JP4924813B2 - Dye-containing resist composition containing photoacid generator 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.

  Since a photoresist to which a dye is added can form a fine pattern, a high-definition color filter can be produced. For this reason, a color filter for an image sensor such as a charge coupled device (CCD) or a liquid crystal display device (LCD) is mainly manufactured using a method of forming a pattern with a photoresist added with a dye. In this method, a resist composition containing a dye and a polymer resin is used, and after coating and forming on a substrate, 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 stability 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 material that can be cured by an acid, a photoacid generator, and a pigment is disclosed (for example, Patent Document 1). It is disclosed that the resin material consists of a resin containing phenol and a crosslinking agent having an N-methylol structure.

  However, since the pigment itself contains particles having a particle diameter of about several tens to several hundreds of nanometers, there are problems that the pigment itself becomes a foreign substance, and dispersion is not stable and aggregation occurs. For this reason, it has become difficult to produce a color filter for a CCD that requires high resolution by using conventional pigments.

  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 containing a resin curable with an acid, a crosslinking agent, a photoacid generator, a dye and a solvent is disclosed (for example, Patent Document 2).

  In addition, a resist-added pigment for a color filter which is an amine salt of an acid dye and is soluble in an organic solvent and an alkaline aqueous solution is disclosed (for example, Patent Document 3).

  On the other hand, for a dye having a cation by a nitrogen-containing organic compound, a production method by a method in which an aliphatic amine, an alicyclic amine, an aromatic amine or a quaternary ammonium salt is allowed to act on a tetrakisazo dye is disclosed. Has been. It is described that they can be used for various inks, lacquers, or as colorants for paper, synthetic resins, fiber materials and other general synthetic resin materials, wood, oil, natural and synthetic waxes, and petroleum products. . (For example, patent document 4).

An ink composition containing a reaction mixture of a water-soluble dye having active hydrogen, an epoxy compound, and an amine compound as a colorant is disclosed. It is described that these are used for writing instruments, printing, recording, stamping, and paper coloring (for example, Patent Document 5).
JP-A-4-163552 (Claims) JP-A-6-51514 (Claims) JP-A-6-51115 (Claims) Japanese Patent Laid-Open No. 60-229953 (Claims and Examples) JP-A-61-203182 (Claims and Examples)

  In a dye-containing resist composition using a photoacid generator, when a hydrochloric acid-generating acid generator is used, exposure apparatus contamination with dehydrochlorination gas and device damage due to residual hydrochloric acid occur. In addition, when a conventional sulfonic acid-generating acid generator is used, there is a problem of insufficient sensitivity during light irradiation.

  The dye-containing photoresist composition according to the present invention is an improvement of the problem of the photoacid generator that occurs when a conventional dye-containing resist composition is used. The dye-containing resist composition of the present invention can greatly contribute to improving the physical properties of the color filter.

  When the color filter is further thinned, it is necessary to increase the dye concentration in the resist composition in order to develop a desired spectral spectrum. The object of the present invention is to exhibit high spectral spectrum reproducibility, high heat resistance and light resistance even when the dye concentration is increased in order to cope with the thinning of the color filter, and high resolution of 5 μm or less. The present invention is to provide a color resist composition that is free from development residues.

As a first aspect of the present invention, the formula ( 2 ):

（式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴はそれぞれ水素原子又は有機基を示す。）で表される陽イオンを含有する染料を含む、染料含有レジスト組成物であって、
前記染料が前記染料含有レジスト組成物の固形分全体に対して３０〜９０質量％の量で含まれてなる、染料含有レジスト組成物（但し以下の（ａ）〜（ｈ）に示す光酸発生剤と１
種又は２種の染料との組み合わせを含む染料含有レジスト組成物を除く）。

(Wherein R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom or an organic group, and R ² is an organic group). ):

^{(Wherein, R 1, R 2, R} 3 and R ⁴ each. Represents a hydrogen atom or an organic group) a dye containing a cation represented by a dye-containing photoresist composition,
Dye-containing resist composition comprising the dye in an amount of 30 to 90% by mass based on the total solid content of the dye-containing resist composition (however, photoacid generation shown in the following (a) to (h)) Agent and 1
Except for dye-containing resist compositions comprising a seed or a combination of two dyes).

  As a second aspect, the dye-containing resist composition according to the first aspect, including a combination of one or two kinds of photoacid generators and dyes shown in (I) to (V) below.

As a third aspect, resin (A), the first aspect or photoacid generator according to the second aspect (B), crosslinkable compound (C), dye (D), and a dye-containing containing solvent (E) Resist composition,
As a fourth aspect, a method for producing a color filter comprising the steps of applying the dye-containing resist composition according to any one of the first aspect to the third aspect on a substrate, drying, exposing, and developing. ,
As a fifth aspect , a liquid crystal display device including a color filter manufactured by the method of the fourth aspect ,
As a sixth aspect , an LED display device including a color filter manufactured by the method of the fourth aspect , and as a seventh aspect , a solid-state imaging device including a color filter manufactured by the method of the fourth aspect .

  The dye-containing resist composition of the present invention can cope with the thinning of the color filter, and the dye concentration can be increased to 30% by mass or more in the total solid content of the resist composition. And heat resistance and light resistance can be improved by interaction of dye and a phenol resin. Furthermore, by using a resist composition that combines a resin exhibiting high alkali developability and a dye exhibiting alkali developability, a desired spectral spectrum can be developed, and it has excellent heat resistance and light resistance, and exhibits high resolution. A filter can be produced.

