JP2008009121A - Colored positive radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored positive radiation-sensitive resin composition having high resolution in a colored cured resin pattern. <P>SOLUTION: The colored positive radiation-sensitive resin composition comprises an alkali-soluble resin (A), having curability, a quinonediazide compound (B) and a colorant (C), wherein the alkali-soluble resin (A) having curability is a copolymer, comprising a constituting unit (a1) derived from unsaturated carboxylic acid and a constituting unit (a2) derived from an unsaturated compound having an oxetanyl group, where the unsaturated compound, having an oxetanyl group from which the constitutional unit (a2) is derived, is not an unsaturated carboxylic acid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, a colored cured resin pattern formed using the composition, and a method for producing the pattern.

It is known to form a black matrix using a radiation-sensitive resin composition containing a copolymer obtained by copolymerizing an epoxy compound and other components, a 1,2-quinonediazide compound and a black colorant. (Patent Document 1).
In addition, it is also known that coloring is performed to improve contrast in the formation of photo spacers for color filters (for example, Patent Document 2).

JP-A-2001-343743 Example 1 JP 2002-174817 A

However, color filter photo spacers and the like have been required to be further miniaturized in order to improve the luminance of the liquid crystal panel.
An object of the present invention is to provide a positive colored radiation-sensitive resin composition having a high resolution in a colored cured resin pattern.

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 curable alkali-soluble resin (A), a curable alkali-soluble resin (A), a quinonediazide compound (B), and a colorant (C). A positive colored radiation-sensitive resin composition in which A) is a copolymer containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group [provided that The unsaturated compound leading to the structural unit (a2) is not an unsaturated carboxylic acid], a colored cured resin pattern formed using the positive colored radiation-sensitive resin composition, and the positive type Apply colored radiation-sensitive resin composition, remove solvent, irradiate with radiation through mask, then develop with alkaline aqueous solution to form predetermined pattern To provide a method of manufacturing a colored cured resin pattern.

  When the positive colored radiation-sensitive resin composition of the present invention is used, a fine colored cured resin pattern can be formed.

  The curable alkali-soluble resin (A) in the present invention is a copolymer containing a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group. [However, the unsaturated compound leading to the structural unit (a2) is not an unsaturated carboxylic acid].

Examples of the unsaturated carboxylic acid from which the structural unit (a1) is derived include unsaturated carboxylic acids having one or more carboxyl groups in the molecule. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.
Here, in this specification, the notation of (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and the notation of (meth) acrylate represents the group consisting of acrylate and methacrylate. And (meth) acryloyl notation represents at least one selected from the group consisting of acryloyl and methacryloyl, and (meth) acryloyloxy notation selected from the group consisting of acryloyloxy and methacryloyloxy Represents at least one kind.

Examples of the unsaturated compound having an oxetanyl group that leads to the structural unit (a2) include 3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxymethyl oxetane, and 3-ethyl. -3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- [1- (meth) acryloyloxy] methyl oxetane, 3-ethyl-3- [1- (meth) acryloyloxy] methyl oxetane, 3-methyl- 3- [1- (meth) acryloyloxy] ethyl oxetane, 3-ethyl-3- [1- (meth) acryloyloxy] ethyl oxetane, 2-phenyl-3- (meth) acryloyloxymethyl oxetane, 2-trifluoromethyl -3- (meth) acryloyloxymethyl oxetane, 2-pentafluoroethyl-3- (Meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 2-phenyl-3- (meth) acryloyloxy Examples include ethyl oxetane, 2-trifluoromethyl-3- (meth) acryloyloxyethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloyloxyethyl oxetane, and 3-methacryloxy oxetane, preferably 3 -Ethyl-3-methacryloxymethyl oxetane, 3-methyl-3-methacryloxymethyl oxetane, 3-methyl-3- (1-methacryloxy) ethyl oxetane, 3-methacryloxy oxetane, more preferably 3-ethyl -3-Methacryloxymethyl oxe Down, 3-methyl-3-methacryloxy methyl oxetane and the like.
When a positive colored radiation-sensitive resin composition is prepared using an alkali-soluble resin containing an unsaturated compound having an oxetanyl group as the structural unit (a2), an alkali-soluble resin containing an unsaturated compound having an epoxy group Compared with the case where a positive colored radiation-sensitive resin composition is prepared using, the storage stability of the positive colored radiation-sensitive resin composition tends to be good, which is preferable.

