JP2006048021A - Radiation sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new uncolored radiation sensitive resin composition having a high transmittance to visible light, capable of easily forming a cured resin pattern of an objective shape because of a wide range of proper development condition, and capable of forming a cured resin pattern excellent in chemical resistance because the composition has a crosslinkable group, and to provide a cured resin pattern formed using the radiation sensitive resin composition. <P>SOLUTION: The radiation sensitive resin composition contains: a copolymer (A) containing a constitutional unit (a1) derived from an unsaturated compound having at least one group selected from active methylene and active methine groups and a constitutional unit (a2) derived from an unsaturated compound having a group which reacts under the action of light and/or heat; and a quinonediazido compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation sensitive resin composition.

The radiation-sensitive resin composition is, for example, a TFT insulating film used in a thin film transistor (hereinafter referred to as TFT) liquid crystal display device or an organic EL display device, or a diffuse reflection used in a reflective TFT substrate. It is useful as a material for forming a cured resin pattern including a plate, an organic EL insulating film, a protective film of a solid-state imaging device (hereinafter, sometimes referred to as CCD), and the like (see Patent Document 1). As for the shape of the cured resin pattern, for example, the shape of the intended cross-section is designed for each application, such as a tapered shape or an inversely tapered shape, so the cured resin pattern is formed using the radiation-sensitive resin composition. In some cases, it is necessary to form a cured resin pattern according to the designed cross-sectional shape.
Further, when forming a pattern using a radiation-sensitive resin composition containing a conventional quinonediazide compound, the composition was applied onto a substrate, the coating was exposed through a mask, developed, and dried. Later, the formed pattern is exposed to light, but this pattern is exposed only to make the pattern transparent by decomposing the quinonediazide compound remaining in the pattern (Patent Literature). 2 and Patent Document 3).
Furthermore, in order to obtain a brighter display image, a high transmittance with respect to visible light is required (see, for example, Patent Document 1).

  Moreover, it is known that the binder resin whose alkali-soluble group used for the conventional radiation sensitive resin composition is acrylic acid or methacrylic acid has a narrow development margin. In order to solve this problem, a copolymer having an active methylene group has been proposed (Patent Document 4).

JP-A-9-152625 (see paragraph numbers 0001 and 0010) Japanese Patent Laid-Open No. 11-52560 (see paragraph number 0039) JP 2001-330953 A (see paragraph 0071) Japanese Patent Publication No. 6-54382 (page 3, left column, line 15 to right column, line 17)

  The object of the present invention is that there is no coloring and a high transmittance for visible light, and the range of appropriate development conditions is wide. Therefore, a cured resin pattern having a desired shape can be easily formed, and since it has a crosslinking group, The object is to provide a new radiation-sensitive resin composition capable of forming a cured resin pattern excellent in chemical properties, and a cured resin pattern formed using the radiation-sensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

  That is, the present invention relates to a structural unit (a1) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, and a group that is cured by the action of light and / or heat. There is provided a radiation-sensitive resin composition containing a copolymer (A) containing a structural unit (a2) derived from an unsaturated compound having at least one radiation-sensitive compound.

  Moreover, this invention provides the liquid crystal display device containing the cured resin pattern formed using the said radiation sensitive resin composition, and the said cured resin pattern.

  The radiation-sensitive resin composition of the present invention can provide a cured resin pattern that is not colored and has a high transmittance for visible light. Moreover, when the radiation sensitive resin composition of this invention is used, the cured resin pattern of the target shape can be formed easily and it is excellent also in productivity of a TFT substrate.

  The copolymer (A) in the present invention is a structural unit derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group [hereinafter abbreviated as (a1). is there. ], A structural unit derived from unsaturation having a group that reacts by the action of light and / or heat [hereinafter, it may be abbreviated as (a2). ].

  As the unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, which leads to the structural unit (a1), a compound represented by the formula (I) or the formula (II) Is mentioned.

[In Formula (I) and Formula (II), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.
R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ³ represents a divalent group represented by any one of formulas (1-1) to (1-3).

R ⁴ represents a group represented by any one of formulas (1-4) to (1-7).

R ¹ in Formula (1-4) and Formula (1-5) represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.
X represents Formula (1-8) or Formula (1-9). ]

Here, as a C1-C24 hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentyl group, a hexyl group, a cyclohexyl group, and a dicyclopentanyl group.

  Specific examples of the compound represented by the formula (I) or the formula (II) include the following compounds.

  Especially, as a compound which guide | derived a structural unit (a1), the compound represented by 2- (methacryloyloxy) ethyl acetoacetate [Formula (1)] is preferable.

  The unsaturated compound having a group that reacts by the action of light and / or heat leading to the structural unit (a2) includes an epoxy group, an oxetanyl group, and an unsaturated group as a group that reacts by the action of light and / or heat. Are preferred.

  Examples of the compound having an epoxy group and an unsaturated group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (3,4-epoxycyclohexyl) methyl (meth) acrylate. And epoxidized products of dicyclopentenyl (meth) acrylate, and preferably glycidyl (meth) acrylate.

  Examples of the compound having an oxetanyl group and an unsaturated group include compounds represented by formula (3-1) or formula (3-2).

