TWI375861B - Resist composition containing cobalt system dye and color filter by use of the same - Google Patents

Description

1375861 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a photoresist composition containing a dye and a color filter using the same. «Τ 【Prior Art】 Adding a photoresist composition of a pigment to form a fine pattern can produce a high-color color filter. Therefore, the color filter for imaging elements such as a solid-state imaging device (CCD) or a liquid crystal display device (LCD) is mainly manufactured by a method of forming a pattern by adding a photoresist of a coloring matter. In this method, a photoresist composition containing a pigment and a polymer resin is used, and after coating on a substrate, a colored layer is patterned by lithography, and a coloring pattern is formed by image formation, and this step is repeated for each color. Make color filters. In this case, the pigment used as the colorant is generally a pigment excellent in heat resistance and light stability, and a photoresist which disperses the pigment is proposed. • For example, a photosensitive colored resin composition comprising a resin-based material which can be acid-hardened, a photoacid generator, and a pigment is disclosed (for example, Patent Document *1). It is disclosed that the resin-based material is composed of a phenol-containing resin and a crosslinking agent having an N-hydroxymethyl group structure. However, since the pigment itself contains particles having a particle diameter of several tens of nm to several hundreds of nm, the pigment itself becomes a problem of foreign matter or dispersion of turbidity. Therefore, it is difficult to produce a color filter for CCD which requires high resolution by using a conventional pigment. However, when the dye is used as a dye, the dye is soluble in the organic solvent, and -5-(2) 1375861 is obtained to a uniform photoresist composition. Therefore, a finer pattern can be formed than the photoresist composition of the dispersed pigment. For example, a negative-type photoresist composition comprising an acid-curable resin, a crosslinking agent, a photoacid generator, a dye, and a solvent is disclosed (for example, Patent Document 2). * In addition, an amine salt of an acid dye is disclosed, and a color filter which is soluble in an organic solvent and an alkaline aqueous solution is added with a photoresist (for example, Patent Document 3) 〇 • Further, a dye having a cation having a nitrogen-containing organic compound is disclosed. A method for producing a method of causing an action of an aliphatic amine, an alicyclic amine, an aromatic amine or a fourth-order ammonium salt and a tetrazo dye. These can be used as various inks, paints, or as general synthetic resin materials for paper, synthetic resin, fiber materials, wood, oil, coloring agents for natural and synthetic waxes, and coloring agents for petroleum products (for example, Patent Document 4) ). Further, an ink composition containing a reaction mixture of a water-soluble dye, an epoxy compound, and an amine compound having active hydrogen as a coloring agent is disclosed. These ® can be used for notebooks for printing, recording, ink, and paper coloring (for example, Patent Document 5). A color filter having a dye-colored dye of a compound having a hydroxyl group-containing pyrazole azo structure and chromium formed by 2:1 (for example, Patent Documents 6 and 7). Further, a color filter colored with a sulfonic acid group or a metal-free phthalocyanine having a nitro group (for example, Patent Documents 8, 9, and 10). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. 60-229953 (Patent Document 5). Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 63-226602 (Patent Document 8): Japanese Patent Application Laid-Open No. Hei No. 303407 (Application No.) [Patent Document 9]: Japanese Patent Laid-Open No. 2--98-03 (Application Patent Scope) ♦ 〔 [Patent Document 10] Japanese Laid-Open Patent Publication No. Hei 2-108004 (Application No.) [Draft of the Invention] [Disclosure of the Invention] [Problems to be Solved by the Invention] When it is desired to further increase the thickness of the color filter, It is necessary to increase the concentration of the dye in the photoresist composition to have the desired spectral spectrum. The object of the present invention is to provide a color filter which can be applied to a color filter to improve the dye concentration (7) 1375861. The fifteenth aspect: an LED display device characterized by the method of the thirteenth aspect. sheet. A sixteenth aspect: A solid-state imaging device characterized by comprising the color filter manufactured by the method of the thirteenth aspect. ® [Effect of the Invention] The photoresist composition of the present invention can be applied to the thinning of a color filter'. The dye concentration can be increased to 30% by mass or more in the total solid content of the photoresist composition by dyes and The interaction of the phenol resin improves heat resistance and light resistance. Further, by combining a dye exhibiting a high alkali developability resin and a base developability, as a photoresist composition, a color filter which exhibits a desired spectral spectrum, is excellent in heat resistance and light resistance, and has high resolution can be produced. . The photoresist composition of the present invention can be formed into a thin film at the time of producing a color filter by increasing the dye ® concentration in the photoresist composition. When the film thickness of the color filter is set to 0.3 to 1.5 μm, the dye concentration in the resist composition must be '30 mass% or more. The photoresist composition containing the dye molecule and the color filter produced by the group exhibits a region having a transmittance of at least 703⁄4 or more in a wavelength range of 400 to 700 nm due to the dye molecule, and a display of 103⁄4 or less The spectral spectrum of the region of transmittance. When the dye concentration is such that the transmittance is low at a low concentration, a small amount of the dye molecules per unit volume may be used, but heat resistance and light resistance cannot be sufficiently ensured. When the dye concentration is at a high concentration and the transmittance is displayed, the desired spectrum of the spectrum can be obtained, -11 - (8) 1375861 and the number of dye molecules per unit volume is increased, and sufficient or insufficient adhesion cannot be obtained. Therefore, the photoresist composition of the present invention contains a dye having a transmittance of 70% or more in a visible region (wavelength of 400 to 750 nm), particularly a wavelength of 400 to 700 nm, and a spectroscopic spectrum showing a region of 103⁄4 or less. Dyes such as red, green, and blue have regions where the specific transmittance of each dye exhibits absorption of 10% or less) and regions that do not absorb (where the region is 702⁄4 or more), indicating that the non-absorbed region does not hinder the absorption of the material. Preferably. Each of the dyes has a region which is not originally absorbed, and the dye is sometimes insufficient in heat resistance or light resistance. The dye for use in the photoresist of the present invention has a transmittance of 70% or more in a region which exhibits no absorption in a specific region where absorption is exhibited, and has a spectral spectrum to obtain a clear color filter. The specific structure of the photoresist composition used in the present invention is a combination of a specific structure of a cation and an anion of a counter ion, which is produced by the other main component of the photoresist composition, namely, a resin, a photoacid or a photobase. The composition of the agent, the crosslinkable compound and the solvent are compatible and compatible. The photoresist composition of the present invention containing these components is formed. After the substrate is cured, after exposure, the photoresist pattern resolution obtained by the development is developed. . The dye (D) used in the present invention is a cobalt-containing salt-containing dye, and (D) can be used to obtain a color filter containing a harmful metal such as chromium and having the same heat resistance and light resistance as those containing chromium. The resolution light range has at least a transmittance region (the transmittance is 10% of the composition of the dye when it is absorbed by the dye, and the high-soluble solution of the dye generator is coated with the dye salt dye -12- (9) 1375861 [Best Mode for Carrying Out the Invention] The resin (A) of the photoresist composition selecting photoresist composition of the present invention can be applied to a negative type or a positive type. - More specifically, the photoresist composition of the present invention The resin (A) is selected from the group consisting of resin (AN) and resin (AP), and the photoacid generator or photobase generator (B) is selected from the group consisting of a photoacid generator or a photobase generator (BN) and a photoacid generator ( BP), which can be applied to negative and positive types. • Negative photoresist composition means resin (AN), photoacid generator or photobase generator (BN), crosslinkable compound (C), dye ( D) and a negative photoresist composition of the solvent (E). The positive photoresist composition means a resin (AP), a photoacid generator (BP), a crosslinkable compound (C), a dye (D), and a positive photoresist composition of the solvent (E). The resin (AN) used for the negative photoresist composition is an acid produced by heat or light irradiation. Or a resin which is hardened by a base generated by heat or light irradiation, or a photosensitive resin which is crosslinked by heat or light irradiation, and the coating film of the unexposed portion in the resin can be removed by using a developing solution, that is, no special Resin (AN) is, for example, a resin having a hydroxyl group or a carboxyl group. * For example, an acrylic resin such as polyvinyl alcohol, polypropylene decylamine, polyacrylic acid or polymethacrylic acid, polyamic acid, or polyvinyl phenol. And derivatives thereof, copolymers of polymethacrylate and maleic anhydride, phenol resins, phenolic resins, polyimines containing hydroxyl and/or carboxyl groups, cellulose, cellulose derivatives, starch, chitin, shells Glycan, gelatin, zein, sugar skeleton polymer compound, polyamine, polyethylene terephthalate, polycarb-13- (10) 1375861 acid ester, polyurethane, and polyoxyl These resins may be used singly or in combination of two or more kinds. '' The particularly desirable resin (AN) is polyvinyl phenol and its copolymer. 'The comonomer is, for example, an acrylic monomer such as (meth)acrylic acid. Ester and ethylene deficiency And carboxylic acid. (Meth) acrylates are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylamino (meth) acrylate, Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and epoxy propyl (meth) acrylate. Ethylene unsaturated carboxylic acid can use acrylic acid, methacrylic acid, crotonic acid, Malay Acid, fumaric acid, itaconic acid and these anhydrides or half esters, of which acrylic acid, methacrylic acid, maleic acid, hydroxypropyl (meth) acrylate® are preferred. The weight average molecular weight (in terms of polystyrene) of the copolymer of polyvinyl phenol, polyvinyl phenol and the above acrylic monomer is 1000 to 100,000 • 'from the viewpoint of development and adhesion, it is preferably 2000 to 〜 30000. These may be combined if necessary, for example, a copolymer of vinyl phenol and one kind of the above-mentioned acrylic monomer may be used or a copolymer of a combination of a vinyl phenol and two or more kinds of the above acrylic monomers may be used. For example, acrylic acid derivatives, acrylonitrile, methacrylonitrile, styrene, a-methylstyrene, p-methylstyrene, o--14-(11) 1375861 methylstyrene, p-methoxystyrene, Phenylbenzene such as p-chlorostyrene. Among these, styrene is preferred. • The polyvinyl phenol or its copolymer, that is, the polyhydroxystyrene-styrene derivative, has a weight average molecular weight of 1,000 to 100,000, and is preferably from 2,000 to 30,000 in terms of adhesion. These two or more copolymers are used necessitarily or in combination. In the negative resist composition, when the resin (AN) is used, the photoacid generator is not particularly limited as long as the photoacid generator directly or indirectly generates an acid in the Φ generating agent or the photobase generating agent (BN). For example, a compound such as a triterpenoid compound, an alkene benzene derivative, a two-base compound alkane compound, a sulfonic acid derivative compound, a diaryl sulfonium salt, a triaryl sulfonium salt, an iron aromatic hydrocarbon complex, etc., but The unrestricted body is, for example, diphenyl iodine chloride, diphenyl iodonium trifluoromethyl, diphenyl iodine methyl sulfonium salt, diphenyl io io oxime toluene sulfonium salt iodonium bromide, diphenyl iodine Key tetrafluoroborate, diphenyl iodine, diphenyl iodine hexafluoroarsenate, bis (p-tert-butyl sulfonium hexafluorophosphate, bis (p-tert-butylphenyl) iodine Methanesulfonate (p-tert-butylphenyl) iodine toluene sulfonium salt, bis(p-diyl) iodine trifluoromethanesulfonate, bis (p-tert-butylphenylfluoroborate, bis ( P-tert-butylphenyl)iodonium chloride, phenyl)iodide chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate phenylphosphonium chloride, triphenylsulfonium bromide, tris(p. Oxytetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphonate ethoxyphenyl)phosphonium tetrafluoroborate, triphenyl scale chloride, ethylene derivative or polyhydroxyl The photoacid which can be used alone in development can be obtained by a specific example, a diazo group, a triaryl group, an alkanesulfonate, a diphenyl hexafluoroantimony phenyl iodonium salt, a ditributylbenzene. Iodine tetra-double (p-chlorate, triphenyl) ruthenium, tris (p-triphenyl iron-15-(12) 1375861 bromide, tris(p-methoxyphenyl) scallop tetrafluoroborate, three (p-methoxyphenyl) sulfonium hexafluorophosphonate, tris(p-ethoxyphenyl) scallop tetrafluoroborate. The photoacid generators exemplified in the formulae (5) to (71) can also be used.