In the copolymer containing only the structural unit (a1) and the structural unit (a2), the content of the structural unit (a1) is preferably a molar ratio with respect to the entire structural unit of the copolymer, preferably 5 to 50 mol%. More preferably, it is 15-40 mol%. Moreover, content of a structural unit (a2) is a molar ratio with respect to the whole structural unit of a copolymer, Preferably it is 95-50 mol%, More preferably, it is 85-60 mol%.
When the content of the structural unit (a1) and the structural unit (a2) in the copolymer is in the above range, it is preferable from the viewpoint of an appropriate dissolution rate in the developer and high curability.

In the present invention, the curable alkali-soluble resin (A) further comprises, as a copolymer component, a structural unit (a31) derived from a carboxylic acid ester having a carbon-carbon unsaturated bond bond, a carbon-carbon unsaturated bond. A structural unit derived from an aromatic compound having (a32), a structural unit derived from a vinyl cyanide compound (a33), a structural unit derived from a maleimide compound optionally substituted at the N-position (a34), and a carbon-carbon bond. It may contain at least one structural unit (a3) selected from the group consisting of the structural unit (a35) derived from an epoxy compound having a saturated bond.
Examples of the carboxylic acid ester having a carbon-carbon unsaturated bond leading to the structural unit (a31) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , Unsaturated carboxylic acids such as benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate Acid esters;
Unsaturated alkyl 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 carbon-carbon unsaturated bond leading to the structural unit (a32) include aromatic vinyl compounds. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyl toluene, and the like.
Examples of the vinyl cyanide compound that leads to the structural unit (a33) include acrylonitrile, methacrylonitrile, and α-chloro (meth) acrylonitrile.
Examples of the maleimide compound optionally substituted at the N-position leading to the structural unit (a34) include maleimide, 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) fe Le] maleimide, N-(9-acridinyl) maleimide and the like.
Examples of the epoxy compound having a carbon-carbon unsaturated bond leading to the structural unit (a35) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, 3-methyl-3, 4-epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

  The structural units (a1), (a2), (a31), (a32), (a33), (a34), and (a35) are each used as a single unit or a plurality of combinations of units derived from the above exemplary compounds. be able to.

  The alkali-soluble resin (A) may contain a structural unit (a3) in addition to the structural unit (a1) and the structural unit (a2). When the structural unit (a3) is included in addition to the structural unit (a1) and the structural unit (a2), the content of the structural unit (a1) is preferably a molar ratio with respect to the entire structural unit of the copolymer. It is 5-60 mol%, More preferably, it is 15-50 mol%. Moreover, content of a structural unit (a2) is a molar ratio with respect to the whole structural unit of a copolymer, Preferably it is 95-10 mol%, More preferably, it is 85-20 mol%. Furthermore, content of a structural unit (a3) is a molar ratio with respect to the whole structural unit of a copolymer, Preferably it is 95-10 mol%, More preferably, it is 85-20 mol%.

  Examples of the copolymer containing the structural unit (a1) and the structural unit (a2) include 3-ethyl-3-methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl. Oxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / styrene copolymer, 3-ethyl-3-methacryloxymethyloxetane / methacrylic acid / cyclohexyl methacrylate copolymer 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / methyl methacrylate / styrene copolymer, 3-ethyl- 3-methacryloki Methyl oxetane / methacrylic acid / tert-butyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl methacrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / Benzyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / isobornyl acrylate copolymer, 3- Ethyl-3-methacryloxymethyl oxetane / methacrylic acid / dicyclopentanyl methacrylate copolymer, or 3-ethyl-3-methacryloxymethyl oxetane / methacrylic acid / tert-butyl acrylate copolymer 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / phenylmaleimide copolymer, and 3-ethyl-3-methacryloxy methyl oxetane / methacrylic acid / cyclohexyl maleimide copolymer.

  The alkali-soluble resin (A) used in the present invention includes, for example, a compound that leads to the structural unit (a1) and a compound that leads to the structural unit (a2), and optionally a compound that leads to the structural unit (a3). It is obtained by mixing in the presence or absence, in an inert gas atmosphere or air atmosphere, in the presence or absence of a catalyst, and mixing, for example, heating and maintaining at 30 to 200 ° C. for reaction. It is obtained by separating from the reaction solution and purifying as necessary.