[In Formula (3-1) and Formula (3-2), R and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^{6 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
n represents an integer of 1 to 6. ]

  Here, as a C1-C4 alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example.

R and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, or an ethyl group.
R ^{6 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, preferably a hydrogen atom, a methyl group, or an ethyl group.

  Specific compounds for deriving the structural unit (a2) include, for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) ) Acrylate, epoxidized product of dicyclopentenyl (meth) acrylate, 3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl Oxetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyloxetane, 3- Methyl-3- (meth) ac Roxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2- Examples include pentafluoroethyl-3- (meth) acryloxyethyl oxetane, and preferably 3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (Meth) acryloxymethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 2-pentafluoroethyl-3- (meth) acryl Loxymethyloxetane, 3-methyl-3- (meth) actyl Roxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2- And pentafluoroethyl-3- (meth) acryloxyethyl oxetane.

Other groups that react by the action of light and / or heat include groups having an unsaturated bond. As said unsaturated bond, an unsaturated double bond and an unsaturated triple bond are mentioned, Preferably an unsaturated double bond is mentioned.
In order to introduce a group having an unsaturated bond into the copolymer (A), for example, a compound having an unsaturated bond and a carboxyl group in the same molecule is converted into the structural unit (a2) of the copolymer (A). It can introduce | transduce as a side chain of a copolymer (A) by making it further react with the group which reacts by the effect | action of light and / or heat | fever.
For example, when a (meth) acryl group is introduced as a group that reacts by the action of light and / or heat, the following method is exemplified.
A structural unit (a1) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group; an unsaturated compound (a21) having an oxetanyl group; and an unsaturated group having an epoxy group An unsaturated compound having at least one selected from the group consisting of the compound (a22) is reacted to obtain a copolymer, and the oxetanyl group part or epoxy group part of the copolymer and meth (acrylic) acid The copolymer (A) which has a polymerizable double bond as a side chain of a copolymer (A) can be obtained by making it react with the carboxyl group. In the reaction of the oxetanyl group part or epoxy group part of the copolymer with the carboxyl group of meth (acrylic acid), the amount of the meth (acrylic acid) reacted is based on the amount of the oxetanyl group part or epoxy group part. The molar ratio is preferably 1: 0.05 to 1: 0.95, more preferably 1: 0.1 to 1: 0.5. In addition, the quantity with which a meth (acrylic) acid is made to react can be changed suitably with the acid value, molecular weight, etc. of the copolymer (A) obtained.
Also, other compounds having an unsaturated group and a carboxyl group in the same molecule can be reacted in the same manner as described above to obtain a copolymer (A) having a polymerizable double bond at the terminal. it can.

  As the unsaturated compound having an oxetanyl group that leads to the structural unit (a21), 3-ethyl-3-methacryloxymethyloxetane is particularly preferable.

The copolymer (A) can further have a structural unit (a3) copolymerizable with the structural unit (a1) and the structural unit (a2).
The compound for deriving the structural unit (a3) is at least one compound selected from the group consisting of a maleimide compound, a carboxylic acid ester compound, an aromatic compound having a polymerizable carbon-carbon unsaturated bond, and a vinyl cyanide compound. Can be mentioned.

  Examples of the maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N- (4-acetylphenyl) maleimide, N -(2,6-diethylphenyl) maleimide, N- (4-dimethylamino-3,5-dinitrophenyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N- Succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N- (1-anilinonaphthyl-4) -maleimide, N- [4- (2-benzoxazolyl) phenyl] maleimide, N- (9-acridinyl) male Such as soil and the like.

Examples of the carboxylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Unsaturated carboxylic acid esters such as isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate; unsaturated carboxylic acid aminoalkyl esters such as aminoethyl (meth) acrylate;
Examples thereof include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate.

  Examples of the aromatic compound having a polymerizable carbon-carbon unsaturated bond include aromatic vinyl compounds. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and the like.

Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and α-chloro (meth) acrylonitrile.
Of these, N-cyclohexylmaleimide, N-phenylmaleimide, dicyclopentanyl (meth) acrylate, and styrene are preferably used as the compound for deriving the structural unit (a3).

  When the copolymer (A) includes the structural unit (a3), (a1), (a2), and (a3) are each used as a single unit or a combination of a plurality of units derived from the above exemplary compounds. it can.

  The copolymer (A) of the present invention can also contain a structural unit (a5) derived from an unsaturated carboxylic acid as long as the effects of the present invention are not impaired. Specific examples of the unsaturated carboxylic acid that leads to the structural unit (a5) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

The ratio of the structural unit in the copolymer (A) is preferably as follows.
The component ratio of (a1) is preferably 10 to 90 mol%, more preferably 20 to 60 mol%, based on the total number of moles of all the structural units.
The component ratio of (a2) is preferably 90 to 10 mol%, more preferably 25 to 75 mol%, based on the total number of moles of all the structural units.
When (a3) is used, the structural ratio is preferably 0.01 to 60 mol%, more preferably 0.01 to 45 mol%, based on the total number of moles of all structural units.