  The dye-containing resist composition of the present invention can be thinned when a color filter is produced by increasing the dye concentration in the resist composition. In order to set the film thickness of the color filter to 0.3 to 1.5 μm, the dye concentration in the resist composition needs to be 30% by mass or more. The resist composition containing the dye molecule and the color filter produced therefrom have a transmittance of 70% or more and a transmittance of 10% or less in the wavelength region of 400 to 700 nm due to the dye molecule. The optical characteristic which has at least the area | region to show is shown. When the dye concentration is low and this transmittance value is shown, the number of dye molecules per unit volume is small, but sufficient heat resistance and light resistance cannot be ensured. In addition, when the dye concentration is high and exhibits this transmittance, the number of dye molecules per unit volume increases in order to obtain a desired spectral spectrum, and sufficient resolution and adhesion cannot be ensured. Therefore, the dye-containing resist composition of the present invention has a visible light region (wavelength 400 to 750 nm), particularly a region showing a transmittance of 70% or more and a region showing a transmittance of 10% or less in the wavelength region of 400 to 700 nm. And a dye having a spectral spectrum having at least.

  Dyes such as red, green, and blue have specific areas where each dye absorbs (area where the transmittance is 10% or less) and areas where the dye does not absorb (area where the transmittance is 70% or more) It is not preferable that the region that does not exhibit absorption inhibits the absorption of other dyes. When each dye exhibits absorption in a region that does not inherently exhibit absorption, it indicates that the heat resistance and light resistance of the dye are insufficient. The above-mentioned dye used in the dye-containing resist composition of the present invention has a transmittance of 10% or less in a specific region showing absorption, and a transmittance of 70% or more in a region not showing absorption. By expressing the spectrum, a clear color filter can be obtained.

  The photoacid generator having a specific structure used in the dye-containing resist composition of the present invention exhibits high compatibility with the other main components of the resist composition, that is, the resin, the crosslinkable compound, the dye and the solvent. And the resist pattern obtained by apply | coating the dye containing resist composition of this invention containing these components to a board | substrate, hardening | curing, and exposing has high developability.

  The dye-containing resist composition of the present invention is a dye-containing resist composition containing a photoacid generator having a specific structure.

  More specifically, the dye-containing resist composition of the present invention is a negative resist composition containing a resin (A), a photoacid generator (B), a crosslinkable compound (C), a dye (D), and a solvent (E). It is a thing.

  Hereinafter, the negative resist composition will be described.

  The resin (A) used in the negative resist composition is a resin that cures with an acid generated by heat or light irradiation, or a base generated by heat or light irradiation, or a photosensitive resin that crosslinks by heat or light irradiation. There is no particular limitation as long as the unexposed coating film in the resin can be removed by a developer.

  Examples of the resin (A) include resins having a hydroxyl group or a carboxyl group.

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

  Particularly preferably, the resin (A) is polyvinylphenol or a copolymer thereof.

  Examples of the copolymerization monomer include acrylic monomers, and examples thereof include (meth) acrylic acid esters and ethylenically unsaturated carboxylic acids.

  (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, maleic acid and hydroxypropyl (meth) acrylate are preferred.

  Polyvinylphenol and a copolymer of polyvinylphenol and the acrylic monomer are 1000 to 100,000 in terms of weight average molecular weight (polystyrene conversion), and preferably 2000 to 30,000 in terms of developability and adhesion. These can be combined as necessary, and are used by copolymerizing vinylphenol and one of the above acrylic monomers, or using a copolymer consisting of a combination of vinylphenol and two or more of the above acrylic monomers. It is possible.

  Other compounds used for copolymerization include acrylic acid derivatives, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorostyrene, and other styrene derivatives. Is mentioned. Of these, styrene is preferred.

  Polyvinylphenol or a copolymer thereof, that is, polyhydroxystyrene or a polyhydroxystyrene derivative 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 can be combined as necessary, and can be used alone or in combination of two or more kinds of copolymers.

  In the negative resist composition, the photoacid generator (B) used when the resin (A) is used generates an acid directly or indirectly by light irradiation.

Specifically, it is a compound having the structure of the formula (1) in the molecule. R ¹ is an organic group derived from a substituted or unsubstituted heterocyclic compound. Examples of the hetero atom of the heterocyclic compound include organic groups derived from 5- and 6-membered heterocyclic compounds, condensed rings of heterocycles, and condensed rings of heterocycles and homocycles. An organic group derived from is exemplified. Specific examples include furan, thiophene, pyrrole, pyridine, thiazole, imidazole, pyrazole, pyrimidine, indole, quinoline, purine, and pteridine. These rings can have a substituent. In particular, the hetero atom is preferably a sulfur atom, and examples thereof include an organic group derived from thiophene.
Examples of the substituent include alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group, halogen groups such as chlorine and bromine, nitro group, cyano group, and amino group. Furthermore, organic groups derived from the above heterocyclic compounds and homocyclic compounds such as phenyl group, naphthyl group and anthryl group can be used as a substituent.

The photoacid generator (B) used in the dye-containing resist composition of the present invention is preferably a compound corresponding to the formula (2). R ³ , R ⁴ and R ⁵ are each independently an alkyl group such as a methyl group, an ethyl group, a propyl group and an isopropyl group, a halogen group such as chlorine and bromine, a nitro group, a cyano group and an amino group. can give. Furthermore, organic groups derived from the above heterocyclic compounds and homocyclic compounds such as phenyl group, naphthyl group and anthryl group may be used as a substituent.

R ² is exemplified by a substituted or unsubstituted alkyl group and a substituted or unsubstituted aromatic group. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a trifluoromethyl group, a trifluoroethyl group, a tolyl group, and a trifluoromethylphenyl group.

  As a preferable compound corresponding to the formula (2), for example, the formula (3) to the formula (7):

Can be illustrated.

  The photoacid generator (B) can be used as a photoacid generator (B) by further combining the following photoacid generators with less than 50% by mass of the total photoacid generator. Specific examples of these photoacid generators include triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivative compounds, diaryliodonium salts, triarylsulfonium salts, triarylphosphonium salts, iron. Although an arene complex etc. can be used, 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) io 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-methoxyphenyl) ) Phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, Li (p- ethoxyphenyl) phosphonium tetrafluoroborate and the like.

  Moreover, the photo-acid generator shown to Formula (8)-Formula (71) can also be used.

