WO2008032736A1

WO2008032736A1 - Dye-containing resist composition containing photoacid generator, and cyclohexadiene-type oxime sulfonate compound

Info

Publication number: WO2008032736A1
Application number: PCT/JP2007/067726
Authority: WO
Inventors: Hideo Suzuki; Tomoe Miyazawa; Takamasa Kikuchi
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-09-13
Filing date: 2007-09-12
Publication date: 2008-03-20
Also published as: JP2009282052A; TW200832054A

Abstract

[PROBLEMS] To provide a dye-containing resist composition which can provide a color filter suppressed in the coloration at the visible region (400 to 730 nm). [MEANS FOR SOLVING PROBLEMS] A dye-containing resist composition containing a photoacid generator comprising a cyclohexadiene-type oxime sulfonate compound represented by the formula [1]. [1] wherein R1, R2, R5, R6 and R7 independently represent a hydrogen atom, a halogen atom, CN, NO2, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or the like; R3 represents a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or the like; R4 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, or the like; and W represents a halogen atom, CN, an alkyl group having 1 to 10 carbon atoms, or the like; and n represents an integer of 1, 2, 3 or 4.

Description

Specification

Dye-containing resist composition containing photoacid generator and cyclohexagen-based oxime sulfonate compound

Technical field

The present invention relates to a dye-containing resist composition containing a photoacid generator and a cyclohexagen-based oxime sulfonate compound. More specifically, the present invention relates to a dye-containing composition containing a photoacid generator corresponding to i-line (365 nm). The present invention relates to a resist composition.

Background art

[0002] A color filter for an image sensor such as a charge coupled device (CCD) or a liquid crystal display device (LCD) is capable of producing a high-definition color filter mainly because a fine pattern can be formed. Therefore, it is produced 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. After coating the film on a substrate, the colored layer is patterned and developed by a photolithography method to form a single colored pattern. Then, this process is repeated for each color to produce a color filter.

In this case, pigments that are excellent in heat resistance and light stability are generally used as the coloring agent used as the colorant, and resists in which pigments are dispersed have been proposed. For example, there is disclosed a photosensitive colored resin composition comprising a resin material that can be hardened by an acid, a photoacid generator, and a pigment (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 size of several tens of nm! / And several hundreds of nm, the pigment itself becomes a foreign substance, or the dispersion is not stable and causes aggregation. There was a problem. For this reason, using conventional pigments makes it difficult to produce color filters for CCDs that require high resolution.

On the other hand, when a dye is used as a pigment, a uniform resist composition can be obtained because the dye is soluble in an organic solvent. Therefore, a resist composition in which pigments are dispersed It is possible to form a fine pattern as compared with an object. For example, a negative resist composition comprising a resin curable with an acid, a crosslinking agent, a photoacid generator, a dye and a solvent is disclosed (for example, Patent Document 2).

In addition, a resist-added dye for a color filter that 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 and 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).

Also disclosed is an ink composition containing a reaction mixture of a water-soluble dye having active hydrogen, an epoxy compound, and an amine as a colorant. It is described that these are used for writing instruments, printing, recording, stamping, and paper coloring (for example, Patent Document 5). As a photoacid generator! /, An oxime sulfonate compound that has an excellent absorption coefficient (photosensitivity) for g-line, h-line and i-line, and excellent solubility in solvents. It is known (for example, Patent Document 6).

Recently, a dye-containing resist composition using a thiophene-based oxime sulfonate compound has been found, and it has been reported that a thin film can be formed when a color filter is produced (for example, Patent Document 7). ).

Patent Document 1: Japanese Patent Laid-Open No. 4 163552

Patent Document 2: Japanese Patent Laid-Open No. 6-51514

Patent Document 3: JP-A-6-51115

Patent Document 4: JP-A-60-229953

Patent Document 5: Japanese Patent Laid-Open No. 61-203182

Patent Document 6: Special Table 2002-508774

Patent Document 7: International Publication No. 2006/046398 Pamphlet

Disclosure of the invention Problems to be solved by the invention

[0004] A dye-containing resist composition using a thiophene oxime sulfonate compound as a photoacid generator is colored by exposure and subsequent heat treatment. Have it!

The present invention has been made in view of such circumstances, and an object thereof is to provide a dye-containing resist composition that provides a color filter in which coloring in the visible region (400 nm to 730 nm) is suppressed.

Another object of the present invention is to provide a photoacid generator that is excellent in sensitivity to active light used for exposure, in particular, sensitivity to i-line (365 nm), has little coloration by exposure and subsequent heat treatment, and can produce a resist. To do.

Means for solving the problem

As a result of intensive investigations to achieve the above object, the present inventors have found that a dye-containing resist composition containing a cyclohexagen-based oxime sulfonate compound as a photoacid generator. In addition, among the cyclohexagen-based oxime sulfonate compounds, the maximum absorption wavelength of the compound having a 2,6-substituted phenyl group almost coincides with the i-line wavelength of 365 nm. The present inventors have completed the present invention by finding that a resist produced using the resist has high light transmittance and little coloring.

