JP4614054B2 - Dye-containing resist composition and color filter using the same - Google Patents

Description

  The present invention relates to a dye-containing resist composition and a color filter using the same.

  Color filters for image sensors such as solid-state image sensors or liquid crystal display elements can be used to produce high-definition color filters mainly because fine patterns can be formed. It is manufactured using the method of forming. In this method, a resist composition containing a dye and a polymer resin is used, applied to a substrate, and then a colored layer is patterned and developed by a photolithography method to form a single colored pattern. This process is repeated for each color to produce a color filter.

In that case, a pigment having excellent heat resistance and light resistance is generally used as a coloring agent used as a colorant, and a resist in which the pigment is dispersed has been proposed. For example, a photosensitive colored resin composition comprising a resin-based material that can be cured by an acid, a photoacid generator, and a pigment is disclosed. There is disclosed a crosslinking agent having a resin-based material containing phenol and a N-methylol structure. (For example, Patent Document 1)
However, since the pigment itself contains particles of about 1 μm, the fine particles cannot be formed due to the influence of the particles. Therefore, it has become difficult to produce a color filter for a charge coupled device (CCD) that requires high resolution.
On the other hand, when a dye is used as the pigment, since the dye is soluble in an organic solvent, a uniform resist composition can be obtained. Therefore, it is possible to form a fine pattern as compared with a resist composition in which a pigment is dispersed. For example, a negative resist composition comprising a resin curable with an acid, a crosslinking agent, a photoacid generator, a dye and a solvent is disclosed. Examples of the solvent include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, Examples include cyclohexanone, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, ethyl pyruvate, dimethylformamide and the like. (For example, patent document 2).
JP-A-4-163552 JP-A-6-51514

  Since dyes generally have low solubility in organic solvents, it is difficult to increase the dye concentration in the resist composition. In particular, when the color filter is further thinned, it is necessary to increase the dye concentration in the resist composition in order to develop a predetermined spectral spectrum. In addition, when the compatibility between the dye and the resin is low, the dye is insolubilized or precipitated during the preparation of the resist composition using the dye, the resin and the organic solvent, and further, the resist composition is added to the organic solvent during storage. There is a problem that a dye having low solubility is easily reprecipitated and recrystallized to easily generate foreign matters.

  The present invention is to provide a color resist composition that does not cause problems such as the generation of foreign matter even when the dye concentration is increased in order to cope with the reduction in the thickness of the color filter.

As a first aspect of the present invention, a dye-containing resist composition containing a ketol-based solvent,
As a second aspect, containing a resin (a-1), a photoacid generator or a photobase generator (b-1), a crosslinkable compound (c-1), a dye (d), and a ketol-based solvent (e) Negative resist composition,
As a third aspect, a negative resist composition containing a resin (a-2), a photoradical generator (b-2), a crosslinkable compound (c-2), a dye (d), and a ketol-based solvent (e) ,
As a fourth aspect, a positive resist composition containing a resin (a-3), a photoacid generator (b-3), a crosslinkable compound (c-3), a dye (d) and a ketol solvent (e) ,
As a fifth aspect, the resist composition according to any one of the first to fourth aspects, wherein the solvent contains at least 1% by weight of ketol relative to the whole solvent,
As a sixth aspect, the resist composition according to any one of the first to fifth aspects, in which ketol is β-hydroxyketone,
As a seventh aspect, the resist composition according to any one of the first aspect to the fifth aspect, in which ketol is 4-hydroxy-4-methyl-2-pentanone,
As an eighth aspect, a method for producing a color filter comprising the steps of coating, drying, exposing, and developing the resist composition according to any one of the first to seventh aspects on a substrate,
As a ninth aspect, a color filter manufactured by the method according to the eighth aspect,
As a tenth aspect, a solid-state imaging device having a color filter manufactured by the method according to the eighth aspect,
As an eleventh aspect, a liquid crystal display element having a color filter manufactured by the method described in the eighth aspect, and as a twelfth aspect, a light emitting diode display element having a color filter manufactured by the method described in the eighth aspect. is there.

  The invention of the present application ensures sufficient dye solubility even when the dye concentration is increased in order to cope with the thinning of the color filter, and there is no problem such as generation of foreign matter due to dye precipitation even under long-term storage, and storage stability is improved. In order to provide a high color resist composition, it has been found that a ketol-based solvent, preferably β-hydroxyketone, particularly preferably 4-hydroxy-4-methyl-2-pentanone, is used as a solvent.

  Ketol is also called hydroxyketone and is a general term for ketones having a hydroxyl group. Among the ketols, β-hydroxyketone is particularly preferable. The presence of the hydroxyl group and the carbonyl group of the ketone in a specific positional relationship (β position) in the molecule increases the interaction with the dye molecule and improves the solubility, and the dye is resistant to temperature changes and long-term storage. There is no generation of foreign matter or the like due to precipitation of components. Among the β-hydroxy ketones, 4-hydroxy-4-methyl-2-pentanone is particularly excellent in terms of these effects.

  As a result, the solubility of the dye and the compatibility between the dye and the resin are increased, and a predetermined dye concentration can be secured, so that a color filter capable of expressing a desired spectral spectrum can be produced.

  The present invention is a dye-containing resist composition containing a ketol-based solvent.

  More specifically, the resist composition of the present invention can be applied to a negative type and a positive type.

  As a negative resist composition, first, resin (a-1), photoacid generator or photobase generator (b-1), crosslinkable compound (c-1), dye (d), and ketol series A negative resist composition containing a solvent (e), and secondly a resin (a-2), a photoradical generator (b-2), a crosslinkable compound (c-2), a dye (d) and a ketol It is a negative resist composition containing a system solvent (e).

  The positive resist composition contains a resin (a-3), a photoacid generator (b-3), a crosslinkable compound (c-3), a dye (d), and a ketol-based solvent (e). It is a positive resist composition.

  The resin used in the negative resist composition is a resin (a-1) that is cured by an acid or base generated by heat or light irradiation, or a photosensitive resin (a-2) that is crosslinked by heat or light irradiation, If the coating film of the unexposed part in this resin can be removed with a developing solution, it will not specifically limit.

  Examples of the resin (a-1) include a resin having a hydroxyl group or a carboxyl group.

  For example, acrylic resins such as polyvinyl alcohol, polyacrylamide, polyacrylic acid and polymethacrylic acid, polyamic acid, polyhydroxystyrene, polyhydroxystyrene derivatives, copolymers of polymethacrylate and maleic anhydride, phenol resins, novolak resins , Polyimides containing a hydroxyl group and / or a carboxyl group, cellulose, cellulose derivatives, starch, chitin, chitosan, gelatin, zein, sugar skeleton polymer compound, polyamide, polyethylene terephthalate, polycarbonate, polyurethane and polysiloxane. These resins are used alone or in combination of two or more.

  Particularly preferred are polyhydroxystyrene, polyhydroxystyrene derivatives, phenolic resins and novolac resins.

  Examples of the carboxyl group-containing acrylic resin include an acrylic copolymer having (meth) acrylic acid ester as a main component and copolymerized with an ethylenically unsaturated carboxylic acid and other monomers as required.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl Examples include (meth) acrylate, benzyl (meth) acrylate, dimethylamino (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

  Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and acid anhydrides and half esters thereof. Of these, acrylic acid, methacrylic acid, and maleic acid are preferred.