  These photoacid generators (8) to (71) are used in combination with the photoacid generators of the above formulas (1) to (2) and the above formulas (3) to (7). Can do.

  The photoacid generators listed here are examples, and are not limited to these compounds.

  A photo-acid generator can be used individually or can be used in combination of 2 or more types. Moreover, the introduction amount is selected in the range of 1 to 300 parts by mass, preferably 2 to 100 parts by mass with respect to 100 parts by mass of the resin (A) component. When this amount is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently and a desired resist pattern is difficult to obtain, and when it exceeds 300 parts by mass, the storage stability of the resist composition is poor. Therefore, the introduction amount of the acid generator is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the resin (A) component.

  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.

  In the negative resist composition, the crosslinkable compound (C) used for the resin (A) 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. Can be used.

  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), 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. The 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 (above, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel Methoxymethylated butoxymethylated melamine such as 235, 236, 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel A methoxymethylated ester such as 1123 Xymethylated 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 Industries Co., Ltd. (former Mitsui Cyanamid Co., Ltd.) can be mentioned. Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, methoxymethylolated glycoluril such as Powderlink 1174 (Nippon Cytec Industries, Inc.) (Former Mitsui Cytec Co., Ltd.).

  Examples of benzene or phenolic compounds having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) 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 crosslink formation group can also 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-epoxypropoxy) phenyl) -1- Methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

  These crosslinkable compounds (C) can be used alone or in combination of two or more. Moreover, the introduction amount is selected in the range of 1 to 300 parts by mass, preferably 20 to 200 parts per 100 parts by mass of the resin (A) component. When this amount is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently, making it difficult to obtain a desired resist pattern, and when it exceeds 300 parts by mass, the storage stability of the resist composition is poor. Therefore, the introduction amount of the crosslinking agent is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the resin component.

  The dye (D) used in the dye-containing resist composition of the present invention has a desirable spectral spectrum when used as a color filter and is dissolved in a solvent as it is or dissolved in a modified form of the dye. be able to.

  The dye (D) used in the dye-containing resist composition of the present invention has the formula (72):

(Wherein R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an organic group).

At least one in formula (72) R ¹ and R ² are those having a nitrogen Motoyu Kimoto, and particularly preferably both of R ¹ and R ² is a nitrogen-containing organic group.

At least one of the nitrogen-containing organic groups of R ¹ and R ² has an imino structure (—NH—R ⁵ ), and in particular, both R ¹ and R ² have an imino structure (—NH—R ⁵ ). It is preferable.

R ⁵ is an alkyl group or a substituted or unsubstituted aromatic group, such as a phenyl group, a naphthyl group, an anthryl group, and an alkyl group such as methyl, ethyl and propyl, a nitro group, a chloro and a bromo group. An aromatic group substituted with a halogen group such as R ⁵ is preferably a phenyl group or a tolyl group.

At least one of R ³ and R ⁴ is a hydrogen atom, and the other is an alkyl group such as methyl, ethyl and propyl, or a substituted or unsubstituted aromatic group. Examples of the aromatic group include a phenyl group, a naphthyl group, an anthryl group, and an aromatic group obtained by substituting an alkyl group such as methyl, ethyl, or propyl, or a halogen group such as nitro group, chloro, or bromine. It is done. In particular, it is preferable when both R ³ and R ⁴ are hydrogen atoms, or when one of R ³ and R ⁴ is a hydrogen atom and the other is the above aromatic group.

  Specific examples of the cation contained in the dye (D) used in the dye-containing resist composition of the present invention include formulas (73) to (84):

Is mentioned. The cation contained in this dye (D) is:

It is particularly preferable that R represents a hydrogen atom or a methyl group.

  In addition, the compound of the formula (85) has a resonance structure, and the formula (86):

There is also a cation having the structure (wherein R represents a hydrogen atom or a methyl group). This cation can also be used in the dye-containing resist composition of the present invention.

  The dye (D) is an organic salt composed of the cation and anion, and a carboxylate or a sulfonate is preferably used.

  The anion in the dye (D) is a counter ion of the cation and is a compound having at least one anion in the molecule, but may have a cationic group depending on the case. Is possible.

  Examples of the compound used as an anion in the dye (D) include a compound having a phthalocyanine structure, a compound having a pyrazole azo structure, a compound having a metal complex structure and a pyrazole azo structure, and a compound having a xanthene structure. The In particular, a compound having only an anionic group, a compound having a phthalocyanine structure, a compound having a pyrazole azo structure, and a compound having a metal complex structure and a pyrazole azo structure are preferable.

In a compound having a phthalocyanine structure as an anion component, a sulfonic acid group (—SO ₃ ⁻ ) and / or a carboxylic acid group (—COO ⁻ ) is anionic. The sulfonic acid group and the carboxylic acid group can be contained together in a ratio of 1 to 4 in one molecule of phthalocyanine. As this anionic group, a sulfonic acid group can be preferably used. In addition to this anionic group, a sulfonic acid amino ester group (—SO ₂ NHR, where R is an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, an ether group or an ester group), a hydroxyl group. , A nitro group, an amino group, a halogen group such as chloro and bromo, and an alkyl group such as a methyl group and an ethyl group, and all of these nonionic groups are 1 to 4 per molecule of phthalocyanine. It can contain in the ratio. In particular, a sulfonic acid amino ester group can be preferably used as the nonionic group. As the phthalocyanine, a metal-containing and metal-free phthalocyanine can be used. Examples of the central metal include Cu, Zn, Al, Ni, and Co. Cu is particularly preferable.

  Examples of the dye (D) that can be used in the dye-containing resist composition of the present invention comprising a combination of a sulfonic acid group-containing phthalocyanine as an anion and a cation represented by the above formulas (73) to (86) include: The compound of (87)-Formula (89) can be illustrated.

