4-hydroxyisophthalic acid, 4-methylisophthalic acid, 4-methoxyisophthalic acid and the like. Of these, 5-nitroisophthalic acid and 5-hydroxyisophthalic acid are preferred.

  Since the imidazole compound and the tetrakisphenol compound or dicarboxylic acid compound form a stable inclusion compound, the storage stability of the radiation-sensitive resin composition at room temperature is improved. Moreover, since an imidazole compound is excellent in the reactivity with an epoxy group, it contributes to 200 degreeC or less low temperature hardening.

  Examples of the imidazole compound include compounds represented by the above formula (15) described in the section of the imidazole ring-containing compound.

  Specific examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1 , 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2 Ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'- Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl-)-ethyl-s-triazine, 2,4-diamino-6- [2 ′ -Ethyl-4-imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethy Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazo Examples include lithium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, and the like.

  The imidazole compound preferably has one or more substituents having 1 to 6 carbon atoms. Since such an imidazole compound is stably included, it does not adversely affect the storage stability of the radiation-sensitive resin composition, and since the steric hindrance is small, the reactivity is excellent and the inclusion is disintegrated. It can exhibit low temperature curability.

Examples of the imidazole compound having one or more substituents having 1 to 6 carbon atoms include imidazole compounds having one substituent having 1 to 6 carbon atoms such as 2-methylimidazole and 2-phenylimidazole;
Examples thereof include imidazole compounds having two substituents having 1 to 6 carbon atoms such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

  The method for including the imidazole compound with the tetrakisphenol compound or the dicarboxylic acid compound is not particularly limited, and examples thereof include the method described in JP-A No. 11-071449.

  Among these imidazole compounds, 2-phenyl-4-methyl-5-hydroxymethylimidazole is preferable from the viewpoint that both the storage stability of the composition and the acceleration of curing can be achieved at a high level.

  Examples of the benzimidazole compound include compounds represented by the above formula (16) described in the section of the imidazole ring-containing compound.

  Examples of the benzimidazole compound include 2-methylbenzimidazole, 4-methylbenzimidazole, 5-methylbenzimidazole, 6-methylbenzimidazole, 7-methylbenzimidazole, 2-methyl-6-methylbenzimidazole, and 2-methyl. -6-methylbenzimidazole, 2-methyl-5-methylbenzimidazole, 2-methyl-5-methylbenzimidazole, 2-ethyl-6-methylbenzimidazole, 2-methyl-6-ethylbenzimidazole, 2-ethyl Examples include -5-methylbenzimidazole and 2-methyl-5-ethylbenzimidazole.

  Of these, 2-methylbenzimidazole, 2-methyl-6-methylbenzimidazole, and 2-methyl-5-methylbenzimidazole are used from the viewpoint that both the storage stability and curing acceleration of the composition can be achieved at a high level. preferable.

  The benzimidazole compound preferably has one or more substituents having 1 to 6 carbon atoms. Since such an imidazole compound is stably included, it does not adversely affect the storage stability of the radiation-sensitive resin composition, and since the steric hindrance is small, the reactivity is excellent and the inclusion is disintegrated. It can exhibit low temperature curability.

  Examples of the benzimidazole compound having one or more substituents having 1 to 6 carbon atoms include benzimidazole compounds having one substituent having 1 to 6 carbon atoms such as 2-methylbenzimidazole; Examples thereof include benzimidazole compounds having two substituents having 1 to 6 carbon atoms such as methylbenzimidazole and 2-methyl-5-methylbenzimidazole.

  The inclusion compound can be used alone or in admixture of two or more. As a content rate of an inclusion compound, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an inclusion compound into the said specific range, the storage stability and low-temperature baking of the said radiation sensitive resin composition can be made compatible at a higher level.

<Other optional components>
In addition to the above [A] alkali-soluble resin, [B] quinonediazide compound, and [C] curing agent, the radiation-sensitive resin composition includes a surfactant and an adhesive as necessary within a range not impairing the effects of the present invention. Optional components such as an auxiliary agent, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[Surfactant]
The surfactant can be used to further improve the film-forming property of the radiation sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group at at least one of the terminal, main chain and side chain is preferable. 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 fluoro-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 0.7 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.

[Adhesion aid]
Adhesion aids can be used to further improve the adhesion between the resulting pattern and the substrate. As the 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-methacryloxypropyltrimethoxy Examples include silane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  As the usage-amount of an adhesion assistant, 20 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 15 mass parts or less are more preferable. When the usage-amount of an adhesion assistant exceeds 20 mass parts, there exists a tendency for it to become easy to produce the image development remainder.