That is, the present invention provides:

1. Formula [1]

[Chemical 1]

(Where

R ² , R ⁵ , R ⁶ and R ′ are each independently a hydrogen atom, a halogen atom, CN, NO, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Represents a haloalkyl group having 1 to 5 carbon atoms or a haloalkoxy group having 1 to 5 carbon atoms,

R ³ represents a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. When 1 represents a haloalkoxy group of 1 to 5 and n represents 2 3 or 4, each R ³ may be the same as or different from each other, and when R ³ is adjacent The two adjacent R ³ groups are — CH CH —CH O— — CH N (R ⁸ ) — — CH CH CH —CH CH O— CH CH N (R CH CH CH CH —CH CH CH O— — By forming CH CH CH N (R CH CH CH CH CH CH CH CH CH O— or one CH CH CH CH N (R ⁸ ) —, a four-membered ring with the carbon atom to which each of the two R ³ bonds is attached. , 5-membered ring or 6-membered ring may be formed

R ⁴ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms,

Substituted with W! /, May! /, Phenyl group, substituted with W! /, May! /, Naphthyl group or substituted with W! /, May! /, Anthranyl group Represents

R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

W is a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, or the number of carbon atoms

An alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 carbon atom and 5 haloalkoxy groups,

n represents an integer of 1 2 3 or 4. )

A dye-containing resist composition comprising a photoacid generator comprising a cyclohexadiene oxime sulfonate compound represented by:

2. R ⁵ to R ⁷ are all hydrogen atoms, and R ¹ and R ² are each independently a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. The dye-containing resist composition according to 1, which is an alkoxy group having 5 or 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms,

3. The dye-containing resist composition according to 2, wherein R ¹ and R ² are halogen atoms, 4. The dye-containing resist composition according to 3, wherein the halogen atom is a chlorine atom,

5. The dye-containing resist composition according to any one of 1 to 4, wherein R ³ is a hydrogen atom

6. A photoacid generator (A), a resin (B), a crosslinkable compound (C), a dye (D) and a solvent (E) comprising a cyclohexadiene oxime sulfonate compound represented by the above formula [1]. Dye-containing resist composition containing

7. The dye (D) is represented by the formula [2]

[Chemical 2]

(Wherein R ⁹ to R ¹² each independently represents a hydrogen atom or an organic group). The dye-containing resist composition according to 6, which comprises a cationic compound represented by:

8. The dye-containing resist composition according to 7, wherein the dye (D) contains an anion compound which is a counter ion of the cationic compound represented by the formula [2].

9. The dye-containing resist composition according to 8, wherein the anionic compound is a compound having a phthalocyanine structure,

10. The dye-containing resist composition according to 8, wherein the anionic compound is a compound having a pyrazole azo structure,

11. The dye-containing resist composition according to 8, wherein the anionic compound is a compound having a pyrazole azo structure and a metal complex structure,

12. The dye-containing resist composition according to 8, wherein the anionic compound is a compound having a xanthene structure,

13. A method for producing a color filter comprising the steps of: applying one dye-containing resist composition onto a substrate, drying, exposing and developing;

14. A liquid crystal display device including a color filter manufactured by 13 methods,

15. LED (light emitting diode) display device including color filters manufactured by 13 methods Place

16. A solid-state imaging device including a color filter manufactured by 13 methods,

17. Formula [3]

[Chemical 3]

(Wherein R ¹ and R ² are each independently a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or Represents a haloalkyl group or a haloalkoxy group having 1 to 5 carbon atoms,

R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

W is a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, or the number of carbon atoms An alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 carbon atom and 5 haloalkoxy groups,

n represents an integer of 1 2 3 or 4. )

A cyclohexadiene oxime sulfonate compound represented by the formula:

18. The cyclohexadiene oxime sulfonate compound according to 17, wherein R ¹ and R ² are each independently a halogen atom,

19. The cyclohexadiene oxime sulfonate compound according to 18, wherein the halogen atom is a chlorine atom,

20. The power of 17 to 19, wherein R ³ is a hydrogen atom, one cyclohexadiene oxime sulfonate compound,

21. Equation [4]

[Chemical 4]

R ³ represents a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. When 1 represents a haloalkoxy group of 1 to 5 and n represents 2 3 or 4, each R ³ may be the same as or different from each other, and when R ³ is adjacent The two adjacent R ³ groups are — CH CH —CH O— — CH N (R ⁸ ) — — CH CH CH —CH CH O— CH CH N (R CH CH CH CH —CH CH CH O— — By forming CH CH CH N (R CH CH CH CH CH CH CH CH CH O—or one CH CH CH CH N (R ⁸ ) — A 4-membered ring, a 5-membered ring or a 6-membered ring may be formed together with the carbon atom to which each R ³ is bonded.

R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

n represents an integer of 1, 2, 3 or 4. )

A cyclohexadiene oxime compound represented by:

22. A photoacid generator comprising a cyclohexadiene oxime sulfonate compound represented by the formula [3],

23. An i-line photoacid generator comprising a cyclohexadiene oxime sulfonate compound represented by the formula [3]

I will provide a.