The weight average molecular weight calculated | required by the gel permeation chromatography on the basis of polystyrene in the copolymer containing a structural unit (a1) and a structural unit (a2) becomes like this. Preferably it is 2,000-100,000, More preferably It is 2,000 to 50,000, particularly preferably 3,000 to 20,000. When the weight average molecular weight is in the above range, a high development speed tends to be obtained while maintaining the remaining film ratio during development, which is preferable.
The content of the copolymer containing the structural unit (a1) and the structural unit (a2) in the present invention is preferably 50 to 90% by mass, more preferably 60 to 60%, based on the solid content of the radiation-sensitive resin composition. 90% by mass.

  Examples of the quinone diazide compound (B) used in the present invention include 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, and 1,2-naphtho. And quinonediazide sulfonic acid amide.

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-5-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-4-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-naphtho Quinonediazide-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-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, or 2, 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester Is mentioned.

  The quinonediazide compound (B) is used alone or in combination of two or more. The content of the quinonediazide compound (B) in the present invention is preferably 2 to 50 mass%, more preferably 5 to 40 mass%, based on the solid content of the radiation-sensitive resin composition. When the content of the quinonediazide compound is in the above range, the difference in the dissolution rate between the unexposed area and the exposed area tends to be high, so that the residual film ratio during development tends to be kept high, which is preferable.

Examples of the colorant (C) used in the present invention include dyes and pigments, which can be used alone or in combination.
The pigment may be an inorganic pigment or an organic pigment, and these can be used alone or in combination.
Among these, it is preferable to include at least one pigment selected from the group consisting of organic pigments and black inorganic pigments. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and a combination of carbon black and two or more organic pigments is particularly preferable.
As the pigment, a pigment having high color developability and high heat resistance and light resistance is preferable. Further, two or more kinds of combinations selected from carbon black and organic pigments can be used according to the required absorption spectrum. More specifically, a combination of carbon black and one or more organic pigments or a combination of two or more organic pigments is preferably used.

  Examples of carbon black include C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like. More specifically, SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, SRF, SRF-LM, SRF -Furnace black such as LS, GPF, ECF, N-339 and N-351; Thermal black such as FT and MT; Acetylene black and the like. These carbon blacks can be used alone or in admixture of two or more. In addition, examples of inorganic pigments other than carbon black in the present invention include metal oxides such as titanium black, Cu—Fe—Mn oxide, and synthetic iron black. These inorganic pigments can be used alone or in admixture of two or more.

  Furthermore, as the organic pigment in the present invention, for example, a compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colorists), specifically, as follows: The color index (CI) number is attached. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168; I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 71; C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254; C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29; C.I. I. Pigment blue 15, C.I. I. Pigment blue 60, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment Blue 15: 6; C.I. I. Pigment green 7, C.I. I. Pigment green 36; C.I. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment Black 1.

  These organic pigments are appropriately selected and used so as to obtain a desired hue. The said pigment can be used with an extender depending on the case. Examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, satan white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of extender used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 40 parts by mass or less with respect to 100 parts by mass of the black pigment.

  The positive colored radiation-sensitive resin composition of the present invention preferably further contains a solvent (D).

Examples of the organic solvent (D) 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 dipropyl ether or diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate or ethyl cellosolve acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or propylene glycol monopropyl ether acetate;
Aromatic hydrocarbons such as benzene, toluene or xylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerin;
Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, butyl acetate, amyl acetate, isoamyl acetate or methyl pyruvate, and cyclic esters such as γ-butyrolactone.

  The organic solvent (D) can be used alone, but it is also preferable to use a mixture of two or more organic solvents.

  Specific preferred solvent combinations include diethylene glycol dimethyl ether and butyl lactate, diethylene glycol ethyl methyl ether and butyl lactate, propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate and butyl lactate, ethyl 3-ethoxypropionate and butyl lactate , Ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether and butyl acetate, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate and butyl lactate, 3 -Ethyl ethoxypropionate and acetic acid Combination of chill and butyl lactate and the like.

  Content of a solvent (D) is a mass fraction with respect to positive type colored radiation sensitive resin composition, Preferably it is 50-95 mass%, More preferably, it is 65-90 mass%. When the content of the solvent (D) is in the above range, a film having good flatness tends to be formed, which is preferable.