OH formula (6)

0H

Formula (1 0) C F3SO3

Formula (1 1 ) C F3SO3 -16- (13)1375861 [Chem. 6]

-17- (14)1375861 [Chem.7]

-18- (15)1375861 [Chem. 8]

η

-19- (16)1375861 [Chemistry 9]

-20- (17)1375861 [Chem. 10]

-21 - (18)1375861 [Chem. 11]

Formula (5 9) fCCI3 cc, 3 yCCI, formula (6 0)

-22- (19) 1375861 [Chem. 12]

Equation (6 4)

23- (20)1375861 [Chem. 13]

The N photoacid generator uses the photoresist φ of the compounds of the formulae (55) to (58), (68) and (69) to (71) to a more vivid resist pattern. The photoacid generator represented by the above formula is only an example and is not limited. The photoacid generator may be used singly or in combination of two or more kinds, and the amount of introduction is 100 parts by mass of the resin (AN) component, preferably 300 parts by mass, preferably 2 to 100 parts by mass. When the introduction amount is 5, the crosslinking reaction cannot be sufficiently performed, and it is difficult to obtain the desired amount. When the amount exceeds 300 parts by mass, the storage of the photoresist composition is such that the introduction amount of the acid generator is for the resin (AN) n parts. It is preferred to introduce 1 to 30,000 parts by mass. The composition of (6 3 )~ can be obtained by these compounds. Further, it can select 1 to ^ up to 1 part by mass of the photoresist pattern, which is inferior in character. The mass of 100 is -24 - (21) 1375861 The photobase generator is not particularly limited as long as it is directly or indirectly produced by light irradiation. For example, bis[[(2.nitrophenylmethyl)oxy]carbonylhexan-1,6-diamine], nitrophenylcyclohexylaminocarboxylic acid vinegar, bis(methoxybenzyl) A compound having a structure of a hexamethylene methyl carbazate and a compound of the following formula (72) to formula (> 74). [Chem. 14]

Ri style (7 2) »2

/R3 II 式 Formula (7 4) , R2 (7 3) (But in the formula (72) to formula (74), Ri'112 and R3 represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted Phenyl). These photobase generators are the same as the photoacid generator, and may be used singly or in combination of two or more. In addition, the amount of introduction is 1 to 300 parts by weight, preferably 2 to 100 parts by weight, based on 100 parts by mass of the resin (AN) component. As the photosensitizer, a conventionally known photo sensitizer can be used, for example, a thiophene, a xanthene, an anthraquinone, a thiopyridylium salt, an anthracene based system, or a merocyanine-25-(22) 1375861 system. , 3-substituted coumarin, 3,4_substituted coumarin, cyanine, acridine, thiazine, phenothiazine, lanthanide, benzophenone, benzopyrene, lanthanide , keto-enrich, original opiate, borate. These can be used individually or in combination • - 2 or more. • In the negative resist composition, the crosslinkable compound (C) used for the resin (AN) may be at least one crosslinked group having a group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. Compound. • For example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, a guanamine resin, a glycoluril-formaldehyde resin, an amber oxime-formaldehyde resin, an ethylene urea-formaldehyde resin, or the like. The crosslinkable compound (C) can be, for example, a melamine derivative, a benzoguanamine derivative or a glycoluril in which a hydrogen atom of an amine group is substituted with a hydroxymethyl group or an alkoxymethyl group or both. The melamine derivative and the benzoguanamine derivative may be in the form of a dimer or a trimer. It is preferred that these have an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups in one triazine ring. ® This melamine derivative or benzoguanamine derivative, such as a triazine ring of a commercial product, is averaged by 3.7 methoxymethyl substituted MX-750 and a triazine ring averaged 5.8 Oxymethylated MW-30 (manufactured by Sanwa Chemical Co., Ltd.) or saimel 300, 301, 350, 370, 771, 325, 327, 703, 712, etc. methoxymethylated melamine, saimel Methoxymethylated butoxymethylated melamine of 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine of saimel 506, 508, etc., such as carboxyl group of saimel 1 141 Oxymethylated isobutoxymethylated melamine, such as methoxymethylated ethoxy-26-(23) 1375861 methylated benzoguanamine of saimel 11 23, such as saimel 1123-10 Methoxymethylated butoxymethylated benzoguanamine, such as butoxymethylation of saimel 1128 • benzoguanamine, carboxyl group-containing methoxylate such as saimel 1 1 25-80 - · Ethoxymethylated benzoguanamine (above is SCITECH Industries, Japan) (old Mitsui Sainamide). Further, the glycoluril includes, for example, butanoxymethylated glycoluril of saimel 1170, methylolated glycoluril of saimel 1172, and the like, such as methoxymethylolated glycoluril of powderink 1174 (above • is SCITECH Industries of Japan ( Share)) (Old Mitsui Sainaimde (share) system). Further, a benzene or a phenolic compound having a hydroxyl group or an electrophilic group, for example, 1 '3' 5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1,4·bis(second butoxymethyl)benzene, 2,6-dimethylol to p-butylphenol, etc., which may also contain an epoxy group, an isocyanate group, and have a crosslinking group. Compound. Specific examples are bisphenol acetone epoxy propyl ether, benzoquinone ring oxy resin, cresol novolac epoxy resin, triepoxypropyl isocyanurate, tetraglycidyl propyl biphenyl, tetracyclic Oxypropyl-m-m-xylylenediamine, tetra-epoxypropyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether ethane, tris-phenyl epoxidized ether ethyl ether, Bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl Benzene, 4' 4-bis(2,3-epoxypropoxy) octafluorobiphenyl 'triepoxypropyl-aminophenol, tetraepoxypropylm-xylenediamine, 2-(4) -(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)benzene Propyl, 1,3·bis (4·( -27- 1375861 24 phenyl phthalyl) lyyl oxypropyloxy ring 3 2 phenyl oxypropyloxycycloethyltolylethyl benzene, etc. 2 I. Oxygen·- These crosslinkable compounds (C) may be used singly or in combination of two or more. In addition, the amount of introduction is 100 parts by mass of the resin (AN) component. It can be selected from 1 to 300 parts by mass, preferably from 20 to 20 parts by mass. When the amount is less than 1 part by mass, the crosslinking reaction cannot be sufficiently performed, and it is difficult to obtain the desired photoresist pattern and exceeds When the amount is 300 parts by mass, the storage stability of the photoresist composition is inferior. Therefore, when the amount of the crosslinking agent is 100 parts by mass based on the resin component, it is preferably 1 to 300 parts by mass. The resin (AP) is a resin which is hardened by heat, and is heated or irradiated with an acid to decompose the resin to change the polarity or molecular weight, and is soluble in the developing solution, and the exposed portion of the resin can be coated. The resin (AP) is, for example, a resin having a hydroxyl group or a carboxyl group, etc. Specific examples are: polyvinyl alcohol, polypropylene decylamine, polyacrylic acid, polymethacrylic acid, polyproline Polyhydroxystyrene, polyhydroxystyrene derivatives, copolymers of polymethacrylate and maleic anhydride, phenolic resins and phenolic resins, polyimines containing hydroxyl groups and/or carboxyl groups, cellulose derivatives, Sugar skeleton polymer ' Polyamide, polyethylene terephthalate, polycarbonate, polyurethane, and polyoxyalkylene. These resins may be used alone or in combination of two or more. a resin, that is, an acrylic copolymer mainly composed of (meth) acrylate, an ethylenically unsaturated carboxylic acid and, if necessary, other mono- 28-(25) 1375861. These resins may be used alone or Two or more types are used in combination. The photoacid generator (BP) used in the positive photoresist composition is, for example, a naphthoquinone--diazide compound. Generally, a 1,2-quinonediazide compound such as *1 can be used. 2-benzoquinonediazide sulfonate, 1,2-naphthoquinonediazide sulfonate, 1,2 benzoquinone diazide sulfonamide and 1,2-naphthoquinone diazidesulfonate Amines, etc. These photoacid generators may be used singly or in combination of two or more. Further, the amount of introduction is #1 to 50 parts by mass in the case of 100 parts by mass of the resin component. When the amount of introduction is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently, and it is difficult to obtain a desired photoresist pattern. When the amount exceeds 50 parts by mass, the storage stability of the photoresist composition is inferior. Therefore, when the amount of the naphthoquinone diazide compound is 100 parts by mass based on the resin component, it is preferably 1 to 50 parts by mass. The crosslinkable compound (C) used in the positive-type resist composition may be a crosslinkable compound having at least one cross-linking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. A compound or a compound having an epoxy group-containing cyanate group and having a crosslink-forming group and having a polymerizable unsaturated group. ' These crosslinkable compounds can be used individually or in combination of 2 or more types. Further, when the amount of introduction is 100 parts by mass of the resin (ΑΡ) component, it may be 1 to 200 parts by mass. When the amount is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently, and it is difficult to obtain a desired photoresist pattern, and when it exceeds 200 parts by mass, the storage stability of the photoresist composition is inferior. Therefore, when the amount of the crosslinkable compound (C) is 100 parts by mass based on the resin component, it is preferably 1 to 200 parts by mass. -29- (29) (29) 1376861 is the following formula ( 4) It is especially ideal.化γΝΗύ + νη2 (wherein R is a hydrogen atom or a methyl group). The compound of the formula (4) of the above formula (3) and its specific example compound has a resonance structure, and when the compound of the formula (4) is exemplified, the formula (81) is also contained.