  The acrylic copolymer has a weight average molecular weight of 1,000 to 100,000, and preferably 2000 to 30,000 from the viewpoint of developability and adhesion. These can be combined as necessary, and can be used alone or in combination of two or more.

  Examples of polyhydroxystyrene and polyhydroxystyrene derivatives include vinylphenol homopolymers and copolymers obtained by copolymerizing vinylphenol and other compounds. Other compounds at this time include acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorostyrene, etc. Examples thereof include styrene derivatives.

  The polyhydroxystyrene and the polyhydroxystyrene derivative have a weight average molecular weight of 1,000 to 100,000, preferably 2000 to 30,000 from the viewpoint of developability and adhesion. These can be combined as necessary, and can be used alone or in combination of two or more.

  Examples of the novolak resin include those obtained by condensing a phenol compound and an aldehyde compound or a ketone compound in the presence of an acid catalyst.

  Phenol compounds include phenol, m-cresol, p-cresol, o-cresol, m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethyl. Phenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, p-methoxyphenol, m-methoxy Phenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4- I Sopropenylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, resorcinol, hydroquinone, 4,4-dihydroxybiphenyl, phenylphenol, catechol, pyroganol, Examples include naphthol, bisphenol C, and bisphenol A. These phenol compounds can be used alone or in combination of two or more.

  Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, trioxane, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde Alude cinnamic acid Hydride and the like. These aldehyde compounds can be used alone or in combination of two or more.

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, and the like. These ketone compounds can be used alone or in combination of two or more.

  Examples of the acid catalyst used in the condensation reaction include hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid and the like.

  The novolak resin has a weight average molecular weight of 1,000 to 100,000, preferably 2000 to 30,000 from the viewpoint of developability and adhesion. These may be combined as necessary, and may be used alone or in combination of two or more.

  As the resin (a-2) having a photosensitive group that is cross-linked by heat or light irradiation, a carboxyl group-containing acrylic resin can be used. That is, it is an acrylic copolymer comprising (meth) acrylic acid ester as a main component and copolymerizing an ethylenically unsaturated carboxylic acid and other monomers as required.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl Examples include (meth) acrylate, benzyl (meth) acrylate, dimethylamino (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

  Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and acid anhydrides and half esters thereof. Of these, acrylic acid, methacrylic acid, and maleic acid are preferred.

  Examples of other monomers include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, alkyl vinyl ether, and the like.

  The acrylic copolymer has a weight average molecular weight of 1,000 to 100,000, and preferably 2000 to 30,000 from the viewpoint of developability and adhesion. These can be combined as necessary, and can be used alone or in combination of two or more.

  Among the photoinitiators (b-1) used when the resin (a-1) is used, the photoacid generator is particularly limited as long as it generates an acid directly or indirectly by light irradiation. Not. Specific examples include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryliodonium salts, triarylsulfonium salts, triarylphosphonium salts, iron arene complexes, and the like. However, it is not limited to these. Specifically, for example, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, Bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium Trifluoromethanesulfonate, bis (p-tert-butylphenyl) Donium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tri (P-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxy Phenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate , Tri (p- ethoxyphenyl) phosphonium tetrafluoroborate and the like.

  Moreover, the photo-acid generator mentioned by Formula (1)-Formula (68) can also be used.

  These photoacid generators can be used alone or in combination of two or more. Moreover, the introduction amount is selected in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the resin (a-1) component. When this amount is less than 1 part by weight, the crosslinking reaction does not proceed sufficiently, making it difficult to obtain a desired resist pattern, and when it exceeds 100 parts by weight, the storage stability of the resist composition is poor. Therefore, the introduction amount of the photoacid generator is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin (a-1) component.

  The photobase generator is not particularly limited as long as it generates a base directly or indirectly by light irradiation. For example, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexyl carbamate, di (methoxybenzyl) hexamethylene dicarbamate, and the following formulas (69)- And a compound having the structure (71).

However, in Formula (69)-Formula (71), R < ₁ >, R < ₂ > and R < ₃ > show a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted phenyl group.

  These photobase generators can be used alone or in combination of two or more, like the photoacid generator. Moreover, it is preferable that the introduction amount is 1-100 weight part with respect to 100 weight part of resin (a-1) components for the same reason as the above.

  Examples of the photo radical generator (b-2) used for the resin (a-2) include tert-butylperoxy-iso-butarate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (Iso-propylphenyl) -iso-propylhydroperoxide, 2,5-dimethylhexane, tert-butylhydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl -4,4-bis (tert-butyldioxy) valerate, cyclohexanone peroxide, 2,2 ', 5,5'-tetra (tert-butylpe Oxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,4′-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldi Organic peroxides such as peroxyisophthalate, quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, benzoin methyl, benzoin ethyl ether, α-methylbenzoin, - and the like benzoin derivatives such as phenyl benzoin.

  These photo radical generators can be used alone or in combination of two or more. Moreover, it is preferable that the introduction amount is 1-100 weight part with respect to 100 weight part of resin (a-2) components for the same reason as the above.

  Further, conventionally known photosensitizers can be used as photosensitizers. For example, thioxanthene, xanthene, ketone, thiopyrylium salt, base styryl, merocyanine, 3-substituted coumarin, 3,4-substituted coumarin, cyanine, acridine, thiazine, phenothiazine, anthracene , Coronene, benzanthracene, perylene, merocyanine, ketocoumarin, fumarine, and borate. These can be used alone or in combination of two or more.

  The crosslinkable compound (c-1) used for the resin (a-1) is a compound having at least one crosslinkable group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. There is no particular limitation.

  For example, amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like can be mentioned.

  As the crosslinkable compound (c-1), for example, a melamine derivative, a benzoguanamine derivative or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. This melamine derivative and benzoguanamine derivative may exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

  As an example of such a melamine derivative or a benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring in a commercially available product, and an average of 5. methoxymethyl groups per one triazine ring. Eight-substituted MW-30 (from Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated ethoxy Mitylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cytec). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and the like.

  Also, benzene or phenolic compounds having a hydroxyl group or an alkoxyl group, such as 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, 1,4-bis (sec -Butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

  Moreover, the compound which contains an epoxy group and an isocyanate group and has a bridge | crosslinking formation group can be used. Specific examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (amino). Ethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2 , 2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetrag Sidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxyphenyl) -1-methyl) And ethyl) phenyl) ethyl) phenoxy) -2-propanol.

  These crosslinkable compounds (c-1) can be used alone or in combination of two or more. The amount introduced is selected in the range of 1 to 200 parts by weight per 100 parts by weight of the resin (a-1) component. When this amount is less than 1 part by weight, the crosslinking reaction does not proceed sufficiently, making it difficult to obtain a desired resist pattern, and when it exceeds 200 parts by weight, the storage stability of the resist composition is poor. Therefore, the introduction amount of the crosslinkable compound is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the resin component.

  Examples of the crosslinkable compound (c-2) used for the resin (a-2) include compounds having the following polymerizable unsaturated groups. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) Compounds having three polymerizable unsaturated groups in the molecule such as acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) ) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, etc. A compound having two unsaturated groups in the molecule, in addition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meta) ) Acrylate, 2- (meth) acryloyloxyethyl phosphate ester, N-methylol (meth) acrylamide, etc., and a compound having one polymerizable unsaturated group in the molecule.