The invention's effect

The dye-containing resist composition of the present invention is less colored by exposure and subsequent heat treatment, thereby making it possible to improve the characteristics of the color filter. In addition, a color filter having high heat resistance and light resistance can be produced by the interaction between the phenolic resin and the dye. 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 from 0.3 to 1.5 111, the dye concentration in the resist composition must be 30% by mass or more. The resist composition containing the dye molecule and the color filter produced from the resist composition have a region exhibiting a transmittance of 70% or more and a wavelength of 10% or less in the wavelength region of 400 to 700 nm due to the dye molecule. And an optical characteristic having at least a region exhibiting transmittance. When the dye concentration is low and this transmittance value is shown, sufficient force S, heat resistance, and light resistance cannot be ensured because the number of dye molecules per unit volume is small. 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 desired optical characteristics, and sufficient resolution and adhesion cannot be ensured. Therefore, the dye-containing resist composition of the present invention has a region showing a transmittance of 70% or more and a region showing a transmittance of 10% or less in the visible region (400 nm to 730 ηm), particularly 400 to 700 nm. It contains at least a dye exhibiting a spectral spectrum. 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 preferable that the region does not show absorption, and that the region inhibits absorption of other dyes! When each dye has absorption in a region that does not inherently exhibit absorption, the heat resistance or light resistance of the dye is insufficient. The 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 has a transmittance in a region showing no absorption.

It is 70% or more, and it is possible to obtain a clear color finisher by expressing the target spectrum. The photoacid generator comprising the cyclohexadiene oxime sulfonate compound 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.

In addition, the cyclohexagen-based oxime sulfonate compound having a 2,6-substituted phenyl group according to the present invention has a maximum absorption wavelength almost coincident with the i-line wavelength of 365 nm, and the resist produced using the compound is colored. Has a high light transmittance.

By using a color filter obtained by coating the dye-containing resist composition of the present invention on a substrate, curing, exposing, and developing, it is possible to produce an image sensor with high device sensitivity.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] Hereinafter, the present invention will be described in more detail.

The dye-containing resist composition according to the present invention contains a photoacid generator composed of a cyclohexagen-based oxime sulfonate compound represented by the formula [1].

In the above formula [1], R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a nitrogen atom, CN, NO, or an alkyl having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, R ³ represents a hydrogen atom, a halogen atom, a nitro group, or a CN group Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms or a haloalkoxy group having 1 to 5 carbon atoms, and n is 2, 3 or 4 represents each R ³ may be the same or different from each other. In addition, when R ³ is adjacent, two adjacent R ³ are CH ₂ CH ₂ --CH O CH N (R ⁸ )--CH CH CH CH CH O CH CH N (R ⁸ DOO, -CH CH CH CH -CH CH CH O CH CH CH N (RCH CH CH CH CH CH CH CH CH O or by forming a ^{CH CH CH CH N (R 8} ), each of the two R ³ May form a 4-membered ring, a 5-membered ring or a 6-membered ring with the carbon atom to which R is bonded. R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is 1 2 3 Or represents an integer of 4.

[0010] Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, an n-amyl group, an i-aminole group, s Amino group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n propoxy group, an i propoxy group, an _n -butoxy group, and an n amyloxy group. A haloalkyl group having 1 to 5 carbon atoms Specific examples thereof include trifluoromethyl group, pentafluoroethyl group, perfluoro n propyl group, perfluoro n butyl group, perfluoro n amyl group and the like.

Specific examples of the haloalkoxy group having 1 to 5 carbon atoms include trifluoromethoxy group, pentafluoroethoxy group, perfluoro n propoxy group, perfluoro n butoxy group, perfluoro n amyloxy group, and the like.

[0011] Among the above substituents, considering the sensitivity to i-line (365 nm) and the light transmittance of a resist prepared from the dye-containing resist composition, R ⁵ R ⁶ and R ⁷ are all hydrogen atoms. Some force S Preferably, R ¹ and R ² are each independently a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. R ³ is preferably a hydrogen atom, preferably a haloalkyl group of 5 or a haloalkoxy group of 1 to 5 carbon atoms. Furthermore, it is more preferable that R ¹ and R ² are each independently a halogen atom or a halogen atom, preferably an alkyl group having 1 to 10 carbon atoms.

Specifically, R ¹ and R ² are each independently a chlorine atom or a methyl group, and more preferably a chlorine atom.

[0012] In the formula [1], R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or 1 carbon atom. To 5 haloalkoxy groups, a phenyl group that may be substituted with W, a naphthyl group that may be substituted with W, or an anthranyl group that may be substituted with W; W is a halogen atom, CN , NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms.

Specific examples of the halogen atom, the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, and the haloalkoxy group having 1 to 5 carbon atoms include the above R ¹ to R ³ and Examples thereof are the same as those described for R ⁵ to R ⁸ .

Specific examples of the phenyl group which may be substituted with W include a phenyl group, o-tolyl group, m-trinole group, p-trinole group, o-ethino-lefinino group, m-ethino-lefinenole group. P- (ethyl) phenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- ( s-butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl Enyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- ( i-propoxy) phenyl, p- (n-butoxy) phenyl P- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-amyloxy) phenyl Group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2, 4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4— Difluorophenyl group, 2, 4, 6-dichlorophenyl group, 2, 4, 6-trifluorophenyl group, 2, 4, 6-trifluorophenyl group, pentachlorophenyl group, pen tab A lomophenyl group, a pentafluorophenyl group, a p-biphenylyl group, and the like.