The cation of the structure (wherein R is a hydrogen atom or a methyl group), but this cation can also be used in the photoresist composition of the present invention. A mixed salt dye composed of an anion and a cation, for example, a compound represented by the formula (82) to the formula (9 9 ). -33- (30)1375861 [Chem. 21]

So2nh2

o HNV yNHv ^ (8 2) [Chem. 22]

03S

N〇2 02N. >' \ 0~N"n>n^s〇3 CH3 )=N H3C HNV NHv - x 3 Formula (8 3) [Chem. 23]

PhHNOzS

34- (31)1375861

[Chem. 24]

[化27] -35- (32)1375861

[化 28]

[化29]

[化 30] -36- (33)1375861

[化31]

[化32]

HNV NH ^ type (9 3 > [Chem. 33] -37- (34) 1376861

[34]

[化35]

[化36]

-38- (35)1375861 [化37]

[化38]

As the dye (D) used in the photoresist composition of the present invention, a commercially available product can be used. These dyes (D) can be easily synthesized by a known method. For example, a method of reacting an 'amine' corresponding to the structures of the above formulas (3) to (4) and formulas (75) to (80) with a dye molecule having a sulfonic acid group or a carboxylic acid group (parent) Got it. In other words, an aqueous solution of a compound having a sulfonic acid group or a carboxylic acid group and having a complex structure is reacted with an amine of a molar ratio required to form a salt, and a salt which is poorly soluble in water is precipitated to be synthesized. When the salt of the dye is soluble in water, salting out can be carried out to obtain a salt. More specifically, in the aqueous solution of the above dye having sodium sulfonate or sodium carboxylate and having a cobalt-coordinated-39-(36) 1375861 structure, the formula (3) to the above formula (4) is added. An aqueous solution of an ammonium salt having a structure of the formulae (75) to (80) is reacted to produce a cobalt-stack salt dye having the cations of the above formulas (3) to (4) and (75) to (80). The structure of the above formula (3) to formula (4) and formula (75) to formula (8) is added to an aqueous solution of the above dye having sodium sulfonate or sodium carboxylate and having the structure of the complex. The aqueous solution of the corresponding hydrochloride salt of the amine is reacted to produce a dye having the cations of the above formula (3) Φ to formula (4) and formula (75) to formula (80). The dye (D) used in the photoresist composition of the present invention may be used by mixing any dye having 60% by mass or less of the entire dye. These optional dyes are, for example, acid dyes, oil-soluble dyes, disperse dyes, reactive dyes, direct dyes and the like. For example, azo dyes, benzoquinone dyes, naphthoquinone dyes, oxime dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, anthraquinone dyes, diphenylmethane dyes , triphenylmethane dyes, fluoranthene dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, phthalocyanine dyes, nickel complex dyes, and dyes. Specifically, for example, the following color index numbers are shown. CISoIvent Yellow 2, 3, 7, 12, I 3, 14, I 6, 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, -40- (37) 1375861 187, 18 9' 190, 191, CI Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31 , 40: 1, 41, 45, 54, 5 6 , 58, 60 , 62 ' 63 , 70 , 75 , 77 , 80 , 81 , 86 , 99 , 1 02 , 103 ' 105 , 106 , 107 , 108 , 109 , 110, 111, 112, 113, CI S o 1 ve nt Re d 2, 3, 4, 8, 1, 6, 7, 7, 18, 2, 3, 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,: 2 29, 230, 233, 234, 235, 236 '238, 239, 240, 241, 242, 243 ' 244, 245, 247, 248, CI 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 ' CI 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, CI Solvent Green 1, 3, 4, 5, 7, 28, 29 ' 32, 33, 34, 35, CI Solvent Brown 1, 3, 4, 5 12, 20, 22, 28, 38' 41 '42, 43, 44, 52, 53, 59, 60, 61, 62, 63, CI Solvent Black 3 -41 - (38) 1375861, 5, 5: 2. 7, 13, 22, 22: 1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49, 50, CI Acid Red 6, 16, 26, 60, • 88, 111, 186, 215, CI acid green 25, 27' CI acid blue 22, - 25, 40, 78, 92, 113, 129, 167, 230, CI acid yellow 17, • 23, 25, 36, 38, 42, 44, 72, 78, (:.1. alkali red 1, 2, 13, 14, 22, 27, 29, 39, CI alkali green 3, 4, CI alkali blue 3, 9, 41, 66, C. I_ alkali purple 1, 3, 18, 39, 66, CI alkali yellow 11, φ 23, 25, 28, 41, CI direct red 4, 23, 31, 75, 76, 79, 80, 81, 83 , 84, 149, 224, CI · Direct Green 26, 28, CI Direct Blue 71, 78, 98, 106, 108, 192, 201' CI Direct Purple 51, CI Direct Yellow 26, 27, 28, 33, 44 , 50, 86, 142, CI direct orange 26, 29, 34, 37, 72, CI sulfur red 5, 6, 7, CI sulfur green 2, 3, 6, CI sulfur blue 2 3,7,9,13,15, CI sulfur violet 2, 3, 4, CI sulfur yellow 4, CI瓮 (vat) red 13, 21, 23, 28, 29, 48' CI瓮 green 3, 5, 8, CI Indigo 6, _ 14, 26, 30, CI 瓮 purple 1, 3 ' 9, 13, 15, 16, CI 瓮 yellow 2, 12, 20, 33, CI 瓮 orange 2, 5, 11, 15 , 18, 20, CI azo couple synthesis 2, 3, 4, 5, 7, 8, 9, 10' 11' 13, 32, 37, 41 • , 48, CI activity (reactive) red 8, 22, 46 , 120, CI reactive blue 1, 2, 7, 19, CI active violet 2, 4, CI active yellow 1, 2, 4, 14, 16, CI active orange 1, 4, 7, 13, 16, 20, CI Disperse red 4, 11, 54, 55, 58' 65, 73, 127, 129, 141, 196, 210, 229, 3 54 > 356, CI disperse blue 3, 24, 79, 82, 87, 106, 125 , 165, 183, C_I. Disperse Violet 1, 6, 12, 26, 27, 28, CI Disperse Yellow-42- (39) 1375861 3, 4, 5, 7, 23, 33, 42, 60, 64, CI Disperse Orange 13, 29 30 〇 • Dye (D) shows a wavelength range of 4 〇〇 to 700 nm, with a transmittance of 70% or more and a display of less than 1%. Transmittance. The optical characteristics of the region are better than the temperature at 200 ° C or higher * the transmittance change is within 5%. The photoresist composition of the present invention and the color filter produced by the composition also have The same optical properties. # The negative and positive photoresist composition of the present invention is applied to a substrate and fired at a temperature of 50 to 150 ° C, and is exposed and developed, but even if the degree of firing is 200 to 270 ° C (200) The temperature is 30 minutes at ° C and 30 seconds at 270 ° C. In the wavelength range of 400 to 700 nm, the transmittance of the transmittance above % is higher than that of the high temperature. Preferably, the amount of the dye (D) introduced into the negative resist composition of the present invention is related to the resin (AN), the photoacid generator or the photobase generator (BN), the ® compound. When (c) and 100% of the solid content of the dye (D) are all, 1 to 90% by mass is selected. When the amount of introduction of the dye is small, it is difficult to have a desired spectral spectrum when the film is formed into a thin film, and the storage stability of the photoresist composition is poor when the amount of the dye is large. However, in the photoresist composition of the present invention, a dye which uses a cation having a specific structure, in particular, a dye which combines a cation of a specific structure with an anion of a counter ion, is introduced, and thus the amount of the above dye is introduced (the dye in the whole solid portion is concentrated) It can be a low concentration of several mass%, and even when it is set to a concentration of 3 〇 to 9 〇 mass%, the dye can be sufficiently dissolved. In addition, the amount of the dye (D) is introduced into the positive resistive composition of the present invention. For the resin (AP), the amount of dye (D) is introduced into the positive resistive composition of the present invention. When the solid content of the photoacid generator or the photobase generator (BP), the cross-linking compound (C), and the dye (D) is (? - 1 〇〇%), I to 90% by mass is selected. When the amount of introduction of the dye is small, it is difficult to have a desired spectral spectrum when the light-blocking film is formed into a thin film, and the storage stability of the photoresist composition is poor when the amount of the dye introduced is large. However, the composition of the photoresist of the present invention is poor. In the case of using a dye having a specific structure of a cation, especially a combination of a cation of a specific structure and an anion of a counter ion, the amount of the dye introduced (the dye concentration in the whole solid part) can be used in the mass The low concentration of %, even when set to a high concentration of 30 to 90% by mass, ensures sufficient solubility of the dye. The solvent (E) used in the negative and positive resist compositions of the present invention is, for example, acetone. Methanol, ethanol, isopropanol Methoxymethylpentanol, dipentene, ethyl pentanone 'methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, 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 monoacetate - propylene glycol tert-butyl ether 'dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol single Acetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl 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-44- (41) 1375861 ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, dibutyl ether, diisobutyl hydrazine, methyl ring Hexene , propyl ether, dihexyl ether, dioxane, * N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, -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, Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, • ethyl 3-methoxypropionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, etc. These can be used individually or in combination of 2 or more types. Among these solvents, the compatibility with the dye (D) for the photoresist composition of the present invention is preferably an ethyl ketone alcohol solvent. The ethyl ketone alcohol has, for example, a 'dot-hydroxy group' ketone, and specifically, a 4-hydroxy-4-methyl-2-pentanone is preferred. The reason why the compatibility between the dye (D) and the ethyl ketone alcohol solvent used in the photoresist composition of the present invention is particularly preferable is that the hydroxyl group in the ethyl ketone alcohol solvent molecule has a relative position to the carbonyl group. In particular, the cation of the dye exerts an effect of a preferred ligand, and thus exhibits a very high solubility*, and when used, it has high solubility. In the solvent used in the present invention, an ethyl ketone alcohol solvent may be used alone, but a solvent containing 10% by mass or more of an ethyl ketone alcohol solvent in the total solvent is preferred. In the negative resist composition of the present invention, the resin (AN), the photoacid generator or the photobase generator (BN), the crosslinkable compound (C), and the dye (D) are produced in the resin (AN) and photoacid. Or a photobase generator (BN), a ratio of -45-(42) 1375861, a compound (C), a dye (D), and a solvent (E), that is, a solid content concentration of 5 to 50% by mass. Preferably, it is 10 to 30% by mass '. When the ratio is less than 5% by mass, the film thickness of the coating film is too low to have a spectral spectrum. When the amount is more than 50% by mass, the viscosity of the photoresist composition is too high. The uniformity of the film thickness of the coating film is affected.