  In addition to the alkali-soluble resin (A), the quinonediazide compound (B), the colorant (C) and the organic solvent (D), the positive colored radiation-sensitive resin composition of the present invention includes a polymerization initiator (E), a polyvalent You may contain a phenolic compound (F), a crosslinking agent (G), and a polymeric compound (H).

Examples of the polymerization initiator (E) include onium salts that are cationic polymerization initiators. 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 (p-tert-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 (p-tert-butylphenyl) sulfonium, tris (p-si Nophenyl) 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 (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitroo) Yloxy) sulfonium, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium or dimethyl (tris (trichloromethyl) methyl) and the like sulfonium.
Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-butylphenyl). ) Sulfonium and the like.
Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, 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 polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexa Fluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , 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 (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethylnaphthyls Honium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluoro Phosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium Hexafluorophosphate, 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 hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate , Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;
Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-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 Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;
Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) 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 (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium 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 (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Diethyl naphthylsulfonium 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) bo Dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-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 tetra (Pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) Methyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, preferably bis (p-tolyl) Donium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate Nate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoroarsenate, Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Nates, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) Borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt rt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) ) Borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butyl) Phenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenyl sulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

  When the polymerization initiator (E) is contained, the content thereof is a mass fraction with respect to the solid content of the positive colored radiation-sensitive resin composition, preferably 0.01 to 10% by mass, more preferably 0. .1 to 5% by mass. When the content of the polymerization initiator (E) is within the above range, by increasing the curing rate at the time of thermosetting, a decrease in resolution at the time of thermosetting is suppressed, and the solvent resistance of the cured film is further improved. Is preferable.

Examples of the polyhydric phenol compound (F) include a compound having two or more phenolic hydroxyl groups in the molecule, a polymer obtained using at least hydroxystyrene as a raw material monomer, or a novolak resin.
Examples of the compound having two or more phenolic hydroxyl groups in the molecule include trihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, or (polyhydroxy) exemplified in the description of the quinonediazide compound. Phenyl) alkanes and the like.

Specific examples of the polymer obtained using at least hydroxystyrene as a raw material monomer include polyhydroxystyrene, hydroxystyrene / methyl methacrylate copolymer, hydroxystyrene / cyclohexyl methacrylate copolymer, hydroxystyrene / styrene copolymer or hydroxy Examples thereof include resins obtained by polymerizing hydroxystyrene such as styrene / alkoxystyrene copolymers.
Further, the novolak resin may be, for example, one or more compounds selected from the group consisting of phenols, cresols and catechols and one or more compounds selected from the group consisting of aldehydes and ketones. Examples thereof include resins obtained by polymerization.

  When the polyhydric phenol compound (F) is contained, the content thereof is a mass fraction with respect to the solid content of the positive colored radiation-sensitive resin composition, preferably 0.1 to 40% by mass. Preferably it is 0.1-25 mass%.

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

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

  When it contains a crosslinking agent (G), the content is a mass fraction with respect to solid content of positive type colored radiation-sensitive resin composition, Preferably it is 0.1-15 mass%. When the content of the crosslinking agent is in the above range, the performance as the cured resin pattern is improved, which is preferable.

  Examples of the polymerizable compound (H) include a polymerizable compound capable of radical polymerization by heating or a polymerizable compound capable of cationic polymerization. A preferable polymerizable compound (H) includes a polymerizable compound capable of cationic polymerization.

  Examples of the polymerizable compound capable of radical polymerization include compounds having a polymerizable carbon-carbon unsaturated bond. The compound having a polymerizable carbon-carbon unsaturated bond may be a monofunctional polymerizable compound, a bifunctional polymerizable compound, or a polyfunctional (trifunctional or higher functional) polymerizable compound. There may be.

  Examples of the monofunctional polymerizable compound 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, or N-vinyl pyrrolidone.

  Examples of the bifunctional polymerizable compound 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 polyfunctional polymerizable compound include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol pentaacrylate, pentaerythritol. Examples include pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.
Among the compounds having a polymerizable carbon-carbon unsaturated bond, a bifunctional or polyfunctional polymerizable compound is preferably used. Specifically, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate is preferable, and dipentaerythritol hexaacrylate is more preferable. A bifunctional or polyfunctional polymerizable compound and a monofunctional polymerizable compound may be used in combination.

Examples of the polymerizable compound capable of cationic polymerization include compounds having a cationic polymerizable functional group such as a vinyl ether group, a propenyl ether group, an epoxy group, or an oxetanyl group.
Examples of the compound containing a vinyl ether group include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, and dodecyl vinyl ether.
Examples of the compound containing a propenyl ether group include 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one.