  In the composition of the present invention, when the constituent ratios of (a1) to (a3) in the copolymer are in the range described above, an appropriate dissolution rate and a development margin for the developer can be obtained, and the formed pattern is It is preferable because it has high curability and is excellent in reliability.

  The copolymer can be produced according to a known method (for example, JP 2001-302712 A). Specifically, a predetermined amount of a compound that leads to a unit constituting the copolymer, a polymerization initiator, and a solvent are charged into a reaction vessel, and oxygen in the reaction vessel is replaced with nitrogen in the absence of oxygen. The polymer can be produced by stirring, heating and keeping warm.

  As the copolymer containing the structural units (a1) and (a2) and the copolymer containing the structural units (a1) to (a3), specifically, 2- (methacryloyloxy) ethyl acetoacetate / glycidyl methacrylate copolymer 2- (methacryloyloxy) ethyl acetoacetate / (3,4-epoxycyclohexyl) methyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyl oxetane copolymer, 2- (methacryloyloxy) ethyl acetoacetate / glycidyl methacrylate / 3-ethyl-3-methacryloxymethyl oxetane copolymer, 2- (methacryloyloxy) ethyl acetoacetate / glycidyl methacrylate / (3,4-epoxycyclohexyl) Methyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / (3,4-epoxycyclohexyl) methyl methacrylate / 3-ethyl-3-methacryloxymethyl oxetane copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-phenylmaleimide, 2- (methacryloyloxy) ethylacetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-cyclohexylmaleimide, 2- (methacryloyloxy) ethyl Acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-benzylmaleimide, 2- (methacryloyloxy) ethylacetoacetate / 3-ethyl-3-methacryloxymethyloxy Tan / N-phenylmaleimide / styrene copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-cyclohexylmaleimide / styrene copolymer, 2- (methacryloyloxy) ethyl Acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-benzylmaleimide / styrene copolymer, 2- (methacryloyloxy) ethylacetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-phenylmaleimide / Cyclohexyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-cyclohexylmaleimide / cyclohexyl methacrylate copolymer 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-benzylmaleimide / cyclohexyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacrylate Roxymethyloxetane / methacrylic acid / N-phenylmaleimide / methyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-cyclohexylmaleimide / methyl methacrylate copolymer 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-benzylmaleimide / methyl methacrylate copolymer, 2- (methacryloyloxy) Ethyl acetoacetate / 3-ethyl-3-methacryloxymethyl oxetane / N-phenylmaleimide / benzyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyl oxetane / N- Cyclohexylmaleimide / benzyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-benzylmaleimide / benzyl methacrylate copolymer, 2- (methacryloyloxy) ethyl Acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-phenylmaleimide / dicyclopentanyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-e Ru-3-methacryloxymethyloxetane / N-cyclohexylmaleimide / dicyclopentanyl methacrylate copolymer, 2- (methacryloyloxy) ethylacetoacetate / 3-ethyl-3-methacryloxymethyloxetane / N-benzylmaleimide / di Cyclopentanyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / (3,4-epoxycyclohexyl) methyl methacrylate / N-phenylmaleimide, 2- (methacryloyloxy) ) Ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane / (3,4-epoxycyclohexyl) methyl methacrylate / N-cyclohexylmaleimide, 2- (methacryloylio) Xyl) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyl oxetane / (3,4-epoxycyclohexyl) methyl methacrylate / N-benzylmaleimide, etc., preferably 2- (methacryloyloxy) ethyl acetoacetate / glycidyl Methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / (3,4-epoxycyclohexyl) methyl methacrylate copolymer, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane A polymer is mentioned, More preferably, 2- (methacryloyloxy) ethyl acetoacetate / 3-ethyl-3-methacryloxymethyloxetane copolymer is mentioned.

  The polystyrene-converted weight average molecular weight of the copolymer (A) is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. When the weight average molecular weight in terms of polystyrene is in the above range, it is preferable because a high development speed tends to be obtained while maintaining the remaining film ratio during development.

  Content of the copolymer (A) in the radiation sensitive resin composition of this invention becomes like this. Preferably it is 50-90 mass% with respect to solid content of a radiation sensitive resin composition, More preferably, it is 60-90. % By mass.

  Examples of the quinonediazide compound (B) in the radiation-sensitive resin composition of the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, 1,2-naphthoquinonediazide sulfonic acid amide and the like.

Specific examples of the quinonediazide compound (B) include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide. -5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones such as acid esters;
2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxy -3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as;
2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphtho 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as quinone diazide-5-sulfonic acid ester;
2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester or 3,4, 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as 5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester;
Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri ( p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( 2,3,4-Trihydroxyphenyl) methane-1,2-naphthoquinonediazide 4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) Propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1 , 3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4 -Hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane- 1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3, 3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3, 3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphth Toquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester or 2,2,4-trimethyl- And 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester.

  The quinonediazide compound (B) is used alone or in combination of two or more. Content of the quinonediazide compound (B) in the radiation sensitive resin composition of this invention is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 2-50 mass%, More preferably, it is 5-5. 40% by mass. When the content of the quinonediazide compound is within the above range, the difference in dissolution rate between the unexposed area and the exposed area tends to be high, and thus there is a tendency that the developed residual film ratio tends to be kept high.