In the positive resist composition of the present invention, the resin (AP), the photoacid generator (BP), the crosslinkable compound (C), and the dye (D) are in the resin (AP # ), photoacid generator (BP). The ratio of the crosslinkable compound (C), the dye (D) and the solvent (E), that is, the solid content concentration is 5 to 50% by mass, preferably 1 to 30% by mass. When the ratio is less than 5% by mass, the film thickness of the coating film is too low to have a desired spectral spectrum. When it exceeds 50% by mass, the viscosity of the photoresist composition is too high to affect the uniformity of the film thickness of the coating film. The negative electrode and positive resist composition of the present invention may contain a surfactant in order to improve the coating property or planarization property of the photoresist film. Examples of such a surfactant include a fluorine-based surfactant, a polyoxyn surfactant, and a non-ionic surfactant. More specifically, for example, FTOP EF301, EF3 03, EF3 52 (manufactured by Jemco), Megafac F171, F173, R-30 (Major Japan • Ink Chemical Industry Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M) (share) system, ASAHIGARD AG710, Surflon S-3 82, SC 1 01 'SC102 'SC103, SC104, SC 1 05 'SC106 (Asahi Glass Co., Ltd.). When the ratio of use of the surfactant is 100 parts by mass based on the resin (AN) or the resin (AP) component, 0.0 to 2 parts by mass, preferably -46 to (43) 1375861 0.01 to 1 part by mass is used. When the content of the surfactant is more than 2 parts by mass, the resist film is likely to be unevenly formed, and when it is less than 0.01 part by mass, the resist film is easily formed on the resist film. * " In order to improve the adhesion to the substrate after development, it may contain a adhesion promoter. Specific examples of such adhesion promoters include chlorodecanes such as trimethylchlorosilane, dimethylvinylchlorodecane, methyldiphenylchlorodecane, and chloromethyldimethylchlorodecane; trimethylmethoxy Alkoxy groups such as decane 'dimethyl diethoxy decane, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, diphenyl dimethoxy decane, phenyl triethoxy decane a decane; hexamethyldioxane, hydrazine, Ν'-bis(trimethylformamido)urea, dimethyltrimethylformamidinylamine, trimethylmethanealkyl imidazolium Class; vinyl trichlorodecane, γ-chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropoxypropyltrimethoxydecane, γ-glycidoxy a decane such as propyltrimethoxydecane; benzotriazole, benzimidazole, oxazole, imidazole, 2-hydrothiobenzimidazole, 2-hydrothiobenzothiazole, 2-hydrosulfanyl benzene And a heterocyclic compound such as oxazole, urazole, thiouracil, hydrothioimidazole or thiopyrimidin or urea or sulphur-urea such as 1,1-dimethyl or 1,3-dimethylurea Compound. The ratio of use of the adhesion promoter to the resin (AN) or the resin (AP) component is usually 20 parts by mass or less, preferably 0.05 to 10 parts by mass, particularly preferably 1 to 10 parts by mass. In the negative and positive resist compositions of the present invention, additives which are miscible with the photoresist composition may be further added. For example, there are ultraviolet absorbers or antioxidants for improving light resistance, and compatibilizers for suppressing dye precipitation. Specific examples of the compatibilizing agent for inhibiting -47-(44) 1375861 dye are polyoxyethylene octyl ether compound, polyoxyethylene lauryl ether compound, polyoxyethylene alkyl (carbon number 12 to 13) ether * * compound, a polyoxyethylene 2-alkyl group (carbon number 12 to 14) ether compound, a poly--oxyethylene alkyl (carbon number 13) ether compound, a polyoxyethylene whale ether compound, a polyoxyethylene stearyl ether compound, a polyoxyethylene oil ether compound, a polyoxyethylene oxime ether compound, a polyoxyalkylene alkyl group (carbon number 11 to 15) ether compound, a polyoxyalkylene alkyl 2 alkyl group (carbon number 12 to 14) ether compound, An alkylamine group such as an alkyl ether compound such as a polyalkylene whale ether compound, a polyoxyethylene laurylamine ether compound, a polyoxyethylene stearylamine ether compound, or a polyoxyethylene oleyl amine ether compound. Ether compound, polyoxyethylene laurate decyl ether compound, polyoxyethylene decylamine decyl ether compound, polyoxyethylene oleate decyl ether compound, lauric acid diethanol amide compound, stearic acid diethanol amide compound 'Alkyl amide ether combination of oleic acid diethanol amide compound , polyoxyethylene polystyrene phenyl ether compound, polyoxyalkylene polystyryl phenyl ether compound, polyoxyalkylene polystyrylphenyl ether hydrazide® amine condensate, polyoxyethylene Allyl phenyl ether compound such as monostyrylphenyl ether compound, polyoxyethylene distyryl phenyl ether compound, polyoxyethylene naphthyl ether compound, glycerol monolaurate compound, glycerol mono-hard fat A glycerin fatty acid ester compound such as an acid ester compound, a glycerin monooleate compound or a glycerol trioleate compound, a sorbitan monolaurate compound, a sorbitan monopalmitate compound, or a sorbitan single a sorbitan ester compound such as a stearate compound, a sorbitan tristearate compound, a sorbitan monooleate compound, a sorbitan trioleate compound, or a polyoxyethylene dilaurate Acid ester compound, polyoxyethylene lauric acid-48-(45) 1375861 ester compound, polyoxyethylene stearate compound, polyoxyethylene distearate compound, polyoxyethylene dioleate compound, polyoxyethylene B A fatty acid ether ester compound such as an oleate ester compound, a polyoxyethylene castor oil ether compound, a poly-oxyethylene olefin hardened castor oil ether compound, etc., a vegetable oil oxime ester compound 'polyoxy τ ethene sorbitol 酑 single laurel Sorbitol ether ester such as ester compound, polyoxyethylene sorbitan monostearate compound, polyoxyethylene sorbitan monooleate compound, polyoxyethylene sorbitan trioleate compound #化合物, polyoxyalkylene alkyl ether compound, polyoxyalkylene octyl ether compound, polyoxyalkylene alkyl (carbon number 14~15) ether compound, polyoxyalkylene oleyl ether compound, etc. a polyol type polyether compound such as an alcohol type polyether compound or a polyoxyethylene polyoxypropylene condensate, a polyhydric alcohol such as a trimethylolpropane tris(polyoxyalkylene ether) ether compound or a polyoxyalkylene S glyceryl ether compound Polyether compound, methyl laurate compound, methyl oleate compound, isopropyl myristate compound, butyl stearate compound, octyl palmitate compound, octyl stearate compound , lauryl oleate ##, isotridecyl stearate compound, oleyl oleate compound, dioleyl adipate compound, trimethylolpropane tridecanoate compound, trishydroxypropyl propane trilaurate a fatty acid alkyl ester compound such as a compound, pentaerythritol dioleate compound, quaternary pentaerythritol monostearate compound or pentaerythritol distearate compound, an alkylsulfonate compound, a long-chain alkylbenzenesulfonic acid compound, Branched alkylbenzenesulfonic acid compound, long-chain alkylbenzenesulfonate compound, branched alkylbenzenesulfonate compound, branched alkyldiphenyl ether disulfonate compound, monoisopropylnaphthalenesulfonate Acid ester compound, diisopropyl naphthalene sulfonate compound 'triisopropyl naphthalene sulfonate compound, dibutyl naphthalene sulfonate compound -49- (46) 1375861, dioctyl sulfosuccinate compound Sulfate type compound, oleic acid sulfated oil compound, ricin sulfated oil compound, octyl sulfate compound •, lauryl sulfate compound, alkyl sulfate compound, alkyl ether sulfate-ester compound, etc. Compound, cellulose' Cellulose derivatives, sugars bone, a polymer compound carrier. When the ratio of use of these compatibilizing agents is 100 parts by mass of the resin (AN) or resin (AP) component, 0.001 to 20 masses are used. When the amount of use is small • When it is impossible to suppress the precipitation of the dye, it is difficult to obtain a good pattern shape when the use ratio is large. However, when the compatibility agent does not affect the pattern shape, 20 parts by mass or more can be used. Next, a method of producing a color filter using the dye-containing negative and positive resist composition of the present invention will be described. The photoresist composition of the present invention is applied onto a tantalum wafer or a glass substrate by a spin coating method or the like at a number of revolutions at which a desired photoresist film thickness is obtained, and is subjected to light burning (sintering). Lightly burn only the solvent, and it is better to carry out light calcination for 30 seconds to 10 minutes at a temperature of 50 to 15 (TC temperature range of TC. Then, exposure is performed through a mask at an exposure amount of about 10 to 3000 mJ/cm 2 . For example, an ultraviolet ray such as a mercury lamp, a far ultraviolet ray, an electron ray, an X ray, or the like can be used. When the negative photoresist composition is patterned after exposure, post-exposure heating (PEB, post-exposure baking) is preferred. PEB can be cross-linked by exposure to acid or alkali to increase the difference between the solubility of the developing solution and the unexposed portion, and the resolution of the solution can be improved. The PEB system is subjected to a temperature range of 50 to 150 ° C for 30 seconds to 5 seconds. The development is carried out next. The development method is not particularly limited, and development can be carried out by a known method such as stirring method -50-(47) 1375861, dipping method, spray method, etc. The development temperature is 20 ° C to 3 Preferably, 0 ° C is immersed in the developing solution for 10 seconds to 10 minutes. 'The developing solution may be an organic solvent or an alkaline aqueous solution, etc. Specifically, for example, isopropyl alcohol, propylene glycol monomethyl ether, and B Aqueous amine solution, n-propylamine water solution, aqueous solution of diethylamine, two Aqueous solution of n-propylamine, aqueous solution of triethylamine, aqueous solution of methyldiamine, aqueous solution of diethanolamine, aqueous solution of triethanolamine, aqueous solution of tetramethylammonium hydroxide, aqueous solution of sodium hydroxide, aqueous solution of potassium hydroxide, aqueous solution of sodium carbonate, hydrogen carbonate A sodium aqueous solution, an aqueous sodium citrate solution, a sodium metasilicate aqueous solution, etc. When it is desired to increase the removability of the unexposed portion, it is preferred to add a surfactant to the developing liquid. Specifically, for example, a polyoxyethylene octyl ether compound, Polyoxyethylene lauryl ether compound, polyoxyethylene alkyl (carbon number 12 to 13) ether compound, polyoxyethylene 2 alkyl group (carbon number 12 to 14) ether compound, polyoxyethylene alkyl group (carbon number 13) Ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl ether compound, polyoxyethylene oleyl ether compound, ® polyoxyethylene decyl ether compound, polyoxyalkylene alkyl group (carbon number 11~) 15) an ether compound, a polyoxyalkylene alkyl 2 alkyl group (carbon number 12 to 14) ether compound, an alkyl ether compound such as a polyoxyalkylene cetyl ether compound, a polyoxyethylene 'laurylamine ether compound, Polyoxyethylene hard Alkyl amino ether compound such as a fatty amino ether compound, a polyoxyethylene oleyl amine ether compound, a polyoxyethylene laurate decyl ether compound, a polyoxyethylene stearate decyl ether compound, a polyoxyethylene oil An alkylamine ether compound such as an acid hydrazine ether compound, a lauric acid diethanol decylamine compound, a stearic acid diethanol decylamine compound or an oleic acid diethanol decylamine compound, or a polyoxyethylene polystyrene phenyl ether compound, Polyoxyalkylene-51 - (48) 1375861 Alkyl polystyryl phenyl ether compound, polyoxyalkylene polystyryl benzene, methyl ether methamine condensate, polyoxyethylene monostyryl phenyl ether compound , polyoxyethylene distyryl phenyl ether compound, polyoxyethylene naphthalene ether compound, etc. · allyl phenyl ether compound, glycerol monolaurate compound, glycerol mono-hard fat ester compound, glycerin single A glycerin fatty acid ester compound such as an oleate compound or a triolein compound, a sorbitan monolaurate compound, a sorbitan palmitate compound, a sorbitan monostearate compound Φ, a sorbate Sugar alcohol A sorbitan ester compound such as a tristearate compound, a sorbitan monooleate compound, a sorbitan trioleate compound, a polyoxyethylene dilaurate compound, a polyoxyethylene laurate compound a polyoxyethylene stearate compound, a polyoxyethylene distearate compound, a polyoxyethylene dioleate compound, a polyoxyethylene oleate compound, a fatty acid ether ester compound, a polyoxyethylene castor oil ether compound, Polyoxyethylene hardening. Vegetable oil ether ester compound such as castor oil ether compound, polyoxyethylene sorbitan monolaurate compound, polyoxyethylene sorbitan monostearate compound, polyoxyethylene sorbitan A sorbitan ether ester compound such as a monooleate compound or a polyoxyethylene sorbitan trioleate compound, a polyoxyalkylene butyl ether compound, a polyoxyalkylene octyl ether compound, and a polyoxyl a glycol type polyether compound such as a monoalkyl type polyether compound such as a polyalkylene alkyl oleyl ether compound or a polyoxyethylene polyoxypropylene condensate such as an alkylalkyl group (carbon number 14 to 15) ether compound Polyol type polyether compound such as trimethylolpropane tris(polyoxyalkylene ether) ether compound or polyoxyalkylene glyceryl ether compound, methyl laurate compound, methyl oleate compound, isopropyl meat Myristate derivative, butyl stearate compound, octyl palmitate compound-52- (49) 1375861, octyl stearate, lauryl oleate compound, isotridecyl stearate a compound, an oil-based oleate compound, a dioleyl adipate compound, a «* trimethylolpropane tridecanoate compound, a trimethylolpropane trilaurate-compound, a pentaerythritol dioleate compound, a fatty acid alkyl ester compound such as a pentaerythritol monostearate compound or a pentaerythritol distearate compound, an alkylsulfonate compound, a long-chain alkylbenzenesulfonate compound, a branched alkylbenzenesulfonate compound, Long-chain alkyl benzene sulfonate compound, branched alkyl benzene sulfonate compound, branched alkyl diphenyl ether disulfonate compound, monoisopropyl naphthalene sulfonate compound, diisopropyl naphthalene Sulfonate compound, triisopropyl Sulfonic acid type compound such as naphthalenesulfonate compound, dibutylnaphthalenesulfonate compound, dioctylsulfosuccinate compound, oleic acid sulfated oil compound, castor oil sulfated oil compound, octyl sulfate A sulfate compound such as a compound, a lauryl sulfate compound, an alkyl sulfate compound, or an alkyl ether sulfate compound. The preferred concentration of the alkaline developing solution is 0.001 to 10% by mass based on the alkali component and 0.001 to 10% by mass of the surfactant component. When the 鹸 component is too high, the imaging ability is too strong. When it is negative, it will penetrate the unexposed part. When it is positive, it will penetrate the exposed part. It is easy to produce a rough surface pattern. When the alkali component is too low, the imaging ability cannot be obtained. Further, when the surfactant component is too high, blistering is liable to cause smear, and when the surfactant component is too low, the imaging ability cannot be obtained. After development, it is preferably washed with water or a general organic solvent. It is then dried to form a pattern. When a negative resist composition containing a dye is used, a negative pattern in which the exposed portion is hardened and the unexposed portion is dissolved is formed, and when a positive resist composition containing a dye is used, a positive pattern in which the exposed portion is dissolved is formed. -53- (50) 1375861 Change the colors and patterns, and repeat the above-mentioned series of steps only in the necessary number. The color pattern of the combination of the necessary color numbers can be obtained. Further, heating may be performed after the pattern is formed or in order to completely react the polymerizable or condensable functional groups remaining in the pattern (post-baking). The post-baking can be carried out after forming the respective color patterns, or after forming all the coloring patterns, preferably at a temperature of 150 to 5001 for 30 minutes to 2 hours. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Preparation of a negative-type photoresist composition containing a dye) Resin A1: VP80 00 (manufactured by Nippon Soda Co., Ltd.), and the composition is polyvinylphenol. The weight average molecular weight is 8,000 (in terms of polystyrene). _ Resin A2: MARUKA LYNCUR CHM (manufactured by Nippon Petrochemical Co., Ltd.) The composition is a polymer composed of p-vinylphenol/2-hydroxyethyl methacrylate = 50 parts by mass / 50 parts by mass. Weight average score • Sub-quantity 10000 (in terms of polystyrene). Resin A3: a polymer composed of a ratio of vinyl phenol/styrene = 80 parts by mass / 20 parts by mass. The weight average molecular weight is 9000 (polystyrene conversion). Photoacid generator B1 : Formula (70) (Ciba Specialty Chemicals) -54- (51)1375861 [Chem. 39]