Examples of the compound containing an epoxy group include a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and a heterocyclic ring. An epoxy resin etc. are mentioned. The weight average molecular weight of these epoxy resins is preferably 2,000 or less, and more preferably 1,500 or less.
Examples of the compound containing the oxetanyl group include 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 or And 3- (3-ethyloxetanyl) methylated novolak resin. The weight average molecular weight of the resin containing these oxetanyl groups is preferably 2,000 or less, and more preferably 1,500 or less.

The said polymeric compound (H) is used individually or in combination of 2 or more types.
When the polymerizable compound (H) is contained, the content thereof is a mass fraction with respect to the solid content of the positive colored radiation-sensitive resin composition, and preferably 0.1 to 20% by mass.

  The positive type colored radiation-sensitive resin composition of the present invention may further comprise other components as necessary, for example, surfactants, antioxidants, dissolution inhibitors, sensitizers, ultraviolet absorbers, light stabilizers, adhesives. Various additives such as a property improving agent or an electron donor can also be contained.

In the positive colored radiation-sensitive resin composition of the present invention, for example, the alkali-soluble resin (A), the quinonediazide compound (B), and the colorant (C) are dissolved or dispersed in an organic solvent (D) and mixed. Can be prepared. A method in which the alkali-soluble resin (A), the quinonediazide compound (B), and the colorant (C) are previously dissolved in the organic solvent (D) and mixed is also preferable. Moreover, you may add and mix an organic solvent (D) with the liquid after preparation. The organic solvent (D) used for the alkali-soluble resin (A), the quinonediazide compound (B) and the colorant (C) may be the same as or different from each other. In addition, a plurality of organic solvents (D) may be used as long as they are compatible with each other.
Furthermore, it is preferable to remove solids by filtration after mixing the solutions. The filtration is preferably performed using a filter having a pore size of 3 μm or less (preferably about 0.1 to 2 μm).

  Since the positive colored radiation-sensitive resin composition of the present invention is a positive type, it has a higher resolution than the negative type and is preferable.

  When forming a cured resin pattern using the positive colored radiation-sensitive resin composition of the present invention, for example, a layer made of the positive colored radiation-sensitive resin composition is formed on a substrate and passed through a mask. The layer may be exposed to radiation and exposed, and then developed.

  Examples of the substrate include a transparent glass plate. Circuits such as TFTs and CCDs, color filters, and the like may be formed on the substrate.

  The layer made of the positive colored radiation sensitive resin composition can be formed by, for example, a method of applying the positive colored radiation sensitive resin composition onto the substrate. The coating is performed, for example, by spin coating, casting coating, roll coating, slit and spin coating, or slit coating. After coating, heating-drying (pre-baking) or drying after drying under reduced pressure causes the volatile component such as a solvent to volatilize to form a positive colored radiation-sensitive resin composition layer. Here, the temperature of heating is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The positive colored radiation-sensitive resin composition layer contains almost no volatile component. Moreover, the thickness of the said radiation sensitive resin composition layer is about 1.5-5 micrometers.

  Thereafter, the positive colored radiation-sensitive resin composition layer is irradiated with radiation through a mask. The pattern of the mask is appropriately selected according to the target pattern shape of the resin pattern. 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 so as to be irradiated in parallel over the entire surface or part of the positive colored radiation-sensitive resin composition layer. By irradiating with radiation in this way, alignment between the mask and the positive colored radiation-sensitive resin composition layer can be performed accurately.

  After the exposure, development is performed. The development can be performed on the positive colored radiation-sensitive resin composition layer after exposure by, for example, a paddle method, an immersion method, a shower method, or the like. 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. Content of the alkaline compound in a developing solution is a mass fraction with respect to a developing solution, Preferably it is 0.01-10 mass%, More preferably, it is 0.1-5 mass%.

  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 sulfate salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate;
Alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate;
Examples thereof include alkylaryl sulfonates such as sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate.
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.

  By development, in the positive-type colored radiation-sensitive resin composition layer, the radiation irradiated area irradiated with radiation in the previous exposure is dissolved in the developer, and the unexposed radiation irradiated area is developed. It remains without dissolving in the liquid to form a resin pattern.