  Examples of the photocationic polymerization initiator (C) in the present invention include onium salts. The onium salt is composed of an onium cation and an anion derived from a Lewis acid.

  Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (pt-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (P-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p- Tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (pt-butylphenyl) sulfonium, tris (p-cyanophenyl) Sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, dimethyl ( Isopropoxy) sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) Sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitrooctyloxy) sulfur Ni, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, diphenyl (4-phenylthiophenyl) sulfonium, diphenyl (4-phenyloxyphenyl) sulfonium, or dimethyl (tris (trichloro Methyl) methyl) sulfonium and the like.

  Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (pt-butylphenyl) iodonium, triphenylsulfonium or tris (pt-butylphenyl). ) Sulfonium and the like.

  Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroalcinate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acids include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.

  The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specific examples of the cationic photopolymerization initiator (C) include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (pt-butylphenyl) iodonium hexafluorophosphate, bis (p-octyl). Phenyl) iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyl) Oxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate Fate, methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethyl naphthyl sulfo Um hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate , Dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (t-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexaful Orophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium Hexafluorophosphate, diphenyliodonium hexafluo Arsinate, bis (p-tolyl) iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, bis (p-octylphenyl) iodonium hexafluoroalcinate, bis (p-octadecylphenyl) iodonium Hexafluoroarsinate, bis (p-octyloxyphenyl) iodonium hexafluoroarsinate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsinate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroalcinate, (p- Tolyl) (p-isopropylphenyl) iodonium hexafluoroarsinate, methyl naphthyl iodonium hexafluoroarsinate, ethyl naphthy Iodonium hexafluoroarsinate, triphenylsulfonium hexafluoroarsinate, tris (p-tolyl) sulfonium hexafluoroarsinate, tris (p-isopropylphenyl) sulfonium hexafluoroalcinate, tris (2,6-dimethylphenyl) sulfonium hexa Fluoroalcinate, tris (pt-butylphenyl) sulfonium hexafluoroalcinate, tris (p-cyanophenyl) sulfonium hexafluoroalcinate, tris (p-chlorophenyl) sulfonium hexafluoroalcinate, dimethyl naphthylsulfonium hexafluoroarsi , Diethyl naphthylsulfonium hexafluoroarsinate, dimethyl (methoxy) sulfonium hexafluoro Alcinate, dimethyl (ethoxy) sulfonium hexafluoroarsinate, dimethyl (propoxy) sulfonium hexafluoroarsinate, dimethyl (butoxy) sulfonium hexafluoroarsinate, dimethyl (octyloxy) sulfonium hexafluoroarsinate, dimethyl (octadecanoxy) sulfonium hexa Fluoroalcinate, dimethyl (isopropoxy) sulfonium hexafluoroalcinate, dimethyl (t-butoxy) sulfonium hexafluoroalcinate, dimethyl (cyclopentyloxy) sulfonium hexafluoroalcinate, dimethyl (cyclohexyloxy) sulfonium hexafluoroalcinate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarushi Dimethyl (2-chloroethoxy) sulfonium hexafluoroarsinate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsinate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsinate, dimethyl (8-nitrooctyloxy) Sulfonium hexafluoroarsinate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroalcinate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroalcinate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroalcinate Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, S (pt-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p-octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium Hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Methyl naphthyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenyl sulfate Honium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris (2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p -T-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoro Antimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) Honium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (Isopropoxy) sulfonium hexafluoroantimonate, dimethyl (t-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium Hexafluoroantimonate, dimethyl 2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate Dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate, diphenyliodonium tetrakis ( Pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (penta Fluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (penta) Fluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis ( Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluoropheny ) Borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate , Tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) ) Borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, Lis (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) ) Borate, dimethyl (octadecanoxy) sulfo Nium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (t-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) Borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3- Bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl Ru (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) Examples include borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) borate, and preferably bis (p-tolyl) iodonium. Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (pt Butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (pt-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsinate, (p-tolyl) (p-isopropyl) Phenyl) iodonium hexafluoroarsinate, bis (pt-butylphenyl) iodonium hexafluoroarsinate, triphenylsulfonium hexafluoroalcinate, tris (pt-butylphenyl) sulfonium hexafluoroalcinate, bis (p- Tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p -T-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (P-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt-butylphenyl) ) Sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p- Ril) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (pt-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (pt-butylphenyl) sulfonium hexafluoroantimony Bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (pt-butylphenyl) iodonium tetrakis (penta Fluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, or tris (pt-butylphenyl) sulfonium teto Such as tetrakis (pentafluorophenyl) borate.

  Content of a photocationic polymerization initiator (C) is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 0.01-10 mass%, More preferably, it is 0.1-10 mass%. Particularly preferred is 0.1 to 5% by mass. If the content of the cationic photopolymerization initiator (C) is in the above range, the reduction in resolution during thermosetting is suppressed by increasing the curing rate during thermosetting, and the solvent resistance of the cured film is further improved. This is preferable.

The radiation sensitive resin composition of the present invention contains a solvent (H). Examples of the solvent (H) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Esters such as methyl 2-hydroxyisobutanoate, ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone. Preferred examples of the solvent include methyl 2-hydroxyisobutanoate, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and γ-butyrolactone.