Further, in a compound having a pyrazole azo structure as an anionic component, a sulfonic acid group (—SO ₃ ⁻ ) and / or a carboxylic acid group (—COO ⁻ ) exhibits anionic properties. The sulfonic acid group and the carboxylic acid group can be contained in a ratio of 1 to 4 in one molecule of the compound having a pyrazole azo structure in combination. As the anionic group, a sulfonic acid group can be preferably used. In addition to this anionic group, a sulfonic acid amino ester group (—SO ₂ NHR, where R is an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, an ether group, or an ester group), a hydroxyl group. , A nitro group, an amino group, a halogen group such as chloro and bromo, and an alkyl group such as a methyl group and an ethyl group, and these nonionic groups are contained in one molecule of a compound having a pyrazole azo structure as a whole group. 1 to 4 can be contained. In particular, as the nonionic group, a hydroxyl group and an alkyl group such as a methyl group and ethyl can be preferably used. The compound having a pyrazole azo structure is a compound having at least one of a pyrazole moiety and an azo moiety in one molecule. The pyrazole moiety and the azo moiety can be directly bonded or can be present with another organic group in between. For example, an aromatic group such as a phenyl group or an aliphatic group such as an alkylene group is linked to the pyrazole part or azo part, and the aromatic group or aliphatic group has a sulfonic acid group or other substituent. Compounds.

  Dye (D) that can be used in the dye-containing resist composition of the present invention comprising a combination of a compound having a sulfonic acid group-containing pyrazole azo structure as an anion and a cation represented by the above formulas (73) to (86). Examples of the compound include compounds represented by formulas (90) to (92).

Further, in a compound having a metal complex structure and a pyrazole azo structure as an anionic component, a sulfonic acid group (—SO ₃ ⁻ ) and / or a carboxylic acid group (—COO ⁻ ) exhibits anionic properties. This anion structure is such that a compound having an anionic group-containing pyrazole azo structure forms a complex with a metal. The compound having an anionic group-containing pyrazole azo structure and the metal form a complex at a molar ratio of 2 to 4: 1, and a ratio of 2: 1 is particularly preferable. Examples of the metal present in the center include Cu, Zn, Al, Ni, and Co, and Co is particularly preferable. The sulfonic acid group and the carboxylic acid group can be contained in a ratio of 1 to 4 in one molecule of the compound having a pyrazole azo structure in combination. In particular, a sulfonic acid group can be preferably used as the anionic group. In addition to this anionic group, a sulfonic acid amino ester group (—SO ₂ NHR, where R is an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, an ether group or an ester group), a hydroxyl group. , A nitro group, an amino group, a halogen group such as chloro and bromo, and an alkyl group such as a methyl group and an ethyl group, and these nonionic groups are contained in one molecule of a compound having a pyrazole azo structure as a whole group. 1 to 4 can be contained. In particular, as a nonionic group, a nitro group, a hydroxyl group, an alkyl group such as a methyl group and an ethyl group can be preferably used.

  It can be used in the dye-containing resist composition of the present invention comprising a combination of a compound having a metal complex structure and a sulfonic acid group-containing pyrazole azo structure as an anion and a cation represented by the above formulas (73) to (86). Examples of the dye (D) include compounds of the formulas (93) to (98).

In addition, in a compound having a xanthene structure as an anionic component, a sulfonic acid group (—SO ₃ ⁻ ) and / or a carboxylic acid group (—COO ⁻ ) exhibits an anionic property. The sulfonic acid group and the carboxylic acid group can be contained in a ratio of 1 to 3 in one molecule of the compound having a xanthene structure. In particular, a carboxylic acid group can be preferably used as the anionic group. In addition to this anionic group, a sulfonic acid amino ester group (—SO ₂ NHR, where R is an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, an ether group or an ester group), a hydroxyl group. , A nitro group, an amino group, a halogen group such as chloro and bromo, an alkyl group such as a methyl group and an ethyl group, and these nonionic groups are present in one molecule of a compound having a xanthene structure as a whole group. It can contain in the ratio of 1-3.

  Examples of the dye (D) that can be used in the dye-containing resist composition of the present invention comprising a combination of a compound having a xanthene structure as an anion and the cation represented by the formulas (73) to (86) include, for example, the formula The compounds of (99) to (103) can be exemplified.

  A commercial item can be used for the dye (D) used for the dye-containing resist composition of this invention.

  These dyes can be easily synthesized by a known method. For example, it can be obtained by a method of reacting an amine corresponding to the structure of the formulas (73) to (86) with a dye molecule (matrix) having a sulfonic acid group or a carboxylic acid group. That is, an aqueous solution of a compound having a phthalocyanine structure having a sulfonic acid group or a carboxylic acid group, a compound having a pyrazole azo structure, a compound having a metal complex structure and a pyrazole azo structure, or a compound having a xanthene structure is necessary for salt formation. It can be synthesized by reacting with a desired molar ratio of amine and precipitating a slightly soluble salt in water. When the salt of the dye is soluble in water, the salt is obtained by salting out.

  More specifically, an aqueous solution of an ammonium salt having the structure of the above formulas (73) to (86) is added to an aqueous solution of the above dye having sodium sulfonate or sodium carboxylate and reacted, and the above formula (73) is reacted. ) To dyes having a cation of formula (86) can be produced. In addition, an aqueous solution of an amine hydrochloride corresponding to the structure of the above formulas (73) to (86) is added to an aqueous solution of the above dye having sodium sulfonate or sodium carboxylate, and reacted to obtain the above formula (73). A dye having a cation of formula (86) can be produced.

  In the dye (D) used in the dye-containing resist composition of the present invention, an arbitrary dye can be further mixed and used. Examples of these optional 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, 2 6,238,239,240,241,242,243,244,245,247,248, C. I. Solvent Violet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 4m9, 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.

  The dye (D) exhibits optical characteristics having a region showing a transmittance of 70% or more and a region showing a transmittance of 10% or less in a wavelength region of 400 to 700 nm, and a temperature of 200 ° C. or more. The transmittance change is preferably within 5% even after passing through the temperature. The dye-containing resist composition of the present invention and the color filter prepared from the resist composition also exhibit similar optical characteristics.