  Since the positive colored radiation sensitive resin composition of the present invention contains the quinonediazide compound (B), the irradiation region is easy even if the time for contacting the positive colored radiation sensitive resin composition layer with the developer is short. Dissolved in and removed. In addition, since it contains the quinonediazide compound (B), the unirradiated area does not dissolve and disappear in the developer even when the time for contacting the positive colored radiation-sensitive resin composition layer with the developer is increased. .

  After alkali development, it is usually washed with water and dried. When higher light resistance is required, it is preferable to irradiate the entire or part of the obtained resin pattern with radiation after drying. The radiation to be irradiated here is preferably ultraviolet rays or deep ultraviolet rays, and the irradiation amount per unit area is preferably larger than the irradiation amount in the previous exposure.

  The resin pattern thus formed is preferably further subjected to heat treatment (post-baking) from the viewpoint of improving the heat resistance and solvent resistance of the colored cured resin pattern finally obtained. The heating is performed by a method of heating the substrate with a heating device such as a hot plate or a clean oven. The heating temperature is usually about 150 ° C to 250 ° C, preferably about 180 ° C to 240 ° C, and the heating time is usually about 5 minutes to 120 minutes, preferably about 15 minutes to 90 minutes. By heating, the pattern is cured and a colored cured resin pattern is formed.

  The colored cured resin pattern thus formed is obtained by curing the positive colored radiation-sensitive resin composition of the present invention. For example, the photo spacer for liquid crystal panel, the protrusion for controlling liquid crystal alignment, the black matrix It is useful as a colored cured resin pattern that constitutes the above.

  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.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited by these Examples.

Synthesis example 1
In a 200 mL four-necked flask equipped with a stirrer, cooling tube and thermometer, the following raw materials were charged, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the flask internal temperature was kept at 85 to 95 ° C. The reaction was conducted with stirring for 3 hours to obtain Resin A1. This resin A1 had a polystyrene equivalent weight average molecular weight of 8,000.

Methacrylic acid 7.9g
14.5 g of N-cyclohexylmaleimide
3-ethyl-3-methacryloxymethyloxetane 21.4g
Diethylene glycol methyl ethyl ether 90.7g
Azobisisobutyronitrile 1.1g

  Here, the polystyrene equivalent weight average molecular weight of the resin A1 was measured under the following conditions.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL, TSK-GELG4000HXL in-line column temperature; 40 ° C
Mobile phase solvent; tetrahydrofuran flow rate; 1.0 mL / min
Injection volume: 50 μL
Detector; RI
Measurement sample concentration: 0.6% by mass (solvent: tetrahydrofuran)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 1
Resin A1 (100 parts by mass), compound represented by the following formula (1) (30 parts by mass), KBM-303 (manufactured by Shin-Etsu Silicone, 3 parts by mass), diethylene glycol methyl ethyl ether (3 parts by mass), butyl lactate ( 16 mass parts), SH8400 (manufactured by Toray Dow Corning, 0.03 mass parts) and black colorant (black pigment 19 wt%, dispersant 5 wt%, propylene glycol monomethyl ether acetate 76 wt% mixed, 10 mass Part) to obtain a positive colored radiation-sensitive resin composition 1.

On the transparent glass substrate (# 1737; manufactured by Corning), the positive colored radiation-sensitive resin composition 1 obtained above was spin-coated, and heated (prebaked) at 100 ° C. for 3 minutes using a clean oven to 3 μm. A thick radiation-sensitive resin composition layer was formed. The film thickness was measured with a film thickness meter (DEKTAK3; manufactured by ULVAC, Inc.).
Thereafter, a contact aligner (M-2Li; manufactured by Mikasa Co., Ltd.) was used for the obtained positive-type colored radiation-sensitive resin composition layer, and the radiation (intensity based on a wavelength of 365 nm was 150 mJ / cm through a mask). ² ) and irradiated. The masks used at this time are: line / space = 30 μm / 30 μm, 20 μm / 20 μm, 10 μm / 10 μm, 9 μm / 9 μm,
It includes patterns of 8 μm / 8 μm, 7 μm / 7 μm, 6 μm / 6 μm, 5 μm / 5 μm.

  After the exposure, the film was developed by being immersed in a developer at 23 ° C. (aqueous solution containing 0.1% by weight of potassium hydroxide and containing a nonionic surfactant) for 150 seconds, washed with ultrapure water, and dried. Thereafter, post baking was performed at 220 ° C./30 minutes to obtain a resin pattern. As a result of observing the obtained resin pattern using a scanning electron microscope, it was confirmed that the resin pattern was formed with a line / space pattern of 6 μm / 6 μm or more.