Specific examples of the naphthyl group which may be substituted with W include 1 naphthyl group, 2-naphthinole group, 2-methyl-1 naphthyl group, 3-methyl-1 naphthyl group, 4-methynole 1 naphthyl group, 5 methyl-1 naphthyl group Group, 6 methyl-1 naphthyl group, 7 methyl 1 naphthyl group, 8 methyl-1 naphthyl group, 1-methyl-2 naphthyl group, 3-methyl-2 naphthyl group, 4-methyl-2 naphthyl group, 5 methyl-2 naphthyl group, 6 methyl-2 naphthyl group 7 methyl-2-naphthyl group, 8 methyl-2-naphthyl group and the like.

Specific examples of the anthranyl group which may be substituted with W include 1 anthranyl group, 2 anthranyl group, 2-methyl-1 anthranyl group, 3-methyl-1 anthranyl group, 4-methyl-1 anthranyl group, 5-methyl-1 anthranyl group 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1-anthranyl group, 1-methyl-2-anthranolin group, 3-methyl-2-anthranyl group, Examples include 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group, and 10-methyl-2-anthranyl group.

[0014] Among the above substituents, in consideration of the light transmittance of the resist prepared from the dye-containing resist composition, R ⁴ is substituted with an alkyl group having 1 to 10 carbon atoms or W and V 4 It is preferably a phenyl group, more preferably a W substituted! /, Or even a phenyl group. Here, W is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms.

Specifically, R ⁴ is more preferably a phenyl group or a p-tolyl group, preferably a methinole group, an ethyl group, an n-propyl group, a phenyl group, a p-trinole group, or a pentafluorophenyl group. .

[0015] Specific examples of the photoacid generator comprising the cyclohexadiene oxime sulfonate compound represented by the formula [1] include the following compounds.

[Chemical 5]

The dye-containing resist composition of the present invention includes a negative type (negative type) resist and a positive type.

It can be applied to (positive type) resist.

Preferably, the dye-containing resist composition of the present invention comprises a photoacid generator (A), a resin (B), a crosslinkable compound (A) comprising a cyclohexagen oxime sulfonate compound represented by the above formula [1] A negative resist composition containing C), a dye (D), and a solvent (E). In the negative resist composition, the photoacid generator (A) to be used is one that generates an acid directly or indirectly by light irradiation.

The photoacid generator (A) can be used alone or in combination of two or more thereof. The amount introduced is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the resin (B) component. Is selected in the range of 20 to 200 parts by weight. When this amount is less than 1 part by mass, the bridge reaction does not proceed sufficiently, and it is difficult to obtain a desired resist pattern, and when it exceeds 300 parts by mass, the storage stability of the resist composition is poor.

[0017] The resin (B) 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, heat or light irradiation. If it is a photosensitive resin that crosslinks more and the coating film of the unexposed part in the resin can be removed by a developing solution, it is not particularly limited.

[0018] Examples of the resin (B) include resins having a hydroxyl group or a carboxyl group, for example, acrylic resins such as polybulal alcohol, polyacrylamide, polyacrylic acid, and polymethacrylic acid, polyamic acid, and polybuhlphenol. Derivatives thereof and copolymers thereof, copolymers of polymetatalylate and maleic anhydride, phenol resins, novolak resins, polyimides containing hydroxyl groups and / or carboxyl groups, cellulose, cellulose derivatives, starches, Examples include chitin, chitosan, gelatin, zein, sugar skeleton polymer compound, polyamide, polyethylene terephthalate, polycarbonate, polyurethane, and polysiloxane. These resins are used singly or in combination of two or more. Particularly preferably, the resin (B) is polybutanol or a copolymer thereof.

Yes

[0019] Examples of the copolymerizable monomer include acrylic monomers.

(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl hexyl ( (Meth) Atarylate, Cyclohexyl (Meth) Atylate, Benzyl (Meth) Atarylate, Dimethylamino (Meth) Atarylate, Hydroxyethyl (Meth) Atarylate, Hydroxypropyl (Meth) Atarylate, Glycidyl (Meth) Atallate is mentioned. 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 preferable.

Polybulfenol, a copolymer of polybuhlphenol and the above acrylic monomer has a weight average molecular weight of 1000 to 100,000, and preferably 2000 to 30,000 in terms of developability and adhesion. These can be combined as necessary, and can be used by copolymerizing buluenol with one of the above acrylic monomers, or using buluenol with A copolymer composed of a combination of two or more of the above acrylic monomers can be used. The weight average molecular weight is a relative value in terms of polystyrene.

Examples of other compounds used for copolymerization include styrene derivatives such as acrylic acid derivatives, acrylonitrile, methacrylonitrinole, styrene, α-methylstyrene, ρ methylstyrene, ο methylstyrene, ρ-methoxystyrene, and ρ chlorostyrene. . Of these, styrene is preferred!

Polybutanol or a copolymer thereof, that is, polyhydroxystyrene or polyhydroxystyrene derivative has a weight average molecular weight of 1000 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. The weight average molecular weight is a relative value in terms of polystyrene.

The photoacid generator (Α) used when using a resin (型) in a negative resist composition is one that generates acid directly or indirectly by light irradiation. .

[0020] In the negative resist composition, the crosslinkable compound (C) used for the resin (Β) includes a hydroxyl group, a hydroxyalkyl group, (a carbon number of 1 to 5) alkoxy (a carbon atom number of 1 to 5). ) A compound having at least one cross-linking group selected from the group consisting of alkyl groups can be used.