  These crosslinkable compounds can be used alone or in combination of two or more. The amount of introduction is selected in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the resin (a-2) component. When this amount is less than 1 part by weight, the crosslinking reaction does not proceed sufficiently, making it difficult to obtain a desired resist pattern, and when it exceeds 200 parts by weight, the storage stability of the resist composition is poor. Therefore, the amount of the crosslinkable compound introduced is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the resin (a-2) component.

  The resin (a-3) used in the positive resist composition is a resin that is cured by heat, and the polarity and molecular weight change due to decomposition of the resin by an acid generated by heat or light irradiation. However, it is not particularly limited as long as it exhibits solubility and the coating film of the exposed portion in the resin can be removed by a developer.

  Examples of the resin (a-3) include a resin having a hydroxyl group or a carboxyl group. Specifically, for example, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethacrylic acid, polyamic acid, polyhydroxystyrene, polyhydroxystyrene derivative, copolymer of polymethacrylate and maleic anhydride, phenol resin and novolac resin , A polyimide containing a hydroxyl group and / or a carboxyl group, a cellulose derivative, a sugar skeleton polymer compound, polyamide, polyethylene terephthalate, polycarbonate, polyurethane, and polysiloxane. More specifically, the resin shown with the resin (a-1) mentioned above is mentioned. These resins can be used alone or in combination of two or more.

  A carboxyl group-containing acrylic resin can also be used. That is, it is an acrylic copolymer comprising (meth) acrylic acid ester as a main component and copolymerizing an ethylenically unsaturated carboxylic acid and other monomers as required. Specifically, the resin shown by the resin (a-2) mentioned above is mentioned. These resins are used alone or in combination of two or more.

  Examples of the photoacid generator (b-3) used in the positive resist composition include a naphthoquinone diazide compound. In general, 1,2-quinonediazide compounds are used. Examples 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-naphthoquinone diazide sulfonic acid amide. More specifically, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxylihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzofe -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-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 '-Tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5 -Sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzof Non-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4 4,2 ′, 6-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2 ′, 6-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexa Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahi Droxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-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, tri (p-hydroxyphenyl) methane- 1,2-naphthoquinonediazide-4-sulfonic acid ester, Li (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) ethane-1,2-naphthoquinonediazide-4 -Sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) ethane-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-trihydroxyphene) ) 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-sulfo 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-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan- , 2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4 -Trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid amide etc. are mentioned.

  These naphthoquinonediazide compounds can be used alone or in combination of two or more. Moreover, the introduction amount is selected in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the resin (a-3) component. When this amount is less than 1 part by weight, the crosslinking reaction does not proceed sufficiently, making it difficult to obtain a desired resist pattern, and when it exceeds 50 parts by weight, the storage stability of the resist composition is poor. Therefore, the amount of the naphthoquinone diazide compound introduced is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the resin component.

  As the crosslinkable compound (c-3) used in the positive resist composition, a compound having at least one crosslink forming group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, or A compound containing an epoxy group and an isocyanate group, having a crosslink forming group, and further having a polymerizable unsaturated group can be used. Specifically, (c-1) shown by the above-mentioned negative resist composition is mentioned.

  These crosslinkable compounds (c-3) can be used alone or in combination of two or more. Moreover, the amount introduced is selected in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the resin (a-3) component. When this amount is less than 1 part by weight, the crosslinking reaction does not proceed sufficiently, making it difficult to obtain a desired resist pattern, and when it exceeds 200 parts by weight, the storage stability of the resist composition is poor. Therefore, the introduction amount of the crosslinkable compound is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the resin component.

  The dye (d) used in the negative and positive resist compositions of the present invention should have a spectral spectrum desirable as a color filter and can be dissolved in a solvent as it is or in a modified form of the dye. Can do. Examples of these dyes include acid dyes, oil-soluble dyes, disperse dyes, reactive dyes, and direct dyes. For example, azo dye, benzoquinone dye, naphthoquinone dye, anthraquinone dye, cyanine dye, squarylium dye, croconium dye, merocyanine dye, stilbene dye, diphenylmethane dye, triphenylmethane dye, fluoran dye Examples include dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes. Specific examples of color index numbers include the following. C. I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131 133, 135, 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185 186, 187, 189, 190, 191, C.I. I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112, 113, C.I. I. Solvent Red 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197 , 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 236 238,239,240,241,242,243,244,245,247,248, C. I. Solvent Violet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58 59, 60, 61, C.I. I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59: 1, 63, 64, 67, 68 69, 70, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139, 143 , C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, C.I. I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52, 53, 59, 60, 61, 62, 63, C.I. I. Solvent Black 3, 5, 5: 2, 7, 13, 22, 22: 1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49, 50, C.I. I. Acid Red 6, 11, 26, 60, 88, 111, 186, 215, C.I. I. Acid Green 25, 27, C.I. I. Acid Blue 22, 25, 40, 78, 92, 113, 129, 167, 230, C.I. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, C.I. I. Basic Green 3, 4, C.I. I. Basic Blue 3, 9, 41, 66, C.I. I. Basic Violet 1, 3, 18, 39, 66, C.I. I. Basic Yellow 11, 23, 25, 28, 41, C.I. I. Direct Red 4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149, 224, C.I. I. Direct Green 26, 28, C.I. I. Direct Blue 71, 78, 98, 106, 108, 192, 201, C.I. I. Direct Violet 51, C.I. I. Direct Yellow 26, 27, 28, 33, 44, 50, 86, 142, C.I. I. Direct Orange 26, 29, 34, 37, 72, C.I. I. Sulfur Red 5, 6, 7, C.I. I. Sulfur Green 2, 3, 6, C.I. I. Sulfur Blue 2, 3, 7, 9, 13, 15, C.I. I. Sulfur Violet 2, 3, 4, C.I. I. Sulfur Yellow 4, C.I. I. Vat Red 13, 21, 23, 28, 29, 48, C.I. I. Vat Green 3, 5, 8, C.I. I. Vat Blue 6, 14, 26, 30, C.I. I. Vat Violet 1, 3, 9, 13, 15, 16, C.I. I. Vat Yellow 2, 12, 20, 33, C.I. I. Vat Orange 2, 5, 11, 15, 18, 20, C.I. I. Azoic Coupling Component 2, 3, 4, 5, 7, 8, 9, 10, 11, 13, 32, 37, 41, 48, C.I. I. Reactive Red 8, 22, 46, 120, C.I. I. Reactive Blue 1, 2, 7, 19, C.I. I. Reactive Violet 2, 4, C.I. I. Reactive Yellow 1, 2, 4, 14, 16, C.I. I. Reactive Orange 1, 4, 7, 13, 16, 20, C.I. I. Disperse Red 4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356, C.I. I. Disperse Blue 3, 24, 79, 82, 87, 106, 125, 165, 183, C.I. I. Disperse Violet 1, 6, 12, 26, 27, 28, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64, C.I. I. Disperse Orange 13, 29, 30. These dyes can be used alone or in combination of two or more in order to develop a desired spectral spectrum.