[Heat resistance improver]
Examples of the 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-propoxymethyl) glycoluril, N, N, N ′, Examples thereof include N′-tetra (n-butoxymethyl) glycoluril, N, N, N ′, N′-tetra (t-butoxymethyl) glycoluril and the like. Of these N- (alkoxymethyl) glycoluril compounds, 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 can be mentioned. Of these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is preferred. Examples of commercially available products include Nicarac N-2702 and MW-30M (Sanwa Chemical Co., Ltd.).

  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 [A] alkali-soluble resin. When the compounding quantity of a heat resistance improver exceeds 50 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

[Heat-sensitive acid generator]
A heat-sensitive acid generator is defined as a compound that can release an acidic active substance that acts as a catalyst in curing [A] alkali-soluble resin by applying heat. By using such a heat-sensitive acid generator, the cured reaction of [A] alkali-soluble resin in the heating step after development of the radiation-sensitive composition is further promoted, and a cured film having excellent surface hardness and heat resistance is obtained. Can be formed.

  The heat-sensitive acid generator includes ionic compounds and nonionic compounds. As the ionic compound, those containing no heavy metal or halogen ion are preferable. Examples of the ionic thermosensitive acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethylsulfonium, benzyl. -4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, and these methanesulfonic acids Examples thereof include salts, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, hexafluorophosphonate and the like. Moreover, as a commercial item of benzylsulfonium salt, for example, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L, SI- 145L, SI-150L, SI-160L, SI-180L (Sanshin Chemical Industry Co., Ltd.) and the like.

  Examples of nonionic heat-sensitive acid generators include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphoric acid ester compounds, sulfonimide compounds, and sulfonebenzotriazole compounds. .

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4, 6-bis (trichloromethyl) -s-triazine is mentioned.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. Is mentioned.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like. Preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and 4-chlorophenyl-4-methylphenyldisulfone compound.

  Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred sulfonic acid ester compounds include benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and 2,6-dinitrobenzylbenzenesulfonate. Examples of commercially available products of iminosulfonate include PAI-101, PAI-106 (above, Midori Chemical Co., Ltd.), CGI-1311 (Ciba Specialty Chemicals Co., Ltd.) and the like.

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105”, Midori Chemical Co., Ltd.), N- (camphorsulfonyloxy) succinimide (trade name “SI-106”, Midori Chemical). ), N- (4-methylphenylsulfonyloxy) succinimide (trade name “SI-101”, Midori Chemical Co., Ltd.), N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyl) Oxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) Ruimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105”, Midori Chemical Co., Ltd.), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- ( 2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-100”, Midori Chemical Co., Ltd.), N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2, -Dicarboxylimide (trade name “NDI-101”, Midori Chemical Co., Ltd.), N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name) “NDI-105”, Midori Chemical Co., Ltd.), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109”, Midori Kagaku), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-106”, Midori Kagaku), N- ( Camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2 -Trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2. 2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-e -2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy -2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoro Methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluoropheny Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-105”, Midori Chemical Co., Ltd.), N- (camphorsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-106”, Midori Chemical Co., Ltd.), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101”) ”, Midori Chemical Co., Ltd.), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (trade name“ NAI-100 ”, Midori Chemical Co., Ltd.), N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboximide, N -(4-Fluorophenylsulfonyloxy) naphthy Rudicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI”) -109 ", Midori Chemical Co., Ltd.), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (trade name" NAI- 1004 ", Midori Chemical Co., Ltd.), N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) ) Naphthyl dicarboxyl imide, N- (octyl sulfonyloxy) naphthyl dicarboxyl imide, N- (nonyl sulfonyloxy) naphthyl dicarboxylic imide and the like.

  Examples of other heat-sensitive acid generators include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium. And tetrahydrothiophenium salts such as trifluoromethanesulfonate.

  Among these heat-sensitive acid generators, [A] benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 1- (4,7-dibutoxy-1-naphthalenyl) from the viewpoint of the catalytic action of the curing reaction of [A] alkali-soluble resin. ) Tetrahydrothiophenium trifluoromethanesulfonate and N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide are more preferred.