For example, an amino resin having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril formaldehyde resin, succinylamide formaldehyde resin, ethylene urea formaldehyde resin, etc.

[0021] As the crosslinkable compound (C), for example, a melamine derivative, a benzoguanamine derivative or glycoluril substituted with a hydrogen nuclear S-methylol group or an alkoxymethyl group of an amino group or both can be used. The melamine derivative and benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

[0022] Examples of such melamine derivatives or benzoguanamine derivatives include commercially available tria. MX—750 substituted with an average of 3 · 7 methoxymethyl groups per gin ring, MW—30 substituted with an average of 5.8 methoxymethyl groups per triazine ring (Made by Rochemica Canore), Saimenole 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc., such as methoxymethinorei melamine, Saimenole 235, 236, 238, 212, 253, 254 etc. Me

Toximethylated Benzoguanamine, such as melamine, Cymel 1 123, Toximethylated Benzoguanamine, like Cymel 1123-10, Toximethylinole Benzoguanamine, Saimenole 1125—80 A methoxymethylated oxymethylated benzoguanamine (above, manufactured by Nippon Cite Industries Co., Ltd.) is included. Examples of glycoluril include salylated glycoluril and the like, and methoxymethylolated glycoluril such as Powderlink 1174 (hereinafter, Nippon Cytec Industries, Ltd.).

Also, benzene or phenolic compounds having a hydroxyl group or an alkoxyl group, such as 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethinole) benzene, 1,4 bis (sec Butoxymethylol) benzene, 2,6 dihydroxymethyl-p tert butylphenol.

In addition, a compound containing an epoxy group or an isocyanate group and having a crosslinking group can also be used. Specific examples include, for example, bisphenolacetone glycidyl ether, phenol nopolac epoxy resin, cresol nopolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl m-xylenediamine, tetraglycidyl 1,3 —Bis (aminoethyl) cyclohexane, tetraphenyldaricidyl etherenoethane, triphenenoreglicidinoreethenoethane, bisphenolenohexanoleoroacetodiglycidinoreethenole, 1,3bis (1— (2,3 epoxy Propoxy) 1-trifluoromethyl-2,2,2 trifluoromethyleno) benzene, 4,4 bis (2,3 epoxycyclopropoxy) octafluorobiphenyl, triglycidinole paminophenol, tetraglycidyl Taki Shi range § Min, 2- (4 one (2, 3-epoxypropoxy) phenyl) - 2 1 (4 1 (1, 1 bis (4 1 (2, 3 epoxypropoxy) phenyl) phenyl) phenyl) 1, 3 bis (4— (1— (4— (2, 3 epoxypropoxy) phenyl) ) -1 (4 (1- (4- (2,3-epoxypropoxyphenyl) 1-methylethyl) phenyl) ethyl) phenoxy) 2-propanol and the like.

[0024] These crosslinkable compounds (C) can be used singly or in combination of two or more. The amount introduced is selected in the range of 1 to 300 parts by weight, preferably 20 to 200 parts by weight, per 100 parts by weight of the resin (B) component. When this amount is less than 1 part by mass, the crosslinking reaction does not proceed sufficiently, and it is difficult to obtain a desired resist pattern. When it exceeds 300 parts by mass, the storage stability of the resist composition is poor. . Therefore, the amount of the crosslinking agent introduced is preferably 1 to 300 parts by mass with respect to 100 parts by mass of the resin component.

[0025] The dye (D) used in the present invention has a spectral spectrum that is desirable when a color filter is produced, and uses the ability to dissolve in a solvent as it is, or the dye that dissolves in an organized form. I'll do it with power.

[0026] The dye (D) used in the present invention preferably contains a cationic compound represented by the formula [2].

In the formula [2], at least one of R ⁹ and R ^1Q has a nitrogen-containing organic group. S is preferable. Particularly, both R ⁹ and R ^1Q have a nitrogen-containing organic group. Is preferred.

It is preferable that at least one of the nitrogen-containing organic groups of R ⁹ and R ^1Q has an imino structure (one NH—R ¹³ ). Particularly, both R ⁹ and R ^1Q have an imino structure (one NH—R ¹³ ) Is preferable.

Here, R ¹³ represents an organic group, and is preferably an alkyl group such as a methyl group, an ethyl group, or a propyl group, or a substituted or unsubstituted aromatic group, particularly a substituted or unsubstituted aromatic group. It is preferably a group. Here, the aromatic group is preferably a phenyl group, a naphthyl group, an anthryl group, or the like. The substituent of these aromatic groups is an alkyl group such as a methyl group, an ethyl group, or a propyl group, or a halogen atom. Etc. are preferred.

Specifically, R ¹³ is a phenyl group, o tolyl group, m-tolyl group or p-tolyl group. Are preferred.

[0027] R ^u and R ^12, at least one of time of preferably fitting one is a hydrogen atom a hydrogen atom and the other is a methyl group, Echiru group, alkyl groups such as propyl group, or a substituted or unsubstituted An aromatic group is preferred. Here, the aromatic group is preferably a phenyl group, a naphthyl group, an anthryl group or the like, and the substituent of these aromatic groups is an alkyl group such as a methyl group, an ethyl group or a propyl group, A halogen atom or the like is preferable.