In the dye-containing negative resist composition, the amount of dye (d) introduced is resin (a-1)), photoacid generator or photobase generator (b-1), crosslinkable compound (c-1) and It is selected in the range of 1 to 90% by weight with respect to the entire solid content (100%) comprising the dye (d). When the amount of the dye introduced is small, it becomes difficult to develop a desired spectral spectrum when the resist film is thinned, and when the amount of the dye introduced is large, the storage stability of the resist composition is poor. However, in the negative resist composition of the present invention, the use of the ketol-based solvent (e) allows the introduction amount of the above dye (the concentration of the dye in the solid content) to be used at a low concentration of several weight percent. However, even if the concentration is set to a high concentration of 30 to 90% by weight, the dye can sufficiently ensure solubility.
Similarly, in the dye-containing negative resist composition comprising the resin (a-2), the photoradical generator (b-2), the crosslinkable compound (c-2) and the dye (d), the dye (d) Is introduced in the range of 1 to 90% by weight with respect to the entire solid content (100%). When the amount of the dye introduced is small, it becomes difficult to develop a desired spectral spectrum when the resist film is thinned, and when the amount of the dye introduced is large, the storage stability of the resist composition is poor. However, in the negative resist composition of the present invention, the use of the ketol-based solvent (e) allows the introduction amount of the above dye (the concentration of the dye in the solid content) to be used at a low concentration of several weight percent. However, even if the concentration is set to a high concentration of 30 to 90% by weight, the dye can sufficiently ensure solubility.

  Further, in the dye-containing positive resist composition, the amount of the dye (d) introduced is the resin (a-3), the photoacid generator (b-3), the crosslinkable compound (c-3) and the dye (d). Is selected in the range of 1 to 90% by weight with respect to the entire solid content (100%). When the amount of the dye introduced is small, it becomes difficult to develop a desired spectral spectrum when the resist film is thinned, and when the amount of the dye introduced is large, the storage stability of the resist composition is poor. However, in the positive resist composition of the present invention, the use of the ketol-based solvent (e) enables the introduction amount of the above dye (the concentration of the dye in the solid content) to be used at a low concentration of several weight percent. However, even if the concentration is set to a high concentration of 30 to 90% by weight, the dye can sufficiently ensure solubility.

  The solvent (e) used in the negative and positive resist compositions of the present invention is a ketol solvent. Among these, β-hydroxyketone is preferable, and as β-hydroxyketone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-hexanone, 4-hydroxy-4-ethyl-2 -Hexanone, 4-hydroxy-4-methyl-2-heptanone, 4-hydroxy-4-ethyl-2-heptanone, 4-hydroxy-4-propyl-2-heptanone, 2-methyl-2-hydroxy-4-hexanone 2-methyl-2-hydroxy-4-pentanone, 2,3-dimethyl-3-hydroxy-5-hexanone, 2,6-dimethyl-2-hydroxy-4-heptanone, and the like.

  Of these, 4-hydroxy-4-methyl-2-pentanone is most preferable in terms of solubility and availability of the dye.

  In the present invention, the ketol solvent is based on the use of ketol, preferably β-hydroxyketone, particularly preferably 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) alone. It means that other solvents are mixed and used. From the viewpoint of enhancing the solubility of the dye and the compatibility between the dye and the resin, when the total solvent is 100%, ketol, preferably β-hydroxyketone, particularly preferably 4-hydroxy-4-methyl-2-pentanone The amount introduced is 1 to 100% by weight, preferably 10 to 100% by weight.

  Examples of other solvents mixed with ketol include acetone, methanol, ethanol, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, and ethyl. Cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether , Propylene glycol-tert-butyl ether Dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxy Butanol, diisopre Pyrether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide , N-methylpyrrolidone, γ-butyrolactone, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate Ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropio Examples include acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and diglyme. These can be used alone or in combination of two or more with ketol.

  In the dye-containing negative and positive resist compositions of the present invention, resin (a-1, a-2 or a-3), photoinitiator (b-1, b-2 or b-3), crosslinkable compound The content ratio of (c-1, c-2 or c-3) and the dye (d), that is, the solid content concentration is 5 to 50% by weight, preferably 10 to 30% by weight.

  When this ratio is less than 5% by weight, the film thickness of the coating film becomes too small, and the occurrence of pinholes becomes a problem. On the other hand, when it exceeds 50% by weight, the viscosity of the resist composition becomes excessive, and the film thickness uniformity of the coating film is impaired.

  The dye-containing negative resist composition and the positive resist composition of the present invention can contain a surfactant for the purpose of improving the wettability and flatness of the resist film. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products)), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like.
The use ratio of these surfactants is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the resin component. When the surfactant content is more than 2 parts by weight, the resist film tends to be uneven, and when it is less than 0.01 part by weight, striations are likely to occur in the resist film.

  Moreover, an adhesion promoter can be contained for the purpose of improving the adhesion to the substrate after development. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane. , Alkoxysilanes such as diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole silazanes, vinyltrichlorosilane, γ-chloropropyl Trimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxyp Silanes such as pyrtrimethoxysilane, heterocyclic groups such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine A compound, urea, such as 1, 1- dimethylene urea and 1, 3- dimethyl urea, or a thiourea compound can be mentioned.

  The use ratio of these adhesion promoters is usually 20 parts by weight or less, preferably 0.05 to 10 parts by weight, particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of the resin component.

  Additives miscible with the resist composition can be further added to the dye-containing negative and positive resist compositions of the present invention. For example, ultraviolet absorbers and antioxidants that improve light resistance, compatibilizers that suppress dye precipitation, and the like can be mentioned. Specific examples of the compatibilizing agent that suppresses the precipitation of the dye include a polyoxyethylene octyl ether compound, a polyoxyethylene lauryl ether compound, a polyoxyethylene alkyl (carbon number 12 to 13) ether compound, a polyoxyethylene secondary alkyl ( C12-14) ether compound, polyoxyethylene alkyl (carbon number 13) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl ether compound, polyoxyethylene oleyl ether compound, polyoxyethylene decyl ether compound, poly Alkyl ether compounds such as oxyalkylene alkyl (carbon number 11-15) ether compounds, polyoxyalkylene secondary alkyl (carbon numbers 12-14) ether compounds, polyoxyalkylene cetyl ether compounds, polyoxy Tylene lauryl amino ether compound, polyoxyethylene stearyl amino ether compound, alkylamino ether compound such as polyoxyethylene oleyl amino ether compound, polyoxyethylene lauric acid amide ether compound, polyoxyethylene stearic acid amide ether compound, polyoxyethylene olein Alkylamide ether compounds such as acid amide ether compounds, lauric acid diethanolamide compounds, stearic acid diethanolamide compounds, oleic acid diethanolamide compounds, polyoxyethylene polystilphenyl ether compounds, polyoxyalkylene polystilphenyl ether compounds, polyoxyalkylenes Polystilphenyl ether formamide condensate, polyoxyethylene monostyryl Nyl ether compounds, polyoxyethylene distyryl phenyl ether compounds, allyl phenyl ether compounds such as polyoxyethylene naphthyl ether compounds, glycerol monolaurate compounds, glycerol monostearate compounds, glycerol monooleate compounds, glycerol trioleate compounds, etc. Sorbitan acid ester compounds such as ester compounds, sorbitan monolaurate compounds, sorbitan monopalmitate compounds, sorbitan monostearate compounds, sorbitan tristearate compounds, sorbitan monooleate compounds, sorbitan trioleate compounds, polyoxyethylene dilaurate compounds, poly Oxyethylene laurate compound, polyoxyethylene stearate compound, polyoxyethylene diste Fatty acid ether ester compounds such as allate compounds, polyoxyethylene diolate compounds, polyoxyethylene oleate compounds, vegetable oil ether ester compounds such as polyoxyethylene castor oil ether compounds, polyoxyethylene hydrogenated castor oil ether compounds, polyoxyethylene sorbitan mono Laurate compounds, polyoxyethylene sorbitan monostearate compounds, polyoxyethylene sorbitan monooleate compounds, sorbitan ether ester compounds such as polyoxyethylene sulfitan trioleate compounds, polyoxyalkylene butyl ether compounds, polyoxyalkylene octyl ether compounds, poly Mono, such as oxyalkylene alkyl (carbon number 14-15) ether compound, polyoxyalkylene oleyl ether compound Polyol compounds such as all-type polyether compounds, diol-type polyether compounds such as polyoxyethylene polyoxypropylene condensates, trimethylolpropane tris (polyoxyalkylene) ether compounds, polyoxyalkylene glyceryl ether compounds, methyl laur Rate compounds, methyl oleate compounds, isopropyl myristate compounds, butyl stearate compounds, octyl palmitate compounds, octyl stearate compounds, lauryl oleate compounds, isotridecyl stearate compounds, oleyl oleate compounds, dioleyl adipate compounds, trimethylolpropane Tridecanoate compound, trimethylolpropane trilaurate compound, pentaerythritol diolate compound, pentaerythritol Fatty acid alkyl ester compounds, alkyl sulfonate compounds, long-chain alkyl benzene sulfonate compounds, branched alkyl benzene sulfonate compounds, long-chain alkyl benzene sulfonate compounds, branched alkyl benzene sulfonate compounds, branched alkyl diphenyl ethers, such as alkyl monostearate compounds and pentaerythritol distearate compounds Disulfonate compounds, monoisopropyl naphthalene sulfonate compounds, diisopropyl naphthalene sulfonate compounds, triisopropyl naphthalene sulfonate compounds, dibutyl naphthalene sulfonate compounds, dioctyl sulfosuccinate compounds and other sulfonic acid type compounds, oleic acid sulfated oil compounds, castor sulfate compounds, Octyl sulfate compounds, lauryl sulfate Compounds, alkyl sulfates compounds, sulfate compounds such as alkyl ether sulfate compounds, cellulose, cellulose derivatives, sugar backbone polymer compound.