Comparative Example 1
Resin B1 [copolymer represented by formula (2), the ratio of each structural unit is a / b / c / d = 10/54/21/15, the polystyrene-equivalent weight average molecular weight is 15,000, The weight average molecular weight in terms of polystyrene was measured under the same conditions as for the resin A1. (50 parts by mass), photopolymerization compound KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (50 parts by mass), photoinitiator Irgacure 369 (manufactured by Ciba Specialty Chemicals) (3 parts by mass), photoinitiator auxiliary EAB -F (manufactured by Hodogaya Chemical Co., Ltd.) (1 part by mass), propylene glycol monomethyl ether acetate (113 parts by mass), 3-ethoxyethyl propionate (24 parts by mass) and a black colorant (black pigment 19 weights) %, Dispersant 5% by weight, and propylene glycol monomethyl ether acetate 76% by weight) (10 parts by mass) were mixed to obtain a positive colored radiation-sensitive resin composition 2.

  In the same manner as in Example 1, a radiation-sensitive resin composition layer was formed from the positive colored radiation-sensitive resin composition 2 obtained above. Further, the obtained positive colored radiation-sensitive resin composition layer was exposed in the same manner as in Example 1.

After exposure, the film was developed by immersing in a developer at 23 ° C. (aqueous solution containing 0.05% by weight of potassium hydroxide and containing a nonionic surfactant) for 120 seconds, washed with ultrapure water, and dried. Thereafter, post baking was performed at 220 ° C./30 minutes to obtain a resin pattern. As a result of observing the obtained resin pattern using a scanning electron microscope, it was confirmed that the resin pattern was formed with a line / space pattern of 20 μm / 20 μm or more. However, in the pattern of 10 μm / 10 μm or less, a residue was partially observed.

Claims (9)

  In the radiation-sensitive resin composition containing the curable alkali-soluble resin (A), the quinonediazide compound (B), and the colorant (C), the curable alkali-soluble resin (A) is obtained from an unsaturated carboxylic acid. Positive type colored radiation-sensitive resin composition, which is a copolymer comprising a derived structural unit (a1) and a structural unit (a2) derived from an unsaturated compound having an oxetanyl group [however, oxetanyl led to the structural unit (a2) Unsaturated compounds having groups are not unsaturated carboxylic acids].   The curable alkali-soluble resin (A) is further derived from a structural unit (a31) derived from a carboxylic acid ester having a carbon-carbon unsaturated bond, and a structural unit derived from an aromatic compound having a carbon-carbon unsaturated bond. (A32), a structural unit (a33) derived from a vinyl cyanide compound, a structural unit (a34) derived from a maleimide compound optionally substituted at the N-position, and an epoxy compound having a carbon-carbon unsaturated bond The positive type colored radiation-sensitive resin composition according to claim 12, comprising at least one structural unit (a3) selected from the group consisting of the structural unit (a35).   The positive colored radiation-sensitive resin composition according to claim 1 or 2, wherein the colorant (C) is at least one pigment selected from the group consisting of organic pigments and black inorganic pigments.   Furthermore, the positive colored radiation sensitive resin composition in any one of Claims 1-3 containing an organic solvent (D).   A colored cured resin pattern formed using the positive colored radiation-sensitive resin composition according to claim 1.   A positive colored radiation-sensitive resin composition according to any one of claims 1 to 4 is applied onto a substrate, and after removing the solvent, irradiated with radiation through a mask, and then developed with an aqueous alkali solution to obtain a predetermined The manufacturing method of the colored cured resin pattern which forms a pattern.   The method for producing a colored cured resin pattern according to claim 6, further comprising heating after forming the predetermined pattern.   A positive colored radiation-sensitive resin composition according to any one of claims 1 to 4 is applied onto a substrate, and after removing the solvent, irradiated with radiation through a mask, and then developed with an aqueous alkali solution to obtain a predetermined A method for producing a colored cured resin pattern in which radiation is applied to the entire pattern surface or a part thereof on a substrate after forming the pattern. The method for producing a colored cured resin pattern according to claim 8, wherein the entire surface of the pattern on the substrate or a part thereof is irradiated with radiation and further heated.