Particularly when both of R ¹¹ and R ¹² are hydrogen atoms, or, preferably may other while hydrogen atom of R ^u and R ¹² is the aromatic group! /,.

[0028] Specific examples of the cationic compound include compounds represented by the following formula.

[Chemical 6]

[11]

(Wherein R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom or a methyl group).

In addition, the cationic compound may have a resonance structure. When the compound of the formula [17] is taken as an example, the formula [18]

[Chemical 9]

There is also a cationic compound having the structure (wherein R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom or a methyl group). This cationic compound can also be used as the cationic compound contained in the dye (D).

[0031] The dye (D) used in the present invention is preferably an organic salt composed of a cationic compound and an anionic compound.

Examples of the anionic compound as a counter ion of the cationic compound represented by the formula [2] include a compound having a phthalocyanine structure, a compound having a pyrazole azo structure, a compound having a pyrazono laser structure and a metal complex structure, xanthene Examples include compounds having a structure.

[0032] The compound having a phthalocyanine structure is a compound having at least one phthalocyanine structure in one molecule. Phthalocyanine can be used with or without metal, and examples of central metals include Cu, Zn, Al, Ni, and Co.

In a compound having a phthalocyanine structure, a sulfonic acid group ( -so-) and / or carboxylic acid groups (one coo-). These are

Three

One or a combination of both can be contained in one molecule of phthalocyanine at a ratio of 1 to 4.

In addition to this anionic component, a sulfonic acid ester group (one SO R ¹⁶ , where R ¹⁶ represents an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, an ether group or an ester group). ), Sulfonic acid amino ester group (one SO NHR ¹⁷ , wherein R ¹⁷ represents an aliphatic, aromatic hydrocarbon group, ether group or ester group having 1 to 20 carbon atoms), hydroxyl group, It can have a tro group, an amino group, a chlorine atom such as chloro and bromo, and an alkyl group such as a methyl group and an ethyl group, and these nonionic groups can be any one or a combination thereof to form a phthalocyanine. 1 to 4 can be contained in each molecule. The nonionic group is particularly preferably a sulfonic acid amino ester group!

As a dye (D) used in the present invention comprising a combination of a sulfonic acid group-containing phthalocyanine as an anionic compound and a cationic compound represented by the formulas [5] to [10] 21] can be exemplified.

[Chemical 10]

The compound having a pyrazole azo structure is a compound having at least one of a pyrazole part and a azo part in one molecule.

The direct bond between the pyrazole moiety and the azo moiety can also exist with other organic groups in between. Both are possible. Examples include compounds in which an aromatic group or aliphatic group such as a phenyl group exists between the pyrazole part and the azo part, and the aromatic group or aliphatic group has a sulfonic acid group or other substituent. It is done.

The compound having a pyrazole azo structure preferably has a sulfonic acid group (-so-) and / or a carboxylic acid group (one COO-) as an anion component. These are

Three

Either one or a combination of both may be contained in a ratio of 1 to 4 in one molecule of the compound having a pyrazole azo structure. As the anionic group, a sulfonic acid group can be preferably used.

In addition to this anionic group, a sulfonic acid amino ester group (one SO NHR ¹⁸ , wherein R ¹⁸ is an aliphatic, aromatic hydrocarbon group, ether group or ester group having 1 to 20 carbon atoms). ), A hydroxyl group, a nitro group, an amino group, a chlorine atom such as chloro and bromo, an alkyl group such as a methyl group and an ethyl group, and these nonionic groups are either one or these In combination, it can be contained in a ratio of 1 to 4 per molecule of the compound having a pyrazole azo structure.

As a dye (D) used in the present invention comprising a combination of a compound having a sulfonic acid group-containing pyrazole azo structure as an anionic compound and a cationic compound represented by the formulas [5] to [18], 22] to [24] can be exemplified.

[Chemical 11]

The compound having a pyrazole azo structure and a metal complex structure is a compound in which a compound having an anionic group-containing virazo azo structure forms a complex with a metal.

The compound having an anionic group-containing pyrazole azo structure and the metal have a force S of forming a complex at a ratio of 2 to 4: 1 (molar ratio), and a preferable ratio is 2: 1 (molar ratio). The metal existing in the center is preferably a force Co such as Cu, Zn, Al, Ni, Co and the like.

A compound having a pyrazole azo structure and a metal complex structure preferably has a sulfonic acid group (SO) and / or a carboxylic acid group (COO-) as an anion component. These can be contained in a ratio of 1 to 4 in one molecule of a compound having a pyrazole azo structure, either one or a combination of both. A sulfonic acid group can be preferably used as the anionic group.

In addition to this anionic group, a sulfonic acid amino ester group (one SO NHR ¹⁹ , where R ¹⁹ is an aliphatic, aromatic hydrocarbon group, ether group or ester group having 1 to 20 carbon atoms). ), A hydroxyl group, a nitro group, an amino group, a chlorine atom such as chloro and bromo, an alkyl group such as a methyl group and an ethyl group, and these nonionic groups are either one or these In combination, it can be contained in a ratio of 1 to 4 per molecule of the compound having a pyrazole azo structure. As the nonionic group, an alkyl group such as a nitro group, a hydroxyl group, a methyl group, and an ethyl group can be preferably used. A dye used in 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 anionic compound and a cationic compound represented by the formula [5] to formula [18] ( As D), it is possible to exemplify the one of the formula [25]! And the formula [30].