  The use ratio of these compatibilizers is 0.001 to 20 parts by weight with respect to 100 parts by weight of the resin component. When the amount used is small, the ability to suppress the precipitation of the dye is inferior to when many are used, and when it is large, it is difficult to obtain a good pattern shape. However, when the compatibilizing agent does not inhibit the pattern shape, 20 parts by weight or more can be used.

  Next, a method for preparing a color filter using the dye-containing negative resist composition for color filter and the positive resist composition of the present invention will be described.

The dye-containing negative resist composition and the positive resist composition of the present invention are applied onto a silicon wafer or glass substrate at a rotational speed to obtain a desired resist film thickness by spin coating or the like, and soft baking (baking) is performed. . The soft baking may be performed by evaporating the solvent, and is preferably performed in a temperature range of 50 to 150 ° C. for 30 seconds to 10 minutes. Then, it exposes with the exposure amount of about 100-2000mJ / cm < ² > through a mask. For the exposure, for example, ultraviolet rays such as a mercury lamp, far ultraviolet rays, electron beams, or X-rays are used. When a negative pattern is formed using a dye-containing negative resist composition after exposure, heating (PEB (post-exposure baking)) is preferably performed. By PEB, the crosslinking by the acid or base generated by exposure further proceeds, and the difference in the developer solubility from the unexposed area widens, and the contrast is improved. PEB is preferably performed in a temperature range of 50 to 150 ° C. for 30 seconds to 5 minutes.

  Next, development is performed. There is no restriction | limiting in particular as a image development method, It can carry out by well-known methods, such as a paddle method, a dip method, and a spray method. The development temperature is preferably between 20 ° C. and 30 ° C., and is preferably immersed in the developer for 10 seconds to 10 minutes.

  As the developer, an organic solvent or an alkaline aqueous solution can be used. Specifically, isopropyl alcohol, propylene glycol monomethyl ether, ethylamine aqueous solution, n-propylamine aqueous solution, diethylamine aqueous solution, di-n-propylamine aqueous solution, triethylamine aqueous solution, methyldiethylamine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, tetramethyl Ammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium bicarbonate aqueous solution, sodium silicate aqueous solution, sodium metasilicate aqueous solution and the like can be mentioned.

  Furthermore, it is preferable to add a surfactant to the developer in order to improve the removability of the unexposed area. Specific examples include polyoxyethylene octyl ether compounds, polyoxyethylene lauryl ether compounds, polyoxyethylene alkyl (carbon number 12-13) ether compounds, polyoxyethylene secondary alkyl (carbon numbers 12-14) ether compounds, poly Oxyethylene alkyl (carbon number 13) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl ether compound, polyoxyethylene oleyl ether compound, polyoxyethylene decyl ether compound, polyoxyalkylene alkyl (carbon number 11-15) Ether compounds, polyoxyalkylene secondary alkyl (C12-14) ether compounds, alkyl ether compounds such as polyoxyalkylene cetyl ether compounds, polyoxyethylene lauryl amino ether Compounds, alkylamino ether compounds such as polyoxyethylene stearyl amino ether compounds, polyoxyethylene oleyl amino ether compounds, polyoxyethylene lauric acid amide ether compounds, polyoxyethylene stearic acid amide ether compounds, polyoxyethylene oleic acid amide ethers Compounds, alkylamide ether compounds such as lauric acid diethanolamide compound, stearic acid diethanolamide compound, oleic acid diethanolamide compound, polyoxyethylene polystilphenyl ether compound, polyoxyalkylene polystilphenyl ether compound, polyoxyalkylene polystilphenyl Ether formamide condensate, polyoxyethylene monostyryl phenyl ether compound, polyoxy Allyl phenyl ether compounds such as ethylene distyryl phenyl ether compounds and polyoxyethylene naphthyl ether compounds, glycerin monolaurate compounds, glycerin monostearate compounds, glycerin monooleate compounds, glycerin fatty acid ester compounds such as glycerin trioleate compounds, sorbitan mono Sorbitanate compounds such as laurate compounds, sorbitan monopalmitate compounds, sorbitan monostearate compounds, sorbitan tristearate compounds, sorbitan monooleate compounds, sorbitan trioleate compounds, polyoxyethylene dilaurate compounds, polyoxyethylene laurate compounds , Polyoxyethylene stearate compound, polyoxyethylene distearate compound, polyoxyethylene Fatty acid ether ester compounds such as range oleate compounds, polyoxyethylene oleate compounds, vegetable oil ether ester compounds such as polyoxyethylene castor oil ether compounds, polyoxyethylene hydrogenated castor oil ether compounds, polyoxyethylene sorbitan monolaurate compounds, polyoxy Sorbitan ether ester compounds such as ethylene sorbitan monostearate compound, polyoxyethylene sorbitan monooleate compound, polyoxyethylene sulfitan trioleate compound, polyoxyalkylene butyl ether compound, polyoxyalkylene octyl ether compound, polyoxyalkylene alkyl (carbon number) 14-15) Monool-type polyether compounds such as ether compounds and polyoxyalkylene oleyl ether compounds, Diol-type polyether compounds such as reoxyethylene polyoxypropylene condensate, polyol-type polyether compounds such as trimethylolpropane tris (polyoxyalkylene) ether compound, polyoxyalkylene glyceryl ether compound, methyl laurate compound, methyl oleate compound , Isopropyl myristate compound, butyl stearate compound, octyl palmitate compound, octyl stearate compound, lauryl oleate compound, isotridecyl stearate compound, oleyl oleate compound, dioleyl adipate compound, trimethylolpropane tridecanoate compound, tri Methylolpropane trilaurate compound, pentaerythritol dioleate compound, pentaerythritol monostearate compound, Fatty acid alkyl ester compounds such as intererythritol distearate compounds, alkyl sulfonate compounds, long chain alkyl benzene sulfonate compounds, branched alkyl benzene sulfonate compounds, long chain alkyl benzene sulfonate compounds, branched alkyl benzene sulfonate compounds, branched alkyl diphenyl ether disulfonate compounds, monoisopropyl Sulfonic acid type compounds such as naphthalene sulfonate compound, diisopropyl naphthalene sulfonate compound, triisopropyl naphthalene sulfonate compound, dibutyl naphthalene sulfonate compound, dioctyl sulfosuccinate compound, oleic acid sulfated oil compound, castor sulfate compound, octyl sulfate compound, lauryl sulfate Compound, alkyl sulfate Things, sulfate compounds such as alkyl ether sulfate compounds. The preferred concentration of the alkali developer is 0.001 to 10% by weight for the alkali component and 0.001 to 10% by weight for the surfactant component. If the alkali component is too high, the developing ability is too strong. In the negative type, the unexposed area and the exposed area in the positive type are likely to penetrate into the exposed area, and the pattern surface is likely to be roughened. On the other hand, if the surfactant component is too high, foaming is likely to occur and uneven development tends to occur. If it is too low, the developing ability cannot be obtained.