  As a usage-amount of a thermosensitive acid generator, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1 mass part-5 mass parts are more preferable. By making the usage-amount of a thermosensitive acid generator into the said range, the sensitivity of a radiation sensitive composition can be optimized, and a cured film with high surface hardness can be formed, maintaining transparency.

<Method for preparing radiation-sensitive resin composition>
The radiation sensitive resin composition of the present invention is prepared by uniformly mixing [A] alkali-soluble resin, [B] quinonediazide compound, [C] curing agent and, if necessary, optional components. This radiation-sensitive resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent.

  As a solvent used for the preparation of the radiation sensitive resin composition, a solvent that uniformly dissolves essential components and optional components 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 manufacture the above-mentioned [A] alkali-soluble resin is mentioned.

  Among such solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, and the like. , Ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono -N-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (Poly) alkylene glycol monoalkyl ethers of

  Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-propyl Acetic acid (poly) alkylene glycol monoalkyl ethers such as ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate ;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, 3-methyl-3-methoxybutylpropio Nate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 2 -Other esters such as ethyl oxobutyrate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate Le acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred. The solvent can be used alone or in combination of two or more.

  Furthermore, together with the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination. The said high boiling point solvent can use single or 2 types or more.

  The content of the solvent is not limited, but the total concentration of each component excluding the solvent of the radiation-sensitive resin composition is 5% by mass from the viewpoint of applicability and stability of the resulting radiation-sensitive resin composition. The amount of ˜50% by mass is preferable, and the amount of 10% by mass to 40% by mass is more preferable. 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 a 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 diameter of about 0.5 μm.

<Method for forming cured film>
The radiation-sensitive resin composition is an interlayer insulating film having both low-temperature firing and storage stability, high radiation sensitivity, and excellent surface hardness, solvent resistance, and relative dielectric constant suitable for flexible displays. A cured film as a protective film or a spacer can be formed.

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) 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.

  When a cured film is formed by the above process using the radiation-sensitive resin composition, a pattern is formed by exposure / development using radiation sensitivity, so that a fine and elaborate pattern can be easily formed. Can do. Moreover, the cured film formed using the said radiation sensitive resin composition has sufficient surface hardness etc. even if it is low-temperature baking. Hereinafter, each process is explained in full detail.

[(1) Process]
In this step, the solution of the radiation sensitive resin composition is applied to the substrate surface, and the solvent is removed preferably by pre-baking to form a coating film of the radiation sensitive resin composition. Examples of the substrate that can be used include a glass substrate, a silicon wafer, a plastic substrate, and a substrate on which various metals are formed. Examples of the plastic substrate include resin substrates made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

  As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet method can be employed. Among these coating methods, spin coating, bar coating, and slit die coating are preferable. The prebaking conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 ° C. to 90 ° C. for 30 seconds to 10 minutes. The film thickness of the coating film to be formed is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm as a value after pre-baking.

[(2) Process]
In this step, the coating film formed in step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable. The exposure ^{amount, 30J / m 2 ~1,500J / m} 2 is preferred.

[(3) Process]
In this step, development can be performed on the coating film irradiated with radiation in step (2) to remove a portion irradiated with radiation, and a desired pattern can be formed. Examples of the developer used for the development processing include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the aqueous alkali solution described above, or an alkaline aqueous solution containing a small amount of various organic solvents for dissolving the radiation-sensitive resin composition, Can be used as Furthermore, as a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but can be, for example, 30 seconds to 120 seconds.
After this development step, the patterned coating film is rinsed by running water washing, and subsequently irradiated with a high-pressure mercury lamp or the like (post-exposure) to remain in the coating film [B It is preferable to perform a decomposition treatment of the quinonediazide compound.

[(4) Process]
In this step, the coating film is cured by heating and baking treatment (post-baking treatment) using a heating device such as a hot plate or oven that bakes the coating film developed in step (3). Do. The exposure amount in the post-exposure is preferably about 2,000 J / m ^{2 to} 5,000 J / m ² . Moreover, it is preferable that the calcination temperature in this process is 200 degrees C or less. In addition to the ability to form a fine pattern using radiation sensitivity, the formation method can be used to form a cured film such as an interlayer insulating film on a plastic substrate of a flexible display by being capable of firing at such a low temperature. Preferably used. As baking temperature, 120 to 180 degreeC is more preferable, and 120 to 150 degreeC is especially preferable. The firing time varies depending on the type of heating equipment, but for example, 5 to 40 minutes may be used for heat treatment on a hot plate, and 30 to 80 minutes for heat treatment in an oven. Particularly preferably, it is within 30 minutes when the heat treatment is performed on a hot plate, and within 60 minutes when the heat treatment is performed in an oven. In this manner, a patterned coating film corresponding to a target cured film such as an interlayer insulating film can be formed on the surface of the substrate.