[Chemical 12]

[Chemical 13]

[0038] In addition to this anionic group, a sulfonic acid amino ester group (one SO NHR ² °, in the formula

2

R ² ° represents an aliphatic or aromatic hydrocarbon group, ether group or ester group having 1 to 20 carbon atoms. ), A hydroxyl group, a nitro group, an amino group, a chlorine atom such as chloro and bromo, and an alkyl group such as a methyl group and an ethyl group. These nonionic groups may be any one or a combination thereof. The compound having a pyrazole azo structure can be contained in a ratio of 1 to 4 in one molecule.

[0039] A compound having a xanthene structure has at least one xanthene structure in one molecule. It is a compound.

The compound having a xanthene structure preferably has a sulfonic acid group (one S O—) and / or a carboxylic acid group (one COO—) as an anion component. These can be contained in a ratio of 1 to 3 in one molecule of a compound having a pyrazole azo structure, either or a combination of both. As the anionic group, a carboxylic acid group can be preferably used.

In addition to this anionic group, a sulfonic acid amino ester group (one SO NHR ²¹ , wherein R ²¹ is an aliphatic, aromatic hydrocarbon group, ether group or ester group having 1 to 20 carbon atoms). ), A hydroxyl group, a nitro group, an amino group, a chlorine atom such as chloro and bromo, an alkyl group such as a methyl group and an ethyl group, and these nonionic groups are either one or these In combination, it can be contained in a ratio of 1 to 3 per molecule of the compound having a xanthene structure.

The dye (D) used in the present invention comprising a combination of a compound having a xanthene structure as an anionic compound and a cationic compound represented by the formulas [5] to [18] is represented by the formula [31] to the formula [35]. Can be illustrated.

[Chemical 14]

A commercial item can be used for the dye (D) used for this invention. These dyes can be easily synthesized by known methods. For example, it can be obtained by a method of reacting an amine corresponding to the structure of the above formulas [5] to [18] with a dye molecule (matrix) having a sulfonic acid group or a carboxylic acid group. That is, 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. The solution can be synthesized by reacting with the amine required for salt formation in the desired molar ratio to precipitate a sparingly soluble salt in water. When the dye salt is soluble in water, the salt is obtained by salting out.

More specifically, an aqueous solution of an amine hydrochloride corresponding to the structure of the above formulas [5] to [18] is added to an aqueous solution of the above dye having sodium sulfonate or sodium carboxylate, and reacted. [5] to produce a dye having a cationic compound of formula [18].

The dye (D) used in the present invention can be further used in combination with an arbitrary dye. Examples of these dyes include acid dyes, oil-soluble dyes, disperse dyes, reactive dyes, and direct dyes. For example, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluoranes 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 9

3 94 96 98 104 107 114 116 117 124 130 131 133 135 141 143 145 146 157 160: 1 162 163 167 169 172 174 175 1 76 179 180 181 182 183 184 185 186 187 189 190 191 CI 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 1 10 111 112 1 13 CI 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 11 9 122 124 125 127 130 132 135 141 143 145 146 149 150 1 51 155 160 161 164 164: 1 165 166 168 169 172 175 179 18 0 181 182 195 196 197 198 207 208 210 212 214 215 218 2 22 223 225 227 229 230 233 234 235 236 238 239 240 241 242 243 244 245 247 248 CI Solvent Violet 2 8 9 11 13 14 21 21: 1 26 31 36 37 38 45 46 47 48 4m9 50 51 55 56 57 58 59 60 61 CI Solvent Blue 2 3 4 5 7 18 25 26 35 36 3 7 38 43 44 45 48 51 58 59 59: 1 63 64 67 68 69 70 78 79 83 94 97 98 100 102 104 105 111 112 122 124 128 129 132 136 137 138 139 143 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 5 5: 2 7 13 22 22: 1 26 27 28 29 34 35 43 45 46 48 49 50 CI Acid Red 6 11 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 Yel low 17 23 25 36 38 42 44 72 78 CI Basic Red 1 2 13 14 2 2 27 29 39 CI Basic Green 3 4 CI Basic Blue 3 9 41 66 C. I. Basic Violet 1 3 18 39 66 CI Basic Yellow 11 23 25 28 4 1 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 2 01 CI Direct Violet 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 Vat Re d 13 21 23 28 29 48 CI Vat Green 3 5 8 CI Vat Blue 6 1 4 26 30 CI Vat Violet 1 3 9 13 15 16 CI Vat Yellow 2 12 20 33 CI Vat Orange 2 5 11 15 18 20 CI Azoic Coupling Component 2 3 4 5 7 8 9 10 11 13 32 37 41 48 CI Reactiv e Red 8 22 46 120 CI Reactive Blue 1 2 7 19 CI Reactive Violet 2 4 CI Reactive Yellow 1 2 4 14 16 CI Reactive Orange 1 4 7 13 16 20 CI Disperse Red 4 11 54 55 58 65 73 1 27, 129, 141, 196, 210, 229, 354, 356, CI Disperse Blue 3, 24, 79, 82, 87, 106, 125, 165, 183, CI Disperse Violet 1, 6, 12, 26, 27, 28, CI Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64, CI Disperse Orange 13, 29, 30.