After development, it is preferable to rinse with water or a general organic solvent. Then, a pattern is formed by drying. When the dye-containing negative resist composition is used, a negative pattern is formed in which the exposed portion is cured and the unexposed portion is dissolved, and when the dye-containing positive resist composition is used, the exposed portion is A dissolving positive pattern is formed.
By repeating the above-described series of steps for each color and mask and repeating the necessary number of times, a colored pattern in which the necessary number of colors are combined can be obtained. In addition, after pattern formation, heating (post-baking) may be performed in order to completely react the polymerizable or condensable functional groups remaining in the pattern. The post-baking may be performed every time a pattern of each color is formed or after all the colored patterns are formed, and is preferably performed at a temperature range of 150 to 500 ° C. for 30 minutes to 2 hours.

(Adjustment of dye-containing negative resist composition)
Novolak resin: phenol novolac resin A obtained by condensing phenol and formaldehyde (number average molecular weight 9000 (polystyrene conversion))
Polyhydroxystyrene resin: VP8000 (Nippon Soda)
Polyhydroxystyrene copolymer: Marker linker CHM (a copolymer of p-vinylphenol and 2-hydroxyethyl methacrylate in a molar ratio of 1: 1) (manufactured by Maruzen Petroleum)
Acrylic resin: Acrylic resin A (Propylene glycol monomethyl ether acetate solution having a molar ratio of 9: 25.5: 65.5, which is a copolymer of (meth) acrylic acid, hydroxyethyl (meth) acrylate and methyl (meth) acrylate) Solid content concentration: 22.0% by weight, weight average molecular weight 6000 (polystyrene conversion))
Example 1
In a 50 ml eggplant-shaped flask, 1.76 g of phenol novolac resin A as a novolak resin, 1.10 g of VarifastRed 1355 (manufactured by Orient Chemical) as a red dye, and 9.43 g of 4-hydroxy-4-methyl-2-pentanone as a solvent And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name: Cymel 303, manufactured by Mitsui Cytec) as a crosslinkable compound, and a triazine photoacid generator (trade name: TAZ-108, manufactured by Midori Chemical Co., Ltd.) 0.09 g), 0.009 g of a fluorosurfactant (trade name: Mega-Fac R-30, manufactured by Dainippon Ink & Chemicals) as a surfactant, and further stirred at room temperature to obtain a dye-containing negative resist composition ( 1) was obtained. Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (1) was filtered using a 0.2 μm filter and left in a cleaned sample bottle at room temperature for 1 week. There wasn't.

Example 2
In a 50 ml eggplant-shaped flask, 1.76 g of phenol novolac resin A as a novolak resin, 1.10 g of ValifastRed 1355 as a red dye, 9.43 g of 4-hydroxy-4-methyl-2-pentanone as a solvent are stirred at room temperature. did. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.35 g of a butoxymethylated glycoluril-based crosslinkable compound (trade name Cymel 1170, manufactured by Mitsui Cytec) as a crosslinkable compound, and a sulfonate photoacid generator (trade name NAI-105, Midori Chemical) as a photoacid generator. 0.18 g of a product) and 0.012 g of a fluorosurfactant (trade name Megafac R-30) as a surfactant were added, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (2). . Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (2) was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week. There wasn't.

Example 3
In a 50 ml eggplant-shaped flask, 1.76 g of phenol novolac resin A as a novolak resin, 1.10 g of ValifastRed 1355 as a red dye, 9.43 g of 4-hydroxy-4-methyl-2-pentanone as a solvent are stirred at room temperature. did. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.25 g of an epoxy-based crosslinkable compound (trade name GT-401, manufactured by Daicel Chemical) as a crosslinkable compound, and a sulfonium salt type photoacid generator (trade name DTS-105, manufactured by Midori Chemical) as a photoacid generator. 0.12 g and 0.010 g of a fluorosurfactant (trade name Megafac R-30) as a surfactant were added and stirred at room temperature to obtain a dye-containing negative resist composition (3). Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (3) was filtered using a 0.2 μm filter and left in a cleaned sample bottle at room temperature for 1 week. There wasn't.

Example 4
In a 50 ml eggplant type flask, 1.00 g of phenol novolak resin A as novolak resin, 2.00 g of VarifastRed 1355 as red dye, 4.14 g of 4-hydroxy-4-methyl-2-pentanone as solvent and propylene glycol monomethyl ether 6.21 g was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.30 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) was used as the crosslinkable compound, and a triazine photoacid generator (trade name TAZ-107, manufactured by Midori Chemical Co., Ltd.) was used as the photoacid generator. 15 g and 0.009 g of a fluorosurfactant (trade name Megafac R-30) as a surfactant were added and further stirred at room temperature to obtain a dye-containing negative resist composition (4). Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (4) was filtered using a 0.2 μm filter and left in a cleaned sample bottle at room temperature for 1 week. There wasn't.

Example 5
In a 50 ml eggplant type flask, 1.00 g of phenol novolak resin A as novolak resin, 2.00 g of VarifastRed 1355 as red dye, 3.11 g of 4-hydroxy-4-methyl-2-pentanone as solvent, and 7 of ethyl lactate .25 g was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.15 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.07 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (5). Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (5) was filtered using a 0.2 μm filter and left in a cleaned sample bottle at room temperature for 1 week. There wasn't.

Example 6
In a 100 ml eggplant-shaped flask, 7.07 g of acrylic resin A as an acrylic resin, 0.27 g of RedGS (manufactured by Nissei Kasei) as a red dye, and 36. 4-hydroxy-4-methyl-2-pentanone as a solvent. 80 g was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 3.31 g of a crosslinkable compound (trade name KAYARDADDHA-40H, manufactured by Nippon Kayaku Co., Ltd.), 0.30 g of a photo radical generator (trade name I-369, manufactured by Ciba Specialty Chemicals), a photosensitizer (product) 0.20 g of name ITX, manufactured by First Chemical Corporation), 0.015 g of a fluorosurfactant (trade name Megafac R-30) as a surfactant, and further stirred at room temperature, and a dye-containing negative resist composition (6) was obtained. Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (6) was filtered using a 0.2 μm filter and left in a cleaned sample bottle at room temperature for 1 week. There wasn't.