  The dye-containing resist composition of the present invention is applied to a substrate, then baked at a temperature of 50 to 150 ° C., exposed and developed, and this baking temperature is 200 to 270 ° C. (30 minutes at 200 ° C., 270 ° C. The time-dependent change in transmittance of the portion showing 70% or more transmittance in the wavelength region of 400 to 700 nm even when firing at a high temperature of 30 seconds is preferably within 5% as compared to before performing high temperature firing. .

In the dye-containing resist composition of the present invention, the amount of the dye (D) introduced is the entire solid content (100) of the resin (A), the photoacid generator (B), the crosslinkable compound (C) and the dye (D). %) To 1 to 90% by mass , preferably 30% by mass or more . 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 dye-containing resist composition of the present invention, by using a dye having a cation having a specific structure, and a dye comprising an anion that forms a counter ion with a cation having a specific structure, the amount of the dye introduced as described above Needless to say, the (concentration of the dye in the entire solid content) can be used at a low concentration of several mass%, but even if the concentration is set to a high concentration of 30 to 90 mass%, the dye can sufficiently ensure solubility.

  Examples of the solvent (E) used in the dye-containing resist composition of the present invention include acetone, methanol, ethanol, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, and methyl isopropyl. Ketone, methyl cellosolve, 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 monomethyl -Teracetate, 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 dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate mono Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, dipropylene glycol dipropyl ether, dipropylene glycol diacetate ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, 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 ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3- Examples include ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination of two or more.

  Of these solvents, ketol solvents are particularly preferred for compatibility with the dye (D) used in the dye-containing resist composition of the present invention. Examples of ketol include β-hydroxyketone, and specific examples include 4-hydroxy-4-methyl-2-pentanone.

  The reason why the compatibility between the dye (D) used in the dye-containing resist composition of the present invention and the ketol-based solvent is particularly preferable is that these are based on the relative positional relationship between the hydroxyl group and the carbonyl group in the ketol-based solvent molecule. It can be considered to have a very high solubility in order to work effectively as a convenient ligand for dye ions, in particular the cation of the dye, and therefore has a high solubility when using these dyes. It is thought that it becomes.

  As the solvent (E) used in the dye-containing resist composition of the present invention, this ketol-based solvent can be used alone, and a solvent containing a ketol-based solvent in a proportion of 10% by mass or more in the total solvent is selected. It is preferable.

  In the dye-containing resist composition of the present invention, the resin (A), photoacid generator (B), crosslinkable compound (C), and dye (D) are resin (A), photoacid generator (B), crosslink The ratio contained in the organic compound (C), the dye (D) and the solvent (E), that is, the solid content concentration is 5 to 50% by mass, preferably 10 to 30% by mass. When this ratio is less than 5% by mass, the film thickness of the coating film becomes too small, and the occurrence of pinholes becomes a problem in terms of characteristics. Moreover, when it exceeds 50 mass%, the viscosity of a resist composition becomes excessive and the film thickness uniformity of a coating film is impaired.

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

  More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Gemco Co., Ltd.), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (Sumitomo) 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like.

  The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin (A) component. When the surfactant content is more than 2 parts by mass, the resist film is likely to be uneven, and when it is less than 0.01 parts by mass, 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 mass or less, preferably 0.05 to 10 parts by mass, and particularly preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin (A) component.

  Additives miscible with the resist composition can be further added to the dye-containing resist composition of the present invention. Examples thereof include an ultraviolet absorber and an antioxidant that improve light resistance stability, and a compatibilizing agent that suppresses precipitation of dyes. Specific examples of compatibilizers that suppress dye precipitation include polyoxyethylene octyl ether compounds, polyoxyethylene lauryl ether compounds, polyoxyethylene alkyl (carbon number 12 to 13) ether compounds, and polyoxyethylene secondary alkyls. (C12-14) ether compound, polyoxyethylene alkyl (C13) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl ether compound, polyoxyethylene oleyl ether compound, polyoxyethylene decyl ether compound, Al, such as polyoxyalkylene alkyl (carbon number 11-15) ether compound, polyoxyalkylene secondary alkyl (carbon number 12-14) ether compound, polyoxyalkylene cetyl ether compound Ether ether compounds, polyoxyethylene lauryl amino ether compounds, polyoxyethylene stearyl amino ether compounds, alkyloxy ether compounds such as polyoxyethylene oleyl amino ether compounds, polyoxyethylene lauric acid amide ether compounds, polyoxyethylene stearic acid amide ether compounds , Polyoxyethylene oleic acid amide ether compound, lauric acid diethanolamide compound, stearic acid diethanolamide compound, alkyl amide ether compound such as oleic acid diethanolamide compound, polyoxyethylene polystyryl phenyl ether compound, polyoxyalkylene polystyryl phenyl ether Compound, polyoxyalkylene polystyryl phenyl ether formamide condensation , Polyoxyethylene monostyryl phenyl ether compound, polyoxyethylene distyryl phenyl ether compound, allyl phenyl ether compound such as polyoxyethylene naphthyl ether compound, glycerol monolaurate compound, glycerol monostearate compound, glycerol monooleate compound, glycerol Glycerin fatty acid ester compounds such as trioleate compounds, sorbitan monolaurate compounds, sorbitan monopalmitate compounds, sorbitan monostearate compounds, sorbitan tristearate compounds, sorbitan monooleate compounds, sorbitan trioleate compounds such as sorbitan acid ester compounds, Polyoxyethylene dilaurate compound, polyoxyethylene laurate compound, polyoxyethylene stearate Vegetable oils such as fatty acid ether ester compounds, polyoxyethylene castor oil ether compounds, polyoxyethylene hydrogenated castor oil ether compounds, such as carbonate compounds, polyoxyethylene distearate compounds, polyoxyethylene diolate compounds, polyoxyethylene oleate compounds Ether ester compounds, polyoxyethylene sorbitan monolaurate 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, polyoxyalkylene alkyl (C14-15) ether compounds, polyoxyal Polyols such as monool-type polyether compounds such as xylene oleyl ether compounds, diol-type polyether compounds such as polyoxyethylene polyoxypropylene condensates, trimethylolpropane tris (polyoxyalkylene) ether compounds, polyoxyalkylene glyceryl ether compounds Type polyether 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, geo Rail adipate compound, trimethylolpropane tridecanoate compound, trimethylolpropane trilaurate compound, pentaerythritol Fatty acid alkyl ester compounds such as ludiolate compounds, pentaerythritol monostearate compounds, pentaerythritol 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 naphthalene sulfonate compounds, diisopropyl naphthalene sulfonate compounds, triisopropyl naphthalene sulfonate compounds, dibutyl naphthalene sulfonate compounds, dioctyl sulfosuccinate compounds, oleic acid sulfated oil compounds, castor Oil sulfated oil compound, octyl Rufeto compounds, lauryl sulfate compounds, alkyl sulfates compounds, sulfate compounds such as alkyl ether sulfate compounds, cellulose, cellulose derivatives, sugar backbone polymer compound.