Formula (7 0) Photoacid generator B2: Formula (69) (manufactured by Ciba Specialty Chemicals Co., Ltd.)

Photoacid generator B3: Formula (56) TAZ-1 07 (manufactured by Green Chemical Co., Ltd.)

Photoacid generator B4: Formula (67) TAZ-123C Green Chemical Co., Ltd.) [Chem. 42] -55- (52) 1375861 Crosslinkable compound Cl: saimel 303 (methoxymethylated melamine crosslinkable compound) , Japan SCITECH Industrial Co., Ltd. (old three * well SCITECH (share) system). - Crosslinkable compound C2: saimel 370 (methoxymethylated melamine-based cross-linking compound, Japan SCI TECH Industrial Co., Ltd.) (Old Mitsui SCITECH Co., Ltd.). Crosslinkable compound C3: saimel 1170 (butoxymethylated glycoluril #crosslinking compound, Japan SCITECH Industrial Co., Ltd.) (formerly manufactured by Mitsui SCITECH Co., Ltd.). Dye D 1 : Formula (8 9 ) [Chem. 43]

Dye D2: Formula (90) [Chem. 44]

-56- (53) 1375861 Dyes D3: Formula (94) [Chem. 45]

Dye D4: Formula (98) [Chem. 46]

Dye D5: Formula (100) [Chem. 47] + Formula (1 Ο 0)