  The said solvent (H) is used individually or in combination of 2 or more types, respectively. Content of the solvent (H) in a radiation sensitive resin composition is a mass fraction with respect to a radiation sensitive resin composition, Preferably it is 50-95 mass%, More preferably, it is 60-90 mass%.

  In the present invention, a sensitizer (D) can also be used. Examples of the sensitizer (D) include thioxanthone compounds such as thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone, 2-cyclohexylthioxanthone, 4-cyclohexylthioxanthone and the like. As the benzophenone compounds, benzophenone, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′- Examples thereof include bis (diethylamino) benzophenone and 4,4′-bis (ethylmethylamino) benzophenone.

  When the sensitizer (D) is contained, the content thereof is a mass fraction with respect to the solid content of the radiation-sensitive resin composition, preferably 0.01 to 15% by mass, more preferably 0.1 to 0.1% by mass. 10% by mass. When the content of the sensitizer (D) is in the above range, the photocationic polymerization initiator is sensitized, and the curing rate at the time of thermosetting is increased, thereby suppressing a decrease in resolution at the time of thermosetting and further curing. This is preferable because the solvent resistance of the film tends to be improved.

  In the radiation sensitive resin composition of this invention, a polyhydric phenol compound (E), a crosslinking agent (F), and a polymerizable monomer (G) can be contained as needed.

  The polyhydric phenol compound (E) is preferably a compound having two or more phenolic hydroxyl groups in the molecule. The polyhydric phenol compound (E) is, for example, the same trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, (polyhydroxyphenyl) alkanes and the like described in the quinonediazide compounds. And polyhydric phenols.

  Examples of the polyhydric phenol compound (E) include a polymer having at least hydroxystyrene as a raw material monomer. Specific examples of the polyphenol compound (E) include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer, and hydroxystyrene / alkoxystyrene copolymer. Examples thereof include resins obtained by polymerizing hydroxystyrene such as coalescence. Furthermore, a novolak resin obtained by polycondensation of at least one compound selected from the group consisting of phenols, cresols and catechols and one or more compounds selected from the group consisting of aldehydes and ketones is also included. It is done.

  When it contains the said polyhydric phenol compound (E), the addition amount is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably it is 0.01 to 40%, More preferably, it is 0.00. 1 to 40%, particularly preferably 1 to 25%. When the content of the polyhydric phenol compound (E) is in the above range, the visible light transmittance of the obtained film is preferably increased.

  Examples of the crosslinking agent (F) include methylol compounds.

  Examples of the methylol compound include alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins. Here, as the alkoxymethylated melamine resin, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, etc., as alkoxymethylated urea resin, for example, methoxymethylated Examples include urea resins, ethoxymethylated urea resins, propoxymethylated urea resins, butoxymethylated urea resins. The above crosslinking agents may be used alone or in combination of two or more.

  In the said radiation sensitive resin composition, when using a crosslinking agent (F), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, Preferably 0.01 to 15%, More preferably, it is 0.1-10 mass%. When the content of the crosslinking agent (F) is in the above range, the visible light transmittance of the resulting film is preferably increased.

  Examples of the polymerizable monomer (G) include a polymerizable monomer capable of radical polymerization upon heating, a polymerizable monomer capable of cationic polymerization, and the like, and preferably a polymerizable monomer capable of cationic polymerization. .

  Examples of the polymerizable monomer capable of radical polymerization include compounds having a polymerizable carbon-carbon unsaturated bond, which may be a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, or 3 It may be a polyfunctional polymerizable monomer such as a polymerizable monomer having higher functionality. These may be used alone or in combination of two or more.

  Examples of the monofunctional polymerizable monomer include nonylphenyl carbitol acrylate, nonylphenyl carbitol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-ethylhexyl carbitol acrylate, Examples include 2-ethylhexyl carbitol methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and N-vinyl pyrrolidone.

  Examples of the bifunctional polymerizable monomer include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, and neopentyl glycol dimethacrylate. , Triethylene glycol diacrylate, triethylene glycol dimethacrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, and the like.

  Examples of the tri- or higher functional polymerizable monomer include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate. Pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Among the above polymerizable monomers, bifunctional or trifunctional or higher polymerizable monomers are preferably used. Specifically, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like are preferable, and dipentaerythritol hexaacrylate is more preferable. Further, a bifunctional or trifunctional or higher polymerizable monomer and a monofunctional polymerizable monomer may be used in combination.

  Examples of the polymerizable monomer capable of cationic polymerization include polymerizable monomers having a cationic polymerizable functional group such as a vinyl ether group, a propenyl ether group, an epoxy group, and an oxetanyl group. Specifically, as a compound containing a vinyl ether group Examples thereof include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, dodecyl vinyl ether and the like. As a compound containing a propenyl ether group, 4- (1-propenyloxymethyl)- 1,3-dioxolan-2-one and the like, and as a compound containing an epoxy group, a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy Cis-resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, etc., and bis {3- (3-ethyloxetanyl) methyl} ether, 1,4- Bis {3- (3-ethyloxetanyl) methoxy} benzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} methylbenzene, 1,4-bis {3- (3-ethyloxetanyl) methoxy} cyclohexane 1,4-bis {3- (3-ethyloxetanyl) methoxy} methylcyclohexane, 3- (3-ethyloxetanyl) methylated novolak resin, and the like.