  The usage-amount of these compatibilizers is 0.001-20 mass parts with respect to 100 mass parts of resin (A) components. When the amount used is small, the precipitation of the dye cannot be suppressed, and when it is large, it is difficult to obtain a good pattern shape. However, when the compatibilizer does not inhibit the pattern shape, it can be used in an amount of 20 parts by mass or more.

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

The dye-containing resist composition of the present invention is applied on a silicon wafer or a glass substrate at a rotational speed to obtain a desired resist film thickness by a spinner method 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 10-3000 mJ / 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 pattern is formed using a negative resist composition after exposure, it is preferable to perform post-exposure heating (PEB, Post Exposure Bake). By PEB, the crosslinking by the acid or base generated by exposure further proceeds, and the difference with respect to the developer solution solubility from the unexposed area is further widened, and the resolution contrast is improved. PEB is preferably performed in a temperature range of 50 to 170 ° 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 dipping method, 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 Examples include an aqueous ammonium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, an aqueous sodium bicarbonate solution, an aqueous sodium silicate solution, and an aqueous sodium metasilicate solution.

  Furthermore, it is preferable to add a surfactant to the developer in order to improve the removability of the unexposed area. Specific examples 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 (carbon number 12 to 14) ether compound, poly Oxyethylene alkyl (13 carbon atoms) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl ether compound, polyoxyethylene oleyl ether compound, polyoxyethylene decyl ether compound, polyoxyalkylene alkyl (11 to 15 carbon atoms) Ether compounds, polyoxyalkylene secondary alkyl (C12-14) ether compounds, alkyl ether compounds such as polyoxyalkylene cetyl ether compounds, polyoxyethylene Alkyl amino ether compounds such as lauryl amino ether compounds, 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 ether compounds, alkyl amide ether compounds such as lauric acid diethanolamide compounds, stearic acid diethanolamide compounds, oleic acid diethanolamide compounds, polyoxyethylene polystyryl phenyl ether compounds, polyoxyalkylene polystyryl phenyl ether compounds, polyoxyalkylene poly Styryl phenyl 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 Oxyalkylene alkyl (C14-15) ether compound, polyoxyalkylene oleyl ether compound, etc. Polyol type polyether compounds such as monool type polyether compounds, diol type polyether compounds such as polyoxyethylene polyoxypropylene condensates, trimethylolpropane tris (polyoxyalkylene) ether compounds, polyoxyalkylene glyceryl ether compounds, 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, trimethylol Propane tridecanoate compound, trimethylolpropane trilaurate compound, pentaerythritol diolate compound, pentae Fatty acid alkyl ester compounds such as sitolitol monostearate compounds and pentaerythritol 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 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 oil sulfated Oil compound, octyl sulfate compound, lauryl monkey Examples thereof include sulfate ester compounds such as phosphate compounds, alkyl sulfate compounds, and alkyl ether sulfate compounds. The preferred concentration of the alkali developer is 0.001 to 10% by mass for the alkali component and 0.001 to 10% by mass for the surfactant component. If the alkali component is too high, the developing ability is too strong. In the negative type, the unexposed area penetrates and the surface of the pattern is likely to be rough. If it is too low, the developing ability cannot be obtained. On the other hand, if the surfactant component is too high, foaming tends to occur and development unevenness tends to occur, and 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 a negative resist composition is used, a negative pattern is formed in which the exposed portion is cured and the unexposed portion is dissolved.

  By repeating the above-described series of steps for each color and pattern and repeating the necessary number of times, a colored pattern in which the necessary number of colors are combined can be obtained. Further, heating (post-baking) may be performed after the pattern formation or 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.

  The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

(Preparation of dye-containing negative resist composition)
Resin A1: VP8000 (manufactured by Nippon Soda Co., Ltd.), the component is polyvinylphenol. Weight average molecular weight 8000 (polystyrene conversion).
Resin A2: Marker Linker CHM (manufactured by Maruzen Petrochemical Co., Ltd.), component is a polymer having a ratio of p-vinylphenol / 2-hydroxyethyl methacrylate = 50 parts by mass / 50 parts by mass. Weight average molecular weight 10,000 (polystyrene conversion).
Resin A3: Polymer composed of vinylphenol / styrene = 80 parts by mass / 20 parts by mass. Weight average molecular weight 9000 (polystyrene conversion).

  Photoacid generator B1: Formula (4) (Ciba Specialty Chemicals)

  Photoacid generator B2: Formula (6) (Ciba Specialty Chemicals)

  Photoacid generator B3: Formula (45) NAI-109 (manufactured by Midori Chemical Co., Ltd.)

  Photoacid generator B4: Formula (10) DTS-105 (manufactured by Midori Chemical Co., Ltd.)