Example 7
In a 50 ml eggplant-shaped flask, 1.00 g of phenol novolak resin A as novolak resin, 2.00 g of SavinylFireRedGLS (manufactured by Clariant) as red dye, and 10.35 g of 4-hydroxy-4-methyl-2-pentanone as solvent And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.30 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.15 g of a triazine photoacid generator (trade name TAZ-107) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (7). Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (7) was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week. There wasn't.

Example 8
In a 50 ml eggplant-shaped flask, 1.00 g of phenol novolac resin A as novolak resin, 5.80 g of SavinylFireRedGLS as red dye, and 13.51 g of 4-hydroxy-4-methyl-2-pentanone as solvent are stirred at room temperature. did. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.40 g of a methoxymethylated crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.18 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and a surfactant 0.01 g of a fluorosurfactant (trade name Megafac R-30) was added, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (8). Insoluble matter was not found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (8) was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week. There wasn't.

Example 9
In a 50 ml eggplant-shaped flask, 1.76 g of VP8000 as polyhydroxystyrene, 1.10 g of VarifastGreen 1501 (manufactured by Orient Chemical) as a green dye, and 9.43 g of 4-hydroxy-4-methyl-2-pentanone as a solvent, Stir at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.09 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (9). No insoluble matter was found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (9) was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week. There wasn't.

Example 10
In a 50 ml eggplant-shaped flask, 1.00 g of VP8000 as polyhydroxystyrene, 2.00 g of Varifast Green 1501 as a green dye, 4.14 g of 4-hydroxy-4-methyl-2-pentanone and propylene glycol monomethyl ether acetate as a solvent 6.21 g was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.50 g of a methoxymethylated melamine compound (trade name Cymel 303) as a crosslinkable compound, 0.25 g of a triazine photoacid generator (trade name TAZ-107) as a photoacid generator, and fluorine as a surfactant 0.009 g of a surface active agent (trade name Megafax R-30) was added, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (10). No insoluble matter was found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (10) was filtered using a 0.2 μm filter and left in a washed sample bottle for 1 week at room temperature. There wasn't.

Example 11
In a 50 ml eggplant-shaped flask, 1.76 g of Marker linker CHM as a polyhydroxystyrene copolymer, 1.10 g of VarifastBlue 1621 (manufactured by Orient Chemical) as a blue dye, and 4-hydroxy-4-methyl-2-pentanone as a solvent 9.43 g was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.09 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (11). No insoluble matter was found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (11) was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week. There wasn't.

Example 12
In a 50 ml eggplant-shaped flask, 1.00 g of Marker linker CHM as a polyhydroxystyrene copolymer, 5.80 g of Varifast Blue 1621 as a blue dye, and 13.51 g of 4-hydroxy-4-methyl-2-pentanone as a solvent are placed. And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.50 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.20 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.01 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (12). No insoluble matter was found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (12) was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week. There wasn't.

Example 13
In a 50 ml eggplant type flask, 1.00 g of Marker Linker CHM as a polyhydroxystyrene copolymer, 2.00 g of VariFastBlue 2620 (manufactured by Orient Chemical) as a blue dye, and 4-hydroxy-4-methyl-2-pentanone as a solvent Was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.30 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.15 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.012 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (13). No insoluble matter was found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (13) was filtered using a 0.2 μm filter and left in a washed sample bottle for 1 week at room temperature. There wasn't.

Example 14
In a 50 ml eggplant type flask, 1.00 g of Marker Linker CHM as a polyhydroxystyrene copolymer, 2.00 g of VariFastBlue 2620 as a blue dye, 4.14 g of 4-hydroxy-4-methyl-2-pentanone as a solvent, and 6.21 g of propylene glycol monomethyl ether was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. Thereafter, 0.30 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.15 g of a triazine photoacid generator (trade name TAZ-107) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (14). No insoluble matter was found in the solution, and a uniform solution was obtained. Part of the obtained dye-containing negative resist composition (14) was filtered using a 0.2 μm filter and left in a cleaned sample bottle at room temperature for 1 week. There wasn't.

Comparative Example 1
A 50 ml eggplant-shaped flask was charged with 1.76 g of phenol novolac resin A as a novolak resin, 1.10 g of VarifastRed 1355 as a red dye, and 9.43 g of propylene glycol monomethyl ether as a solvent, and stirred at room temperature. Dye precipitated. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.09 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature, but the dye did not dissolve and a uniform solution could not be obtained. Further, when the dye deposited in the resulting heterogeneous dye-containing negative resist composition (15) was collected by filtration, 0.54 g of a dye was obtained. As a result, a dye-containing negative resist composition containing a predetermined dye concentration could not be obtained. Further, the non-uniform dye-containing negative resist composition (15) obtained by the same adjustment method was filtered using a 0.2 μm filter and left in a washed sample bottle. Foreign objects were observed in the visual observation.

Comparative Example 2
In a 50 ml eggplant type flask, 1.76 g of VP8000 as polyhydroxystyrene, 1.10 g of VarifastGreen 1501 as a green dye, and 9.43 g of propylene glycol monomethyl ether as a solvent were stirred and stirred at room temperature. Precipitated. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.09 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature, but the dye did not dissolve and a uniform solution could not be obtained. Furthermore, when the deposited dye in the obtained nonuniform dye-containing negative resist composition (16) was collected by filtration, 0.46 g of dye was obtained. As a result, a dye-containing negative resist composition containing a predetermined dye concentration could not be obtained. Further, the non-uniform dye-containing negative resist composition (16) obtained by the same adjustment method was filtered using a 0.2 μm filter and left in a washed sample bottle. Generation of foreign matters was observed in visual observation.

Comparative Example 3
A 50 ml eggplant type flask was charged with 1.76 g of Marker linker CHM as a polyhydroxystyrene copolymer, 1.10 g of VarifastBlue 1621 as a blue dye, and 9.43 g of ethyl lactate as a solvent, and stirred at room temperature. Dye deposited inside. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.09 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.006 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature, but the dye did not dissolve and a uniform solution could not be obtained. Further, when the dye deposited in the obtained heterogeneous dye-containing negative resist composition (17) was collected by filtration, 0.55 g of a dye was obtained. As a result, a dye-containing negative resist composition containing a predetermined dye concentration could not be obtained. Further, the non-uniform dye-containing negative resist composition (17) obtained by the same adjustment method was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 day. The generation of foreign matters was observed by visual observation with the eyes.

Comparative Example 4
In a 50 ml eggplant-shaped flask, 1.76 g of Marker linker CHM as a polyhydroxystyrene copolymer, 1.10 g of Varifast Blue 1621 as a blue dye, 4.72 g of propylene glycol monomethyl ether and 4 of propylene glycol monomethyl ether acetate as a solvent When 0.72 g was added and stirred at room temperature, the dye precipitated in the reaction solution. Thereafter, 0.18 g of a methoxymethylated melamine-based crosslinkable compound (trade name Cymel 303) as a crosslinkable compound, 0.09 g of a triazine photoacid generator (trade name TAZ-108) as a photoacid generator, and surface activity 0.009 g of a fluorosurfactant (trade name Megafac R-30) was added as an agent, and the mixture was further stirred at room temperature, but the dye did not dissolve and a uniform solution could not be obtained. Further, when the dye deposited in the resulting heterogeneous dye-containing negative resist composition (18) was collected by filtration, 0.65 g of a dye was obtained. As a result, a dye-containing negative resist composition containing a predetermined dye concentration could not be obtained. Further, the non-uniform dye-containing negative resist composition (18) obtained by the same adjustment method was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 day. The generation of foreign matters was observed by visual observation with the eyes.