  When using the said polymerizable monomer (G), the content is a mass fraction with respect to solid content of a radiation sensitive resin composition, and it is preferable that it is 0.01 to 20%.

  The radiation-sensitive resin composition of the present invention may further comprise other components as necessary, for example, surfactants (silicone, fluorine, anion, cation, nonion, etc.), antioxidants, and dissolution inhibitors. Various additives capable of adjusting coating properties and developability and improving reliability, such as dissolution accelerators, ultraviolet absorbers, adhesion improvers (for example, silane coupling agents), and electron donors. Can also be contained.

  The radiation sensitive resin composition of the present invention includes, for example, a solution in which the copolymer (A) is dissolved in the solvent (H), a solution in which the quinonediazide compound (B) is dissolved in the solvent (H), a photocationic polymerization initiator ( It can be prepared by mixing a solution in which C) is dissolved in the solvent (H) and a solution in which the sensitizer (D) is dissolved in the solvent (H). Moreover, you may add and mix a solvent (H) with the liquid after preparation. Moreover, you may heat when mixing a solution. Furthermore, after mixing a solution, you may remove a solid substance by filtration. The filtration is preferably performed using a filter having a pore size of 3 μm or less (preferably about 0.1 to 2 μm). The solvent used for each component may be the same or different as long as it is compatible.

  In order to form the cured resin pattern (6) using the radiation sensitive resin composition of the present invention, for example, a layer (1) composed of the radiation sensitive resin composition is formed on the substrate (2) [ 1 (a)], the layer (1) is exposed to radiation (4) through a mask (3) and exposed (see FIG. 1 (b)), and then developed [FIG. 1 (1). c) See].

  Examples of the substrate (2) include a transparent glass plate, a plastic substrate, a plastic film, and a silicon wafer. Circuits such as TFTs and CCDs, color filters, and the like may be formed on the substrate.

  The layer (1) comprising the radiation sensitive resin composition can be formed by, for example, a method of applying the radiation sensitive resin composition on the substrate (2). The coating is performed by, for example, spin coating, casting coating, roll coating, slit and spin coating, or slit coating (sometimes referred to as slit die coating, die coating, or curtain flow coating). After application, the radiation-sensitive resin composition layer (1) is formed by heat-drying (pre-baking) or vacuum-drying after heating to volatilize volatile components such as a solvent. The physical layer (1) contains almost no volatile components. Moreover, the thickness of the said radiation sensitive resin composition layer is about 1-5 micrometers.

  Thereafter, the radiation-sensitive resin composition layer (1) is irradiated with radiation (4) through a mask (3). The pattern of the mask (3) is appropriately selected according to the target pattern shape. As the radiation, for example, light rays such as g-line or i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown) so as to be irradiated in parallel over the entire surface of the radiation-sensitive resin composition layer. By irradiating with radiation in this way, alignment between the mask and the radiation-sensitive resin composition layer can be performed accurately.

  After the exposure, development is performed. Development can be performed on the radiation-sensitive resin composition layer (1) after exposure by, for example, a paddle method, a dipping method, or a shower method. As the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

  Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, Examples thereof include potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or ammonia.

  Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. It is done.

  The above alkaline compounds may be used alone or in combination of two or more. The developer usually contains 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass of the alkaline compound per 100 parts by mass of the developer.

  The developer may contain a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants.

  Nonionic surfactants include, for example, polyoxyethylene derivatives such as polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene derivatives, and the like. Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

  Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; sodium dodecylbenzenesulfonate or dodecylnaphthalenesulfone. Examples thereof include alkyl aryl sulfonates such as sodium acid. These surfactants may be used alone or in combination of two or more.

  Further, the developer may contain an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as methanol and ethanol.

  Of the radiation-sensitive resin composition layer (1), the radiation-irradiated region (12) irradiated with radiation in the previous exposure is dissolved in the developer by the development, and the radiation-unirradiated region (not irradiated with radiation) ( 11) remains without being dissolved in the developer to form a resin pattern (5).

  Since the radiation sensitive resin composition of this invention contains a quinonediazide compound (B), even if the time which makes a radiation sensitive resin composition layer (1) contact with a developing solution is short, a radiation irradiation area | region (12) Easily dissolves and is removed. Moreover, since it contains a quinonediazide compound (B), even if the time during which the radiation-sensitive resin composition layer (1) is brought into contact with the developer becomes long, the radiation non-irradiated region (11) dissolves in the developer and disappears. There is nothing to do.

  After alkali development, it is usually washed with water and dried. After drying, the resin pattern (5) obtained is irradiated with radiation using a light source containing radiation having a wavelength of 250 to 380 nm over a part or the entire surface of the obtained resin pattern (5).