Crosslinkable compound C1: Cymel 303 (methoxymethylated melamine-based crosslinkable compound, manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.)).
Crosslinkable compound C2: Cymel 370 (methoxymethylated melamine-based crosslinkable compound, manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.)).
Crosslinkable compound C3: Cymel 1170 (butoxymethylated glycoluril-based crosslinkable compound, manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.)).
Crosslinkable compound C4: GT-401 (epoxy crosslinkable compound, manufactured by Daicel Chemical Industries, Ltd.)

  Dye D1: Formula (93)

  Dye D2: Formula (104)

  Dye D3: Formula (91)

  Dye D4: Formula (105)

Formula (105) is a mixture in which one to four ionic groups substituted on the benzene ring are substituted on one phthalocyanine skeleton. However, there are as many cations as the number of sulfonate ions.

  Dye D5: Formula (89)

Formula (89) is a mixture in which one to four phthalocyanine skeletons are substituted for all substituents including the ionic group and nonionic group substituted on the benzene ring. However, there are as many cations as the number of sulfonate ions.

  Dye D6: Formula (106)

Example 1
Into a 50 ml eggplant type flask, resin A1 (1.76 g), dye D1 (2.15 g), dye D6 (0.5 g) and propylene glycol monomethyl ether (9.43 g) as a solvent were added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Thereafter, crosslinkable compound C1 (0.3 g), photoacid generator B1 (0.2 g), and Megafac R-30 (Dainippon Ink Chemical Co., Ltd.) (0.009 g) as a surfactant were added. The mixture was further stirred at room temperature to obtain a dye-containing negative resist composition (1). Insoluble matter was not found in the solution, and a uniform solution was obtained.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

This dye-containing negative resist composition (1) was filtered using a 0.2 μm filter and left in a cleaned sample bottle for 2 days. Thereafter, the composition was applied on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment at 100 ° C. for 1 minute using a spin coater, and soft-baked on a hot plate at 120 ° C. for 1 minute to obtain a film thickness of 1 A coating film of 0.02 μm was formed. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 600 mJ / cm ² by an ultraviolet irradiation apparatus PLA-501 (F) (manufactured by Canon Inc.) through a test mask. Subsequently, PEB was performed on a hot plate at 130 ° C. for 2 minutes. Thereafter, the film was immersed in a 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 ultrapure water. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a 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 2
In a 50 ml eggplant type flask, resin A1 (1.76 g), dye D2 (2.25 g), 4-hydroxy-4-methyl-2-pentanone (4.72 g) and propylene glycol monomethyl ether (4.72 g) as solvents And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Then, crosslinkable compound C1 (0.15 g), crosslinkable compound C2 (0.15 g), photoacid generator B2 (0.15 g), and Megafac R-30 (0.01 g) as a surfactant are added, Further, the mixture was 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.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

This dye-containing negative resist composition (2) was filtered using a 0.2 μm filter and left in a cleaned sample bottle for 2 days. Thereafter, the composition was applied on a silicon wafer subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater and soft baked on a hot plate at 120 ° C. for 2 minutes to form a coating film having a thickness of 1.04 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 500 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Subsequently, PEB was performed on a hot plate at 130 ° C. for 2 minutes. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a 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 3
In a 50 ml eggplant-shaped flask, resin A2 (1.76 g), dye D3 (0.85 g), dye D4 (0.85 g), 4-hydroxy-4-methyl-2-pentanone (4.72 g) and propylene as solvents Glycol monomethyl ether (4.72 g) was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Thereafter, crosslinkable compound C1 (0.3 g), photoacid generator B2 (0.2 g), and Megafac R-30 (0.012 g) as a surfactant were added, and the mixture was further stirred at room temperature. A resist composition (3) was obtained. Insoluble matter was not found in the solution, and a uniform solution was obtained.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

The dye-containing negative resist composition (3) was filtered using a 0.2 μm filter and left in a washed sample bottle for 2 days. Thereafter, the composition was applied on a silicon wafer subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater and soft baked on a hot plate at 120 ° C. for 1 minute to form a coating film having a thickness of 1.11 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 450 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Then, PEB was performed on a hot plate at 120 ° C. for 2 minutes. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a 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 4
In a 50 ml eggplant type flask, resin A3 (1.76 g), dye D3 (1.65 g) and 4-hydroxy-4-methyl-2-pentanone (9.44 g) as a solvent were added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Thereafter, a crosslinkable compound C1 (0.15 g), a crosslinkable compound C2 (0.15 g), a photoacid generator B1 (0.1 g), and Megafac R-30 (0.01 g) as a surfactant are added. The mixture was 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.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

The dye-containing negative resist composition (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 that had been subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater, and soft-baked on a hot plate at 115 ° C. for 1 minute to form a coating film having a thickness of 1.09 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 500 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Subsequently, PEB was performed on a hot plate at 125 ° C. for 2 minutes. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a 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 5
In a 50 ml eggplant type flask, resin A1 (1.76 g), dye D5 (2.76 g), 4-hydroxy-4-methyl-2-pentanone (4.72 g) as a solvent and propylene glycol monomethyl ether (4.72 g) And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Thereafter, the crosslinkable compound C1 (0.35 g), the photoacid generator B2 (0.2 g), and Megafac R-30 (0.009 g) as a surfactant were added, and the mixture was further stirred at room temperature. A resist composition (5) was obtained. Insoluble matter was not found in the solution, and a uniform solution was obtained.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

This dye-containing negative resist composition (5) was filtered using a 0.2 μm filter and left in a cleaned sample bottle for 2 days. Thereafter, the composition was applied on a silicon wafer subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater and soft baked on a hot plate at 120 ° C. for 2 minutes to form a coating film having a thickness of 1.08 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 800 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Subsequently, PEB was performed on a hot plate at 135 ° C. for 1 minute. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a 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.