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

<[A] Synthesis of alkali-soluble resin>
[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 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 16 parts by weight of methacrylic acid as the compound (A1), 40 parts by weight of glycidyl methacrylate as the compound (A2), 10 parts by weight of styrene as the compound (A4), tricyclomethacrylate [5.2.1.0 ^2,6 ] Charge 14 parts by weight of decan-8-yl and 20 parts by weight of 2-methylcyclohexyl acrylate, purge with nitrogen, raise the temperature of the solution to 70 ° C. while gently stirring, and maintain this temperature for 4 hours for polymerization. As a result, a solution containing the copolymer (A-1) was obtained. The obtained polymer solution had a solid content concentration of 34.4%, and the copolymer (A-1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[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 methyl ethyl ether. Subsequently, 13 parts by weight of methacrylic acid as the (A1) compound, 40 parts by weight of glycidyl methacrylate as the (A2) compound, 10 parts by weight of α-methyl-p-hydroxystyrene as the compound (A3), and 10 parts by weight of styrene as the (A4) compound Part, 12 parts by mass of tetrahydrofurfuryl methacrylate, 15 parts by mass of N-cyclohexylmaleimide and 10 parts by mass of n-lauryl methacrylate, and after replacing with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring. A solution containing the copolymer (A-2) was obtained by polymerization while maintaining the temperature for 5 hours. The obtained polymer solution had a solid content concentration of 31.9%, Mw of the copolymer (A-2) was 8,000, and molecular weight distribution (Mw / Mn) was 2.3.

[Comparative Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of AIBN and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 80 parts by weight of allyl methacrylate and 20 parts by weight of methacrylic acid as the (A1) compound were charged, the temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was maintained for 5 hours to perform polymerization. A solution containing the copolymer (CA-1) was obtained. The obtained polymer solution had a solid content concentration of 31.0%, and the copolymer (CA-1) had an Mw of 10,000 and a molecular weight distribution (Mw / Mn) of 2.3.

<Preparation of radiation-sensitive resin composition>
[Example 1]
The amount of the solution containing the copolymer (A-1) corresponding to 100 parts by mass (solid content) of the copolymer, [B] quinonediazide compound, (B-1) 30 parts by mass, and (C-1) After adding 0.5 parts by mass and further adding diethylene glycol methyl ethyl ether as a solvent so that the solid content concentration becomes 30% by mass, the mixture is filtered through a membrane filter having a pore size of 0.2 μm, whereby a radiation sensitive resin composition A product was prepared.

[Examples 2 to 13 and Comparative Examples 1 and 2]
By mixing the components of the types and blending amounts shown in Table 1 and adding diethylene glycol ethyl methyl ether as a solvent so that the solid content concentration is 30% by mass, by filtering with a membrane filter having a pore size of 0.2 μm, Each radiation sensitive resin composition was prepared. In addition, “-” in the column represents that the corresponding component was not used.

The detail of each component used for preparation of the radiation sensitive resin composition shown in Table 1 is shown below.
<[B] quinonediazide compound>
B-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate B-2 with sulfonic acid chloride (2.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Condensate with

<[C] Curing agent>
C-1: trioctylamine C-2: 2-phenylbenzimidazole C-3: tetramethylammonium chloride C-4: butyltriphenylphosphonium thiocyanate C-5: 1,8-diazabicyclo [5,4,0]- Undecene-7 (DBU) toluenesulfonate C-6: N, N′-diacetyl-p-phenylenediamine C-7: N, N-bis (1,3-dimethylbutylidene) xylenediamine C-8: TPA-B80E (Asahi Kasei Chemicals Corporation, HDI block isocyanate, solid content 80%, effective isocyanate content 12.3%)
C-9: 4,4′-diaminodiphenyl sulfone C-10: ethyl 3-aminobenzenesulfonate C-11: 5-nitroisophthalic acid and 2-phenyl-4-methyl-5-hydroxymethylimidazole 2: 1 Inclusion compound c-1 mixed with: octylamine

<Evaluation>
The following evaluation was performed about the prepared radiation sensitive resin composition and the cured | curing material formed below. The results are shown in Table 1.