(C2H5)2N^C^N(C2H5)2 _ ^COOC2H5 〇H -57- (54) (54)1375861 D6: Formula (1 〇1 ) [Chemical 48] ^NJ〇h IW η〇_ν- ^ + N^>-N=N-0-Q^N=N--(^NN(CH3)4 X 2 Formula (1 〇i ) ch3 ch3 D7 : ORASOL Yellow 4GN (Non-metal azo dye) , Ciba S pecia 11 y C hemica 1 s company) Dye D8: Savinyl Scarlet RLS (chromium metal azo dye, manufactured by Clariant Co., Ltd.) Example 1 Resin Al (1.76 g) was placed in a 50 ml eggplant type flask, The dye D1 (1-2 g) and the solvent of propylene glycol monomethyl ether (9.43 g) were stirred at room temperature. No insoluble matter was found in the reaction solution, which was a homogeneous solution. Then, a crosslinkable compound Cl (0.3 g) was added. , photoacid generator Bl (0.2g), surfactant Megafac R-30 (made by Dainippon Ink Chemicals Co., Ltd.) ( 0.009g), and then stirred at room temperature to obtain dye-containing negative resist composition (1) No insoluble matter was found in the solution, which was a homogeneous solution. One part of the solution was filtered using a filter of 〇.2μηι, and placed in a cleaned sample bottle at room temperature for 1 week, visually observed. No foreign matter found The dye-containing negative resist composition (1) was filtered using a filter of 〇.2μηι-58-(55) 1375861, and placed in a cleaned sample bottle for 2 days. Then, the composition was applied. The machine was applied to a ruthenium wafer treated with hexamethyldioxane (hereinafter referred to as HMDS) at 100 ° C for 1 minute, and dried at 110 ° C on a hot plate - lightly burned for 1 minute to form a film thickness of 1. The coating film of 〇3μηι was irradiated onto the coating film by an ultraviolet ray irradiation apparatus PLA-501 (F) (manufactured by CANON Corporation) with an irradiation dose of 600 mJ/cm 2 at a dose of 3 65 nm through a test reticle, followed by 120 ° C. The PEB was allowed to stand for 2 minutes on a hot plate, and then immersed for a certain period of time using a #NMD-3 developing solution (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C, and then washed with ultrapure water. Post-baking on a hot plate at 180 ° C for 5 minutes to form a negative pattern. The resolution of the pattern can be formed within 2 μm of the line/space to form a non-peeling pattern. No foreign matter was observed by visual observation on the film under a sodium lamp, and no foreign matter was observed by observation with an optical microscope. The dye-containing negative resist composition (1) was filtered using a 0.2 μm filter and placed in a cleaned sample bottle for 2 days. Then, the composition ® was applied onto a 5 x 5 cm glass substrate by a spin coater. The film was sintered (light burn) on a heating plate at 115 °C for 2 minutes to form a coating film having a film thickness of 1.06 μm. Ultraviolet irradiation apparatus PLA-501 (F) was used to irradiate the entire surface of the coating film with ultraviolet rays having an irradiation dose of 365 nm of '600 mJ/cm2. The PEB was then carried out on a hot plate at 120 ° C for 1 minute. Then, it was immersed in an NMD-3 developing solution at 23 ° C for a certain period of time for development, and then washed with ultrapure water. Then, post-baking was performed on a hot plate at 180 ° C for 5 minutes to form an orange film (1) having a film thickness of 1. ΟΙμίΏ. The formed orange film (1) was heated at 220 ° C on a hot plate for 1 〇 -59 * (56) 1375861 minutes to obtain an orange film (2). The yellow film (3) was obtained by irradiating the formed orange film (!) with ultraviolet rays of 30,000 m J/cm 2 at an irradiation dose of 365 nm by an ultraviolet irradiation apparatus PLA-501 (F). Example 2 In a 50 ml eggplant type flask, a resin A1 (rug), a dye di (Φ 1 ·72^), a dye D5 (1.55 g), a solvent of 4-hydroxy-4-methyl-2-pentane were placed. Ketone (4.72 g) and propylene glycol monomethyl ether (4-72 g) were stirred at room temperature. No insoluble matter was found in the reaction solution and it was a homogeneous solution. Then 'addition of crosslinkable compound Cl (0.12g), crosslinkable compound C2 (0.15g), photoacid generator B2 (0.12g), surfactant Megafac R-30 (0.01g), and then at room temperature The mixture was stirred to obtain a dye-containing negative resist composition (2). No insoluble matter was found in the solution and it was a homogeneous solution. One part of the solution was oversized with a 0.2 μηη filter. After washing in a sample bottle, it was left at room temperature for 1 week. No foreign matter was observed by visual observation. This dye-containing negative photoresist was composed. The material (2) was filtered using a 0.2 μm filter and placed in the washed sample bottle for 2 days. Then, the composition was applied by a spin coater to a wafer which was treated with HMDS for 1 minute at 10 °C. The film was lightly baked on a hot plate at 120 ° C for 2 minutes to form a coating film having a film thickness of 1.04 μm. The coating film was irradiated with ultraviolet rays of 550 mJ/cm 2 at an irradiation dose of 365 nm through a test mask using an ultraviolet irradiation apparatus PLA-501 (F). -60- (57) 1375861 Next, PEB was applied to the hot plate at 130 ° C for 1 minute. Then, the image was immersed in a NMD-3 developing solution at 23 ° C for a certain period of time, and then washed with ultrapure water 'flowing water. Post-baking was performed on a hot plate at 180 ° C for 5 minutes to form a negative * " pattern. The resolution of the pattern can be formed within 2μΠ1 of the line/space. The stripped pattern. No foreign matter was observed by visual observation under a sodium lamp on the patterned coating film formed on the wafer. No foreign matter was observed by observation with an optical microscope. Example 3 Resin A2 (l_76 g) and dye D1 were placed in a 50 ml eggplant type flask. 0.92 g), dye D5 (1.16 g), solvent 4-hydroxy-4-methyl-2-pentanone (4.72 g) and propylene glycol monomethyl ether (4.72 g) were stirred at room temperature. No insoluble matter was found in the reaction solution and it was a homogeneous solution. Then, a crosslinkable compound Cl (0.15 g), a crosslinkable compound C3 (0.15 g), a photoacid generator B3 (0.2 g), a surfactant, Megafac R-30 (0.012 g), and a room temperature were added thereto. The mixture was stirred to obtain a dye-containing negative resist composition (3). No insoluble matter was found in the solution and it was a homogeneous solution. * One part of the solution was filtered using a filter of 〇.2μιη, and placed in a cleaned sample bottle at room temperature for 1 week. No visible matter was observed by visual observation. This dye-containing negative-type photoresist composition was observed. (3) Filtered using a 0.2 μm filter and placed in the washed sample bottle for 2 days. Then, the composition was applied on a 矽-61 - (58) 1375861 wafer which was treated with HMDS at 100 ° C for 1 minute using a spin coater. Lightly calcined on a hot plate at 120 ° C for 1 minute to form a film having a film thickness of 1.10 μm • Ultraviolet irradiation device PLA-501 (F) via a test mask • Ultraviolet light at 250 mJ/cm 2 at 365 nm Irradiated on the coating film. .- Next PEB was carried out on a hot plate at 120 °C for 1 minute. Then, using a NMD-3 developing solution at 23 ° C for a certain period of time for development, and then washing with ultrapure water, it is post-baked on a hot plate at 180 ° C for 5 minutes to form a negative pattern. . The resolution of the pattern can be formed within 2μηΐ of the line/space to form a pattern that is free of peeling. No visible foreign matter was observed under the sodium lamp on the patterned coating film formed on the wafer. Further, no foreign matter was observed by observation with an optical microscope. Example 4 A resin A3 (1.76 g), a dye D2 (1.65 g), and a solvent of 4·hydroxy-4-methyl-2-pentanone were placed in a 50 ml eggplant type flask. 9.44 g), stirred at room temperature. No insoluble matter was found in the reaction solution, and it was a homogeneous solution. Then, a crosslinkable compound C2 (0.25 g), a photoacid generator B4 (〇.lg), and a surfactant Megafac R-30 (0.01 g) were added, followed by stirring at room temperature to obtain a dye-containing negative light. Blocking composition (4). No insoluble matter was found in the solution and it was a homogeneous solution. One part of the solution was filtered using a 0.2 μηη filter, and placed in a cleaned sample bottle at room temperature for one week. No visible matter was observed by visual observation of the dye-containing negative-type photoresist composition (4) It was filtered using a 0.22 μm filter and placed in a cleaned sample bottle for 2 days. Then, the composition -62-(59) 1375861 was applied by a spin coater at 100 ° C using HMDS for 1 minute on a sand wafer. Lightly burn for 1 minute on a hot plate with 115 art to form a film having a film thickness of Ι.ΟΟμίη. Ultraviolet irradiation apparatus PLA-501 (F) - ultraviolet light having an irradiation amount of 365 nm of 300 mJ/cm 2 was irradiated onto the coating film through a test mask. The PEB was then carried out on a hot plate at 120 ° C for 1 minute. Then, it was immersed in an NMD-3 developing solution at 23 ° C for a certain period of time, and then washed with ultrapure water. Post-baking was performed on a hot plate at 1880 ° C for 5 minutes to form a negative # pattern. The resolution of the pattern can be formed into a non-peeling pattern within 2 μm of the line/space. No visible foreign matter was observed under the sodium lamp on the patterned coating film formed on the wafer. Further, no foreign matter was observed by observation with an optical microscope. Example 5 Into a 5〇1111 eggplant type flask, resin 8.1 (1.768), dye D3 (0.98 g), and solvent 4·hydroxy-4-methyl·2-pentane were placed. Ketone (4.72 g) and propylene glycol® monomethyl ether (4.72 g) were stirred at room temperature. No insoluble matter was found in the reaction solution, and it was a homogeneous solution. Then, a crosslinkable compound Cl (0.25 g), a photoacid generator B3 (0.18 g), and a surfactant Megafac R-30 ( 0.009 g) were added, followed by stirring at room temperature to obtain a dye-containing negative light. Blocking composition (5). No insoluble matter was found in the solution and it was a homogeneous solution. One part of the solution was filtered using a filter of 〇·2 μπι' in the cleaned sample bottle, left at room temperature for 1 week, and visually observed that no foreign matter was found -63- (60) 1375861 The negative photoresist composition (5) was filtered using a 〇.2μηι filter and placed in the washed sample bottle for 2 days. Then, the composition was applied by a spin coater at 100 ° C for 1 minute using HMDS. The film was lightly baked on a hot plate at 120 ° C for 2 minutes to form a coating film having a film thickness of 1 · 8 μm. Ultraviolet irradiation apparatus PLA-501 (F) was irradiated onto the coating film by ultraviolet rays having an irradiation amount of 800 mJ/cm 2 at 3 65 nm through a test mask. The PEB was then carried out on a hot plate at 130 ° C for 1 minute. Then, it was immersed for a certain period of time using an NMD-3 developing solution at 23 ° C, and then washed with ultrapure water. Post-baking was performed on a hot plate at 180 °C for 5 minutes to form a negative pattern. The resolution of the pattern can be formed into a non-peeling pattern within 2 μm of the line/space. No visible foreign matter was observed under the sodium lamp on the patterned coating film formed on the wafer. Further, no foreign matter was observed by observation with an optical microscope. Example 6 • Resin A1 (1.76 g), dye D4 (2.65 g), solvent propylene glycol monomethyl ether (4.72 g), and ethyl lactate were placed in a 50 ml eggplant type flask. The ester (4-72 g) was stirred at room temperature. No insoluble matter was found in the reaction solution, and it was a homogeneous solution. Then, a crosslinkable compound Cl (0.3 g), a photoacid generator B2 (〇·2 g ), a surfactant 1^§& "3〇11-30 ( 0.009§), and then stirred at room temperature A dye-containing negative photoresist composition (6) is obtained. No insoluble matter was found in the solution and it was a homogeneous solution. One part of the solution was filtered using a 0.2 μm filter and placed in a -64 - (61) 1375861 sample bottle after washing for 1 week at room temperature. No foreign matter was observed by the visual observation. The photoresist composition (6) was filtered using a 0.2 μm filter and placed in a cleaned sample bottle at 2 Torr. Then, the composition was applied by a spin coater at a temperature of ° C for 1 minute using HMDS. The film was lightly baked at a temperature of 11 〇° (: on a hot plate for 2 minutes to form a film thickness of 98.98 μm). The ultraviolet ray irradiation apparatus PLA_501 (F) # was irradiated by a test mask to an ultraviolet ray of 800 mJ/cm 2 at a dose of 3 65 nm. The film was irradiated onto the coating film, and then PEB was applied to the hot plate at 130 C for 1 minute, and then immersed in an NMD-3 developing solution at 23 ° C for a certain period of time for development, and then washed with ultrapure water. After baking at 1000 ° C for 5 minutes on a hot plate, a pattern of negative pattern was formed. The resolution of the pattern could be formed within 2 μm of the line/space, and the pattern formed on the wafer was formed on the film. Under the sodium lamp, visual observation: No foreign matter was observed. No foreign matter was observed by optical microscopy. Example 7 Resin A1 (1.76 g), dye D4 (• 2.0 g), and solvent 4 were placed in a 50 ml eggplant type flask. Hydroxy-4-methyl-2-pentanthene (4.72 g) and propylene glycol monomethyl ether (4.72 g) were stirred at room temperature. No insoluble matter was found in the reaction solution, which was a homogeneous solution. Then, crosslinkability was added. Compound Cl (0.3g), photoacid generator B1 (0.2g), surfactant] ^§3£3〇 11-30 (0.015 £), and then stirred at room temperature to obtain a dye-containing negative resist composition (7). In solution -65- (62) 1375861 No insoluble matter was found, which was a homogeneous solution. Part of the filter was filtered using a filter of 〇·2μηι, and placed in a sample bottle for 1 week at room temperature. No foreign matter was observed by visual observation. 9·Μ 〇. This dye-containing negative resist The composition (7) was filtered using a 0.2 μm filter and placed in a cleaned sample bottle for 2 days. Then, the composition was applied by a spin coater at 1 ° C for 1 minute using HMDS.