  The resin pattern (5) thus formed is preferably further heat-treated (post-baked) from the viewpoint of improving heat resistance, solvent resistance and the like. The heat treatment is performed by a method of heating the substrate after irradiation with radiation over part or the entire surface of the resin pattern (5) with a heating device such as a hot plate or a clean oven. The heating temperature is usually 150 ° C to 250 ° C, preferably 180 ° C to 240 ° C. The heating time is usually 5 minutes to 120 minutes, preferably 15 minutes to 90 minutes. By heat-processing, the resin pattern (5) hardens | cures and a cured resin pattern (6) is formed.

  Here, when the radiation-sensitive resin composition of the present invention is used, the amount of radiation applied to a part or the entire surface of the obtained resin pattern (5) is controlled (for example, change of integrated exposure amount or light source). By doing so, the shape of the cross section perpendicular | vertical with respect to the board | substrate of the cured resin pattern (6) obtained can be controlled easily.

  Specifically, in a cross section perpendicular to the substrate of the cured resin pattern (6) obtained by increasing the amount of radiation applied to a part or the entire surface of the obtained resin pattern (5), The cured resin pattern (6) obtained by increasing the angle θ formed between the ridge line rising from the substrate of the cross section of the resin and the substrate, and reducing the amount of radiation applied to a part or the entire surface of the resin pattern (5) By reducing the angle θ between the ridge line rising from the substrate of the resin cross section and the substrate in the cross section perpendicular to the substrate, the shape of the cross section perpendicular to the substrate of the obtained cured resin pattern can be easily controlled can do.

  Thus, the cured resin pattern (6) formed using the radiation-sensitive resin composition of the present invention includes, for example, a cured resin pattern constituting a TFT substrate, an insulating film of an organic EL element, a protective film of a CCD, and the like. Useful as.

  As mentioned above, although embodiment of this invention was described, embodiment of the said disclosed invention is an illustration to the last, Comprising: The scope of the present invention is not limited to these embodiment. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Synthesis example 1
The following raw materials are charged into a 200 mL four-necked flask equipped with a stirrer, a condenser tube and a thermometer, and the four-necked flask is immersed in an oil bath under a nitrogen stream, and the temperature inside the flask is 75 to 75- While maintaining at 85 ° C., the reaction was carried out by stirring for 5 hours to obtain a resin solution A1. This resin A1 had a polystyrene-reduced weight average molecular weight of 11,000 (molecular weight distribution 2.0).

2- (Methacryloyloxy) ethyl acetoacetate 20.85 g
3-ethyl-3-methacryloxymethyloxetane 17.94 g
90.51 g of ethyl lactate
Azobisisobutyronitrile 0.7g

In addition, the measuring method of the polystyrene conversion weight average molecular weight was as follows.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6 mass% (solvent: THF)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as molecular weight distribution (Mw / Mn).

Synthesis example 2
A resin solution A2 was obtained in the same manner as in Synthesis Example 1 except that the raw materials of Synthesis Example 1 were changed to the components described below and the flask internal temperature was 80 to 90 ° C. This resin A2 had a polystyrene equivalent weight average molecular weight of 12,000 (molecular weight distribution 2.1).

Methacrylic acid 7.10 g
Cyclohexyl methacrylate 15.86 g
3-ethyl-3-methacryloxymethyloxetane 21.71 g
104.25g of ethyl lactate
Azobisisobutyronitrile 1.06g

Example 1
333 parts by mass (100 parts by mass of the resin) of the resin solution A1, 20 parts by mass of the compound represented by the formula (1), 1 part by mass of SANAID SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) (in terms of solid content) Adekaoptomer SP-172 (manufactured by Asahi Denka Kogyo Co., Ltd.) 1 part by mass (in terms of solid content), 133 parts by mass of γ-butyrolactone, 13 parts by mass of ethyl lactate were mixed and dissolved at 23 ° C. And pressure-filtering through a polytetrafluoroethylene cartridge filter to obtain a radiation-sensitive resin composition.

(In the formula, Q ⁴ represents a substituent represented by the following formula (1-1).)

  The radiation-sensitive resin composition obtained above is spin-coated on a 4-inch silicon wafer (2), and heated (prebaked) at 100 ° C. for 2 minutes using a hot plate, the radiation-sensitive resin composition layer (1 ) And the film thickness was measured using a film thickness meter [Lambda Ace VM-8000J; manufactured by Dainippon Screen Mfg. Co., Ltd.] and found to be 2.6 μm [see FIG. 1 (a)].

  Thereafter, radiation was passed through the mask (3) using an i-line stepper [NSR-1755i7A (NA = 0.5); manufactured by Nikon Corporation] on the obtained radiation-sensitive resin composition layer (1). (4) was irradiated and exposed [see FIG. 1 (b)]. As the mask (3), a mask for forming a contact hole pattern with a line width of 3 μm at an interval of 9 μm was used.

After exposure, the film was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 70 seconds for development, washed with ultrapure water, and dried. In the pattern after development, the film thickness of the non-exposed part was 2.57 μm. The effective sensitivity was 120 mJ / cm ^{2 when} the exposure amount in the mask exposure with the contact hole diameter of 3 μm was defined as the effective sensitivity. After drying, irradiated with radiation (600 mJ / cm ^{2 based on} wavelength 313 nm) using a Deep-UV lamp [UXM-501MD; manufactured by Ushio Inc.], heated in a clean oven at 220 ° C. for 30 minutes, A transparent cured resin pattern (5) was formed [see FIG. 1 (c)].