(Production of color filter)
The silicon wafers used in Examples 15 to 28 and Comparative Examples 5 to 8 were all the same size.

  In addition, in the observation of the presence or absence of foreign matter present on the pattern coating film formed on the silicon wafer, visual observation with a sodium lamp is performed by confirming the foreign matter by observation from a position 30 cm away from the silicon wafer surface in a dark room. It was. If foreign matter could be confirmed, the total number seen on the silicon wafer was counted. Moreover, the observation with an optical microscope was performed at a magnification of 1000 times, and the foreign matter was confirmed by measuring the size thereof.

Example 15
The dye-containing negative resist composition (1) obtained in Example 1 was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.95 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 16
The dye-containing negative resist composition (2) obtained in Example 2 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.00 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The resolution of the pattern was 5 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 17
The dye-containing negative resist composition (3) obtained in Example 3 was filtered using a 0.2 μm filter and allowed to stand in a cleaned sample bottle for 2 days. Thereafter, the composition was placed on a silicon wafer. The film was applied using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.98 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The resolution of the pattern was 5 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 18
The dye-containing negative resist composition (4) obtained in Example 4 was filtered using a 0.2 μm filter and left in a washed sample bottle for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.96 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 19
The dye-containing negative resist composition (5) obtained in Example 5 was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.03 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 20
The dye-containing negative resist composition (6) obtained in Example 6 was filtered using a 0.2 μm filter and left in a washed sample bottle for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.05 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The resolution of the pattern was 10 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 21
The dye-containing negative resist composition (7) obtained in Example 7 was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.00 μm. Through this coating film test mask, the Canon ultraviolet irradiation apparatus PLA-501 (F), the amount of irradiation at 365nm was irradiated with ultraviolet rays of 500 mJ / cm ^2. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 22
The dye-containing negative resist composition (8) obtained in Example 8 was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.94 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 23
The dye-containing negative resist composition (9) obtained in Example 9 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.10 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Green negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 24
The dye-containing negative resist composition (10) obtained in Example 10 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.98 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 120 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Green negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 25
The dye-containing negative resist composition (11) obtained in Example 11 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.00 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in a 23 ° C. NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for a certain period of time and developed, and further washed with pure water. Thereafter, post-baking was performed on a hot plate at 150 ° C. for 5 minutes to form a blue negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 26
The dye-containing negative resist composition (12) obtained in Example 12 was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 2 days. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.94 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in a 23 ° C. NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for a certain period of time and developed, and further washed with pure water. Thereafter, post-baking was performed on a hot plate at 150 ° C. for 5 minutes to form a blue negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 27
The dye-containing negative resist composition (13) obtained in Example 13 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.94 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post-baking was performed on a hot plate at 150 ° C. for 5 minutes to form a blue negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Example 28
The dye-containing negative resist composition (14) obtained in Example 14 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.95 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post-baking was performed on a hot plate at 150 ° C. for 5 minutes to form a blue negative pattern. The pattern resolution was up to 2 μm in line / space without pattern peeling. On the patterned coating film formed on the silicon wafer, no foreign matter was found when visually observed under a sodium lamp. Further, when observed with an optical microscope, no foreign matter was found.

Comparative Example 5
The dye-containing negative resist composition (15) obtained in Comparative Example 1 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.04 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Red negative pattern. The pattern resolution could be formed up to 2 μm in line / space without pattern peeling. However, when a visual observation was performed under a sodium lamp on the pattern coating film formed on the silicon wafer, 50 or more foreign substances were observed. Further, when observed with an optical microscope, foreign matter having a size of 2 to 3 μm was observed.

Comparative Example 6
The dye-containing negative resist composition (16) obtained in Comparative Example 2 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 1.00 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post baking was performed on a hot plate at 150 ° C. for 5 minutes to form a Green negative pattern. The pattern resolution could be formed up to 2 μm in line / space without pattern peeling. However, when a visual observation was performed under a sodium lamp on the pattern coating film formed on the silicon wafer, 50 or more foreign substances were observed. Moreover, when the optical microscope observation was performed, the foreign material of a 2-4 micrometers magnitude | size was seen.

Comparative Example 7
The dye-containing negative resist composition (17) obtained in Comparative Example 4 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.94 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post-baking was performed on a hot plate at 150 ° C. for 5 minutes to form a blue negative pattern. The pattern resolution could be formed up to 2 μm in line / space without pattern peeling. However, when a visual observation was performed under a sodium lamp on the pattern coating film formed on the silicon wafer, 50 or more foreign substances were observed. Moreover, when the optical microscope observation was performed, the foreign material of a 2-4 micrometers magnitude | size was seen.

Comparative Example 8
The dye-containing negative resist composition (18) obtained in Comparative Example 5 was filtered using a 0.2 μm filter and allowed to stand at room temperature for 2 days in a washed sample bottle. Thereafter, the composition was applied onto a silicon wafer using a spin coater and soft baked (baked) on a hot plate at 100 ° C. for 1 minute to form a coating film having a thickness of 0.99 μm. The coating film was passed through a test mask, and irradiated with ultraviolet rays having an irradiation dose of 365 m of 300 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) manufactured by Canon. Subsequently, PEB was performed on a hot plate at 130 ° C. for 1 minute. Thereafter, the film was immersed in an NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time for development, and further washed with pure water. Thereafter, post-baking was performed on a hot plate at 150 ° C. for 5 minutes to form a blue negative pattern. The pattern resolution could be formed up to 2 μm in line / space without pattern peeling. However, when a visual observation was performed under a sodium lamp on the pattern coating film formed on the silicon wafer, 50 or more foreign substances were observed. Moreover, when the optical microscope observation was performed, the foreign material of a 2-4 micrometers magnitude | size was seen.

  The present invention relates to a dye-containing negative resist composition or a positive resist composition formed by crosslinking, polymerization or depolymerization by heat or light irradiation, and a ketol solvent, preferably β-hydroxyketone, particularly preferably 4- By including hydroxy-4-methyl-2-pentanone, the solubility of the dye and the compatibility between the dye and the resin are increased, and a predetermined dye concentration can be ensured. As a result, a color filter capable of expressing a predetermined spectral spectrum can be produced, and a solid-state imaging device, a liquid crystal display device, and a light emitting diode display device can be manufactured using these color filters. Furthermore, by containing 4-hydroxy-4-methyl-2-pentanone, it is possible to suppress the generation of foreign matters when the resist composition is stored.

Claims (5)

Negative resist composition containing resin (a-1), photoacid generator or photobase generator (b-1), crosslinkable compound (c-1), dye (d), and ketol-based solvent (e) object. The resist composition according to claim 1 or 2 , wherein the solvent contains at least 1% by weight of ketol based on the whole solvent. The resist composition according to claim 1, wherein the ketol is β-hydroxyketone. The resist composition according to claim 1, wherein the ketol is 4-hydroxy-4-methyl-2-pentanone. A method for producing a color filter comprising the steps of coating, drying, exposing and developing the resist composition according to any one of claims 1 to 4 on a substrate.