矽 φ on the wafer, lightly burned on a hot plate at 120 ° C for 2 minutes to form a coating film with a film thickness of 1.03 μm. The irradiation of the ultraviolet ray irradiation device PLA-501 ( F ) through the test mask was 3 65 nm. Ultraviolet light of 750 mJ/cm 2 was irradiated onto the coating film. Next, PEB was applied to the hot plate at 130 ° C for 1 minute, and then immersed in an NMD-3 developing solution at 23 ° C for a certain period of time for development, and then The ultrapure water was washed with water and post-baked on a hot plate at 180 ° C for 5 minutes to form a negative pattern. A pattern of no peeling can be formed within 2 μm of the resolution line/space. The pattern coating film formed on the wafer is visually observed under a sodium lamp. Φ No foreign matter is observed. In addition, no foreign matter is observed by optical microscopy. The negative photoresist composition (7) was filtered using a 〇.. 2μηι filter and placed in a cleaned sample bottle for 2 days. Then, the composition was applied to a 5x5 cm glass substrate by a spin coater. . The film was lightly baked at 120 ° C for 2 minutes on a heating plate to form a film having a film thickness of 1.06 μm. Ultraviolet irradiation apparatus PLA-501 (F) was irradiated onto the entire surface of the coating film with ultraviolet rays having an irradiation amount of 750 nm of 75 0 mJ/cm 2 . The PEB was then carried out on a hot plate at 30 ° C for 1 minute. Then, it was immersed in an NMD-3 developing solution at 23 ° C for a certain period of time - 66 - (63) 1375861 for development, and then washed with ultrapure water. Then, post-baking was carried out on a hot plate at 1 8 ° C for 5 minutes to form a red film (4) having a film thickness of 0.98 μm. • The formed red film (4) was heated on a hot plate at 220 ° C for 10 minutes to obtain a red film (5). A red film (6) was obtained by irradiating the formed red film (5) with ultraviolet rays having an irradiation amount of 300 nm at 300 nm to a red film (5) of 3,500 mJ/cm 2 by an ultraviolet irradiation device PLA-501 (F). Comparative Example 1 Resin Al (1.76 g), dye D6 (1.92 g), solvent 4-hydroxy-4-methyl-2-pentanone (4.72 g), and propylene glycol monomethyl ether were placed in a 50 ml eggplant type flask ( 4.72 g), stirred at room temperature. No insoluble matter was found in the reaction solution, and it was a homogeneous solution. Then, a crosslinkable compound Cl (0.3 g), a photoacid generator B1 (0.2 g), a surfactant 1^§& £3〇11-30 (0.01§), and then stirred at room temperature. A dye-containing negative photoresist composition (8) is obtained. No insoluble matter was found in the solution, and a solution of the same sentence was obtained. * One part of the solution was filtered using a filter of 〇·2 μηι, and placed in a cleaned sample bottle at room temperature for 1 week. No visible matter was observed by visual observation. The material (8) was filtered using a 0.2 μm filter and placed in the washed sample bottle for 2 days. Then, the composition was applied by a spin coater at 1 ° C for 1 minute on the wafer using HMDS. The film was lightly baked at 12 ° C for 2 minutes on a hot plate to form a film having a film thickness of ΐ. 7 μπΐ -67- (64) 1375861. The coating film was irradiated with ultraviolet rays of 650 m:i/cm 2 at an irradiation dose of 365 nm through an ultraviolet ray irradiation apparatus PLA-501 (F) through a test reticle. Next, PEB was allowed to stand on a hot plate at 130 ° C for 1 minute. Then, use a " 23 ° C NMD-3 imaging solution for a certain period of time for imaging, and then washed with ultra-pure water, running water. Post-baking was performed on a hot plate at 180 ° C for 5 minutes to form a negative pattern. The resolution of the pattern can be formed into a non-peeling pattern within 3 μm of the line/space. The pattern coating film formed on the wafer was visually observed under a sodium lamp. φ No foreign matter was observed. Further, no foreign matter was observed by observation with an optical microscope. The negative photoresist composition (8) containing the dye was filtered using a 0.2 μm filter and placed in a cleaned sample bottle for 2 days. Then, the composition was applied onto a 5 x 5 cm glass substrate by a spin coater. The film was lightly baked at 120 ° C for 2 minutes on a heating plate to form a coating film having a film thickness of 1.05 μπ. Ultraviolet irradiation apparatus PLA-501 (F) was irradiated onto the entire surface of the coating film with ultraviolet rays having an irradiation amount of 650 mJ/cm 2 at 365 nm. Next, a PEB of #1 minute was applied to the hot plate at 130 °C. Then, it was immersed in an NMD-3 developing solution at 23 ° C for a certain period of time for development, and then washed with ultrapure water. Then, post-baking was performed on the hot plate ' at 80 ° C for 5 minutes to form a yellow film (7) having a film thickness of Ι.ΟΟμηη. The formed yellow film (7) was heated at 22 (TC on a hot plate for 10 minutes to obtain a red film (8). Ultraviolet irradiation device PLA-501 (F) was irradiated with ultraviolet rays of 300 mJ/cm 2 at 3 65 nm. Irradiation on the formed yellow film (7) gave a yellow film (9). -68- (65) 1375861 Comparative Example 2 In a 5-1111 eggplant type flask, resin 8.1 (1.768) and dye D7 (2.0 g) were placed. Solvent 4-hydroxy-4-methyl-2-pentanone (4.72g) and propylene glycol** monomethyl ether (4.72g) were stirred at room temperature. No insoluble matter was found in the reaction solution, which was uniform. Then, add cross-linking compound Cl (0.3g), photoacid generator B1 (〇.2£), surfactant 1^8 to 3(:11-30(0.01(^), then to room® Stirring under temperature to obtain a dye-containing negative resist composition (9). No insoluble matter was found in the solution, and a uniform solution was obtained. One part of the solution was filtered using a 0.2 μηι filter, and the sample was washed. The bottle was allowed to stand at room temperature for 1 week, and no foreign matter was observed by visual observation. This dye-containing negative-type photoresist composition (9) was filtered using a 0.2 μηι filter. The sample was placed in the cleaned sample bottle for 2 days. Then, the composition was applied by a spin coater at 10,000 ° C for 1 minute using HMDS, and heated at 120 ° C. The plate was lightly burned for 2 minutes to form a coating film having a film thickness of 1.04 μ. The ultraviolet ray irradiation apparatus PLA-501 (F) was irradiated onto the coating film by ultraviolet rays having an irradiation amount of 70 〇mJ/cm 2 at 3 65 nm through a test mask. Then, carry out PEB for 1 minute on a hot plate at 130 ° C. Then, immerse it in a NMD-3 developing solution at 23 ° C for a certain period of time, and then wash it with ultrapure water. At 180 ° C Post-baking on a hot plate for 5 minutes to form a negative pattern. The resolution of the pattern can be formed into a non-peeling pattern within 3 μm of the line/space. The patterned coating film formed on the wafer is visually observed under a sodium lamp. Foreign matter was found. No foreign matter was observed by optical microscopy -69- (66) 1375861 The negative resistive composition (9) containing the dye was filtered using a filter of 〇.2μηι, in the washed sample bottle. Place for 2 days. Then, the composition was coated with a spin coater. On a glass substrate of 5 x 5 cm, it was lightly baked on a hot plate at 120 ° C for 2 minutes to form a coating film having a film thickness of 1.05 μm. Ultraviolet irradiation apparatus PLA-501 (F) was irradiated with ultraviolet rays of 370 nm at 700 mJ/cm 2 . Irradiated on the coating film. Then, the PEB of #1 minute was carried out on a hot plate at 130 ° C. Then, it was immersed for a certain time for development with an NMD-3 developing solution at 23 ° C, and then flowed with ultrapure water. Wash. Then, post-baking was performed on a hot plate at 1880 ° C for 5 minutes to form a yellow film of film thickness (( ΐ ΐ ΐ 〇) 〇 The yellow film (10) to be formed was subjected to a hot plate at 220 ° C for 10 minutes. Heating to obtain a red film (1 1 ). Ultraviolet irradiation apparatus PLA_501 (F) was irradiated with ultraviolet rays of 300 nm to 300 mJ/crn2 on the formed yellow film (1 Å) to obtain a yellow film (12). Reference Example 1 Resin A1 (1.76 g), dye D8 (2.0 g), solvent 4-hydroxy-4-methyl-2-pentanone (4.72 g) and propylene glycol monomethyl ether were placed in a 50 ml eggplant type flask ( 4.72 g), stirred at room temperature. No insoluble matter was found in the reaction solution, and it was a homogeneous solution. Then, a crosslinkable compound Cl (0_3g), a photoacid generator B1 (〇.2g), a surfactant 1^83 [&〇11-30 (0_0108), and then a chamber-70-(67) 1375861 were added. Stirring under temperature to obtain a dye-containing negative resist composition (10) » No insoluble matter was found in the solution, and a uniform solution was obtained. ' One part of the solution was filtered using a 0.2 μηη filter. After washing in a sample bottle, it was left at room temperature for 1 week. No foreign matter was observed by visual observation. 〇 This dye-containing negative-type photoresist composition was used. (10) Filtered using a 0.2 μm filter and placed in a cleaned sample bottle for 2 days. Then, the composition Φ was applied by a spin coater to a ruthenium wafer treated with HMDS for 1 minute at 10 °C. The film was lightly baked on a hot plate at 125 ° C for 2 minutes to form a coating film having a film thickness of 1.04 μm. The coating film was irradiated with ultraviolet rays having an irradiation amount of 365 nm of 700 m: T/cm 2 through a test reticle by an ultraviolet ray irradiation apparatus PL A-501 (F). The PEB was then carried out on a hot plate at 130 ° C for 1 minute. Then, it was immersed in a 23T NMD_3 developing solution for a certain period of time for development, and then washed with ultrapure water. Post-baking was performed on a hot plate at 180 ° C for 5 minutes to form a negative pattern. The resolution of the pattern can be formed within 3μιη of the line/space to form a pattern without a peeling of the ®. No visible foreign matter was observed under the sodium lamp on the patterned coating film formed on the wafer. In addition, no foreign matter was observed by observation with an optical microscope. • The negative resist composition (10) containing the dye was filtered using a 0.2 μm filter and placed in the cleaned sample bottle for 2 days. Then, the composition was applied onto a 5 x 5 cm glass substrate by a spin coater. The film was lightly baked at 125 ° C for 2 minutes on a hot plate to form a coating film having a film thickness of 1·〇5 μm. The entire surface of the coating film was irradiated with ultraviolet rays having an irradiation amount of 700 mJ/cm 2 at a wavelength of 3 65 nm by an ultraviolet irradiation apparatus PLA-501 (F). Next, enter -71 - (68) 1375861 for 1 minute PEB on a hot plate at 130 °C. Then, it was immersed in an NMD-3 developing solution at 23 ° C for a certain period of time for development, and then washed with ultrapure water. Then, post-baking was performed on a hot plate at 1 80 r for 5 minutes to form a yellow film (13) of film thickness .. 黄色μηΐ. The formed yellow film (13) was heated at 220 ° C for 10 minutes on a hot plate. , obtaining a red film (14) ^ using an ultraviolet irradiation device PLA-501 (F) at an irradiation dose of 365 nm, and irradiating ultraviolet rays of 3 〇〇m J/cm 2 on the formed yellow film (14) to obtain a yellow film (1 5 ). The spectroscopic spectrum was measured using a Shimadzu self-recording spectrophotometer (UV-3100PC) (manufactured by Shimadzu Corporation) to measure the transmittance at a wavelength of 350 nm to 3 70 nm. The obtained colored films (1) to (15) were subjected to spectroscopic measurement, and the transmittances at 400 nm and 500 nm and their rates of change were measured as shown in Tables 1 to 1〇. These measurement wavelengths are selected because the coloring film is likely to have a wavelength at which the transmittance is changed. The rate of change is the degree of change in the transmittance of the formed colored film and the transmittance at the time of reheating treatment or ultraviolet irradiation of the colored film. The larger the 値, the greater the change in heating or ultraviolet treatment. Table 1 (Transmittance and rate of change) Colored film\wavelength 4 0 0 nm 5 OOnm Orange film (1) 7.64 5.03 Orange film (2) 7.33 5.28 Rate of change (%) 4.06 4.73 -72- (69) 1375861 Table 2 ( Transmittance and rate of change) 'Colored film\wavelength 400nm 5 OOnm - Orange film (1) 7.64 5.03 Yellow film (3) 7.55 5.18 Rate of change (%) 1.18 2.90 ® Table 3 (transmittance and rate of change) Colored film\wavelength 400nm 5 0 0 nm Red film (4) 5.43 3.7 1 Red film (5) 5.25 3.90 Rate of change (%) 3.3 1 4.87 Table 4 (Transmittance and rate of change) Colored film\wavelength 400nm 5 0 0 nm • Red film (4) 5.43 3.7 1 Red film (6) 5.38 3.80 Rate of change (%) 0.92 2.37 Table 5 (Transmittance and rate of change) Colored film\wavelength 4 0 Onm 5 OOnm Yellow film (7) 1.2 1 56.3 6 Red film (8) 1.99 63.3 5 Rate of change (%) 39.20 11.03 -73- (70) 1375861 Table 6 (Transmittance and rate of change) . Colored film\wavelength 4 0 Onm 5 OOnm * - Yellow film (7) 1.2 1 56.36 Yellow film (9) 1.3 8 6 1.67 Rate of change (%) 12.32 8 .6 1 #表7 (Transmittance and rate of change) Colored film\wavelength 4 0 Onm 5 00nm Yellow film (10) 1.45 57.15 Red film (1 1) 2.12 65.33 Rate of change (%) 3 1.60 12.52 Table 8 (Transmission rate) And its rate of change) Colored film\wavelength 4 OOnm 500nm Yellow film (10) 1.45 57.15 Yellow film (12) 1.60 6 1.24 Rate of change (%) 9.38 6.67 Table 9 (transmittance and rate of change) Colored film\wavelength 4 0 Onm 5 OOnm yellow film (13) 19.19 2.4 red film (14) 18.58 2.3 rate of change (%) 3.18 4.17 -74- (71) 1375861 Table 10 (transmittance and rate of change) colored film\wavelength 4 0 Onm 5 OOnm yellow film ( 13) 19.19 2.4 Yellow film (1 5) 19.02 2.43 Rate of change (%) 0.88 1.23 • [Industrial use] The photoresist composition of the present invention can be applied to the thinning of a color filter 'When the dye concentration is increased It can also display high refraction spectrum reproducibility, high heat resistance and light resistance' and has a high resolution of 5 μηι or less, and has no visible color resist composition and can be applied to use these color photoresists. Object The color filter.