Reference example 1
Into a 50 ml eggplant type flask, resin A1 (1.76 g), dye D1 (2.15 g), dye D6 (0.5 g) and propylene glycol monomethyl ether (9.44 g) as a solvent were added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Thereafter, crosslinkable compound C3 (0.3 g), photoacid generator B3 (0.2 g), and Megafac R-30 (0.01 g) as a surfactant were added, and the mixture was further stirred at room temperature to obtain a dye-containing negative type. A resist composition (6) was obtained. No insoluble matter was found in the solution, and a uniform solution was obtained.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

This dye-containing negative resist composition (6) was filtered using a 0.2 μm filter and left in a washed sample bottle for 2 days. Then, the composition was applied on a silicon wafer that had been subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater, and soft-baked on a hot plate at 120 ° C. for 2 minutes to form a coating film having a thickness of 1.02 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 1500 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Subsequently, PEB was performed on a hot plate at 130 ° C. for 2 minutes. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a negative pattern. The pattern resolution was up to 5 μm in line / space without pattern peeling. However, the 2 μm pattern has no contrast and could not be formed. 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.

Reference example 2
In a 50 ml eggplant-shaped flask, resin A1 (1.76 g), dye D3 (1.45 g), 4-hydroxy-4-methyl-2-pentanone (4.72 g) as a solvent and propylene glycol monomethyl ether (4.72 g) And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Thereafter, crosslinkable compound C1 (0.3 g), photoacid generator B3 (0.2 g), and Megafac R-30 (0.010 g) as a surfactant were added, and the mixture was further stirred at room temperature. A resist composition (7) was obtained. No insoluble matter was found in the solution, and a uniform solution was obtained.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

This dye-containing negative resist composition (7) was filtered using a 0.2 μm filter and left in a cleaned sample bottle for 2 days. Then, the composition was applied on a silicon wafer subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater and soft baked on a hot plate at 120 ° C. for 2 minutes to form a coating film having a thickness of 1.10 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 1400 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Subsequently, PEB was performed on a hot plate at 130 ° C. for 2 minutes. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a negative pattern. The resolution of the pattern was 5 μm in line / space without pattern peeling. However, the 2 μm pattern has no contrast and could not be formed. 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.

Reference example 3
In a 50 ml eggplant type flask, resin A1 (1.76 g), dye D5 (2.14 g), 4-hydroxy-4-methyl-2-pentanone (4.72 g) and propylene glycol monomethyl ether (4.72 g) as solvents And stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

  Then, crosslinkable compound C4 (0.3 g), photoacid generator B4 (0.22 g), and MegaFac R-30 (0.010 g) as a surfactant were added, and the mixture was further stirred at room temperature to obtain a dye-containing negative type A resist composition (8) was obtained. No insoluble matter was found in the solution, and a uniform solution was obtained.

  Further, when a part of the solution was filtered using a 0.2 μm filter and left in a washed sample bottle at room temperature for 1 week, no foreign matter was observed in visual observation.

This dye-containing negative resist composition (8) was filtered using a 0.2 μm filter and left in a washed sample bottle for 2 days. Then, the composition was applied on a silicon wafer that had been subjected to HMDS treatment at 100 ° C. for 1 minute using a spin coater, and soft-baked on a hot plate at 120 ° C. for 2 minutes to form a coating film having a thickness of 1.11 μm. did. This coating film was irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation amount of 1800 mJ / cm ² by means of an ultraviolet irradiation device PLA-501 (F) through a test mask. Subsequently, PEB was performed on a hot plate at 130 ° C. for 2 minutes. Then, it developed by immersing with NMD-3 developing solution of 23 degreeC for a fixed time, and also performed the ultrapure water running water washing. Thereafter, post-baking was performed on a hot plate at 180 ° C. for 5 minutes to form a negative pattern. The resolution of the pattern was 5 μm in line / space without pattern peeling. However, the 2 μm pattern has no contrast and could not be formed. 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.

  The resolution of the pattern was confirmed using an optical microscope (ECLIPSE L-150 (manufactured by Nikon Corporation)) and an electron microscope (S-4100 (manufactured by Hitachi, Ltd.)), and the shape was confirmed using an electron microscope. confirmed.

  In Reference Examples 1 to 3, a 2.0 μm pattern could not be formed.

  The dye-containing resist composition of the present invention can be provided as a resist composition having a high dye concentration for developing a desired spectral spectrum, corresponding to thinning of a color filter. The dye-containing resist composition of the present invention exhibits high spectral spectrum reproducibility, high heat resistance and light resistance even when the dye concentration is increased, and has a high resolution of 5 μm or less, particularly 2 μm or less. Further, it can be provided as a color resist composition having no development residue.

Claims (7)

Formula (2) :

(Wherein R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom or an organic group, and R ² is an organic group). ):

^{(Wherein, R 1, R 2, R} 3 and R ⁴ each. Represents a hydrogen atom or an organic group) a dye containing a cation represented by a dye-containing photoresist composition,
Dye-containing resist composition comprising the dye in an amount of 30 to 90% by mass based on the total solid content of the dye-containing resist composition (however, photoacid generation shown in the following (a) to (h)) Except for a dye-containing resist composition containing a combination of an agent and one or two dyes).

The dye containing resist composition of Claim 1 containing the combination of the photo-acid generator shown to following (I) thru | or (V), and 1 type or 2 types of dye.

Dye containing resin (A), photoacid generator (B) of Claim 1 or Claim 2 , crosslinkable compound (C), dye (D) of Claim 1, and solvent (E) Containing resist composition. The manufacturing method of a color filter including the process of apply | coating the dye-containing resist composition of any one of Claim 1 thru | or 3 on a board | substrate, drying, exposing and developing. A liquid crystal display device comprising a color filter manufactured by the method of claim 4 . The LED display apparatus containing the color filter manufactured by the method of Claim 4 . The solid-state image sensor containing the color filter manufactured by the method of Claim 4 .