  It was 2.3 micrometers when the thickness of the obtained transparent cured resin pattern (5) was measured using the film thickness meter. In a cross section perpendicular to the substrate of the cured resin pattern, the angle θ formed by the ridgeline of the cross section and the substrate surface was measured and found to be 60 degrees.

  Visible light transmittance was determined by forming a cured resin film on a transparent glass substrate [# 1737; manufactured by Corning Co., Ltd.] by the same method as above except that the stepper exposure process was not performed, and the microspectrophotometer [OSP-200; Olympus Measured by Kogaku Kogyo Co., Ltd.]. The film thickness was measured with a film thickness meter [DEKTAK3; manufactured by ULVAC, Inc.]. The average light transmittance at a wavelength of 400 to 750 nm per 1 μm of the obtained cured resin film was as high as 99.5%, and no coloring was observed.

Comparative Example 1
A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that the resin solution A1 was changed to the resin solution A2.

  As a result of performing the same operation as in Example 1, the film thickness before development was 2.60 μm, and the film thickness of the non-exposed part after development was 1.70 μm. It can be seen that the film thickness change before and after development is large and the development margin for the film thickness change is narrow.

  The radiation-sensitive resin composition of the present invention has a high transmittance for visible light, and is suitably used for organic insulating films, overcoats, photospacers, microlenses, etc. used in liquid crystal display devices, solid-state imaging devices, etc. can do.

It is a schematic diagram which shows the process of forming a transparent film using the radiation sensitive resin composition of this invention. In a cross section perpendicular to the substrate of the cured resin pattern, an angle θ formed by the ridgeline of the cross section and the substrate surface is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Radiation sensitive resin composition layer 11 Radiation non-irradiation area | region 12 Radiation irradiation area | region 2 Board | substrate 3 Mask 4 Radiation 5 Resin pattern 6 Cured resin pattern (theta) In the cross section perpendicular | vertical with respect to the board | substrate of cured resin pattern (6) Between the ridge line rising from the substrate and the substrate

Claims (11)

  From the structural unit (a1) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, and an unsaturated compound having a group that reacts by the action of light and / or heat A radiation-sensitive resin composition comprising a copolymer (A) containing a derived structural unit (a2) and a quinonediazide compound.   Furthermore, the radiation sensitive resin composition of Claim 1 containing a photocationic polymerization initiator. The unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group that leads to the structural unit (a1) is a compound represented by the formula (I) or the formula (II) Item 3. The radiation-sensitive resin composition according to Item 1 or 2.

[In Formula (I) and Formula (II), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.
R ² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ³ represents a divalent group represented by any one of formulas (1-1) to (1-3).

R ⁴ represents a group represented by any one of formulas (1-4) to (1-7).

R ¹ in Formula (1-4) and Formula (1-5) represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.
X represents Formula (1-8) or Formula (1-9). ]

  The group consisting of the unsaturated compound (a21) having an oxetanyl group and the unsaturated compound (a22) having an epoxy group, wherein the unsaturated compound having a group that reacts by the action of light and / or heat and leads to the structural unit (a2) The radiation sensitive resin composition according to any one of claims 1 to 3, which is an unsaturated compound having at least one selected from the group consisting of:   The copolymer (A) is cured by the action of light and / or heat with the structural unit (a1) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group. The radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the ratio of the structural unit (a2) derived from the unsaturated compound having a group is 5:95 to 95: 5 in terms of molar fraction. .   The copolymer (A) is cured by the action of the structural unit (a1) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group, and light and / or heat. The radiation sensitive resin composition according to any one of claims 1 to 5, further comprising a structural unit (a2) derived from an unsaturated compound having a group and a structural unit (a3) derived from a copolymerizable compound.   The compound that leads to the structural unit (a3) is at least one compound selected from the group consisting of a maleimide compound, a carboxylic acid ester compound, an aromatic compound having a polymerizable carbon-carbon unsaturated bond, and a vinyl cyanide compound. The radiation sensitive resin composition of Claim 6.   The structural unit (a1) derived from an unsaturated compound having at least one group selected from the group consisting of an active methylene group and an active methine group with respect to the total number of moles of all the constituent components constituting the copolymer (A) ) Is 15 to 70 mol%, the content of the structural unit (a21) derived from the unsaturated compound having an oxetanyl group is 20 to 80 mol%, and the structural unit copolymerizable with (a1) and (a21) The radiation-sensitive resin composition according to claim 6 or 7, wherein the content of (a3) is 0.01 to 60 mol%.   The content of the copolymer (A) is 60 to 96.9% by mass with respect to the solid content of the radiation-sensitive resin composition, and the content of the quinonediazide compound (B) is 3 to 30% by mass. The radiation-sensitive resin composition according to claim 1, wherein the content of the photocationic polymerization initiator (C) is 0.1 to 10% by mass.   The cured resin pattern formed using the radiation sensitive resin composition in any one of Claims 1-9. A liquid crystal display device comprising the cured resin pattern according to claim 10.

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