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Claims (1)

137-5861 Patent Application No. 094136554 Patent Application Revision of the Chinese Patent Application Revision of the Republic of China on June 15th, 2011. Patent Application No. 1 - A photoresist composition characterized by containing the following cobalt-containing salt dyes A compound containing a cation and an anion having a compound capable of forming a salt of a wrong salt, the cation system (3): [Chemical Formula 3] Formula (3) R\ +^R3 C-N〆R2/ ^ R4 (but R1, R2, R3 and R4 each independently represent a hydrogen atom or an organic group) 〇2. The photoresist composition of claim 1 wherein the compound having the ability to form a salt of a wrong salt dye is A dihydroxy azo structure represented by the following formula (1), [Chemical Formula 1] HO-XN=NX-OH Formula (1) (However, X represents an organic group derived from a substituted or unsubstituted ring compound) 〇3 A photoresist composition according to claim 1 or 2, wherein the compound having the ability to form a salt of a wrong salt dye is a pyrazole azo structure represented by the following formula (2), 1375861 1 (1 1. t>. Year, Month, Day Correction & Stomach [Chemical 2] N=N_ 2) 4. The photoresist composition according to claim 1, wherein the compound having a salt-forming ability is a sulfonic acid group or a carboxyl group. 5. The photoresist composition according to claim 1, wherein The wrong salt dye is a ratio containing: a compound having a ability to form a salt with a wrong salt (Ming): (a compound having a salt-forming ability) having an anion ratio of 1:2. 6 · As claimed in the patent scope 1 The photoresist composition of the item, wherein at least one of R1 and R2 in the formula (3) is a nitrogen-containing organic group. 7 · The photoresist composition of the first aspect of the patent application, wherein R1 in the formula (3) At least one of R2 has a quinone imine structure (-NH-R5). 8. The photoresist composition of claim 7, wherein R5 is a substituted or unsubstituted aromatic group. A photoresist composition according to the item 1, wherein at least one of R3 and R4 in the formula (3) is a hydrogen atom. 10. The photoresist composition according to claim 6 wherein the cation of the stray salt dye is as follows ( 4) Representation, [Chemical 4] R R Formula (4) 137-5861 H 1 June 1 replacement page (but R is a hydrogen atom or a methyl group). Η · A photoresist composition characterized by: resin (A), photoacid generator or photobase generator (Β), crosslinkable compound (C), and claims 1 to 10 of the patent application A dye (D) and a solvent (Ε). A method for producing a color filter, comprising: applying a photoresist composition according to any one of claims 1 to 11 on a substrate, drying, exposing, and then developing step. A liquid crystal display device comprising a color filter manufactured by the method of claim 12 of the patent application. 14. An LED display device characterized by comprising a color filter manufactured by the method of claim 12 of the patent application. A solid-state imaging device characterized by comprising a color filter manufactured by the method of claim 12