[Storage stability]
The obtained radiation-sensitive resin composition was left in an oven at 40 ° C. for 1 week, and the viscosity before and after heating was measured to determine the rate of change in viscosity (%). At this time, the viscosity change rate was defined as storage stability, and when it was 5% or less, the storage stability was judged to be good, and when it exceeded 5%, the storage stability was judged to be poor. The viscosity was measured at 25 ° C. using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.).

[sensitivity]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a silicon substrate using a spinner, the film was pre-baked on a hot plate at 90 ° C. for 2 minutes to have a film thickness of 3.0 μm. A coating film was formed. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, followed by washing with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount capable of forming a line and space pattern having a width of 10 μm was measured. When this value was less than 850 J / m ² , it was judged that the sensitivity was good.

[Solvent resistance]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a silicon substrate using a spinner, the film was pre-baked on a hot plate at 90 ° C. for 2 minutes to have a film thickness of 3.0 μm. A coating film was formed. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated at 150 ° C. for 30 minutes for Examples 1 to 13 and Comparative Examples 1 and 2 on a hot plate. Comparative Examples 3 and 4 were heated at 150 ° C. for 60 minutes. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate was shown below. Calculated from the equation, this was defined as solvent resistance.
Film thickness change rate = {(t1-T1) / T1} × 100 (%)
When the absolute value of this value was less than 5%, the solvent resistance was judged to be excellent.

[surface hardness]
About the board | substrate which has the cured film formed by evaluation of solvent resistance, the pencil hardness of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990, and this was made into surface hardness. When this value was 3H or more, the surface hardness as a cured film was good, and the radiation-sensitive resin composition used to form the cured film was judged to have sufficient curability.

[Relative permittivity]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a SUS substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to have a film thickness of 3.0 μm. A coating film was formed. Using a Canon MPA-600FA exposure machine, the coating film obtained was exposed so that the accumulated irradiation amount was 9,000 J / m ^2, and this substrate was heated in a clean oven at 150 ° C. for 30 minutes. Thus, a cured film was formed on the SUS substrate. A dielectric constant measurement sample was prepared by forming a Pt / Pd electrode pattern on the cured film by vapor deposition. With respect to the substrate having this electrode pattern, the relative dielectric constant was measured by the CV method at a frequency of 10 kHz using a Yokogawa-Hewlett Packard HP16451B electrode and a HP4284A precision LCR meter. When this value was 3.9 or less, the dielectric constant was judged to be good.

  From the results of Table 1, the radiation-sensitive resin composition of the present invention has high radiation sensitivity, and can obtain a cured film having high surface hardness by heating at low temperature for a short time, and the cured film is excellent It was also found that it has both solvent resistance and relative dielectric constant.

  According to the radiation-sensitive resin composition of the present invention, surface hardness and solvent resistance suitable for use in a radiation-sensitive resin composition having a low radiation rate and storage stability and having high radiation sensitivity, and for flexible displays. It is possible to provide a cured film as an interlayer insulating film, a protective film, or a spacer that is excellent in properties and relative dielectric constant.

Claims (6)

[A] (A1) an alkali-soluble resin obtained by copolymerizing at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and (A2) an epoxy group-containing unsaturated compound;
[B] quinonediazide compound, and [C] a compound represented by the following formula (1), a compound represented by the following formula (2), an amine salt, a phosphonium salt, an amidine salt, an amide compound, a ketimine compound, and a blocked isocyanate compound A radiation-sensitive resin composition containing at least one curing agent selected from the group consisting of an imidazole ring-containing compound and an inclusion compound.

(In formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, a nitro group, an alkyloxysulfonyl group, a trifluoromethyl group, or an amino group, provided that at least one of R ^{1 to} R ⁶ One of them is a nitro group, an alkyloxysulfonyl group or a trifluoromethyl group , and at least one of R ^{1 to} R ⁶ is an amino group, and all or part of the hydrogen atoms are carbon atoms. It may be substituted with an alkyl group of formula 1-6.
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 1 to 6 carbon atoms. A is a single bond, 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, in the methylene group and alkylene group, all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group. )   [C] The radiation-sensitive resin composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of compounds represented by the above formulas (1) and (2).   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 1, Claim 2 or Claim 3 on a board | substrate,
(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.   (4) The method for forming a cured film according to claim 4, wherein the firing temperature in the step 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.