[0043] The dye (D) exhibits an optical characteristic having a region showing a transmittance of 70% or more in a wavelength region of 400 to 700 nm and a region showing a transmittance of 10% or less, and 200 The resist composition of the present invention, in which the change in transmittance is preferably within 5% even at a temperature of ≧ C, and the color filter produced from the resist composition exhibit similar optical characteristics.

[0044] 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 set to 200 to 270 ° C (200 ° C). Even if baked at a high temperature of 30 minutes for C and 30 seconds at 270 ° C), it is 400! /, And the transmittance change with time of the portion showing a transmittance of 70% or more in the 700 nm wavelength region is high-temperature baking. Within 5% is preferred compared to before performing.

[0045] In the dye-containing resist composition of the present invention, the amount of the dye (D) introduced is a solid comprising the photoacid generator (A), the resin (B), the crosslinkable compound (C), and the dye (D). It is selected in the range of 1 to 90% by mass with respect to the whole minute (100%). When the amount of dye introduced is small, it becomes difficult to develop a desired spectral spectrum when the resist film is thinned, and when the amount of dye introduced is large, the storage stability of the resist composition is poor. However, in the resist composition of the present invention, a dye having a cationic compound represented by the above formula [2], and further a dye comprising a cationic compound represented by the above formula [2] and an anionic compound As a matter of course, the introduction amount of the above dye (the concentration of the dye in the entire solid content) can be used at a low concentration of several mass%, but it is set to a high concentration of 30 to 90 mass%. The dye is sufficiently soluble.

The solvent (E) used in the dye-containing resist composition of the present invention is, for example, acetone, methanol monoethanol, ethanol, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ester. Tilketone, methyl isoamyl ketone, methinoreisopropenoleketone, methinoresenoresorenolev, ethinoresenoresonolev, methinoreserosolorebu Cetate, ethyl acetate sorb acetate, butyl carbitol, ethyl carbitol, ethylene glycolate, ethylene glycol monoacetate, ethylene glycol monoacetopropylene oleore, ethylene glycol ole monobutenoate, propylene glycol nore, propylene glycol Nole monoacetate, propylene glycol nole monomethylenoate, propylene glycol nore tert butinoleate nore, dipropylene glycol nole monomethinoatenore, diethylene glycol nore, diethylene glycol nore monoacetate, diethylene glyconoremino chinenoate nore, dipropylene Glyconole monoacetate monomethylenoateolene, dipropylene glycolenolemonomethylenoteatere, dipropylene Ricohino Monochinoleetenore, Dipropylene glycolenole monoacetate Monoethinoreethenole, Dipropylene glycolenoremonopropyl ether, Dipropylene glycol monoacetate monopropyl ether, Dipropylene glycolenole monopropenoate, Dipropylene glycolanol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutinoleatenore, diisobutylene, aminoreacetate , Butinolevylate, butinoleate, diisoptyl ketone, methylcyclohexene, propyl ether, dihexyl ester, dioxane, N, N dimethylase Toamide, N, N dimethylformamide, dimethyl sulfoxide, N methylpyrrolidone, γ-butyral rataton, η hexane, η pentane, η-octane, jetyl ether, cyclohexanone, methyl lactate, methyl lactate, methyl acetate , Ethyl acetate, η-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropyl Examples include lopionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone. 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 present invention. Examples of ketol include / 3-hydroxyketone, and specific examples thereof include 4-hydroxy-4-methyl-2-pentanone.

This is because the hydroxyl group and carbonyl group in the ketol solvent molecule are contained in the dye (D). In order to exert an effect as a convenient ligand, it is considered that the compound exhibits extremely high solubility. Therefore, when these dyes (D) are used, they are considered to be highly soluble.

As the solvent (E) used in the present invention, this ketol solvent can be used alone, but it is preferable to select a solvent containing the ketol solvent in a ratio of 10% by mass or more in the total solvent.

[0048] In the dye-containing resist composition of the present invention, the photoacid generator (A), the resin (B), the crosslinkable compound (C) and the dye (D) are combined with the photoacid generator (A), the resin (B ), The crosslinkable compound (C), the dye (D), and the solvent (E) are contained in a proportion, that is, a solid content concentration of 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, which causes pinholes and characteristics. On the other hand, when it exceeds 50% by mass, the viscosity of the resist composition becomes excessive, and the film thickness uniformity of the coating film is impaired.

[0049] The dye-containing resist composition of the present invention may contain a surfactant for the purpose of improving the wettability and flatness of the resist film. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and noion-based surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), MegaFac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florard FC4 30, FC431 ( Sumitomo 3EM Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahiishi Shoko Co., Ltd.).

[0050] The ratio of these surfactants to be used 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 (B) component. If the surfactant content exceeds 2 parts by mass, the resist film becomes uneven, and if it is less than 0.01 parts by mass, striations are likely to occur in the resist film.

[0051] For the purpose of improving the adhesion to the substrate after development, an adhesion promoter can be contained. Specific examples of such adhesion promoters include, for example, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane. Chlorosilanes such as orchid, alkoxysilanes such as trimethylmethoxysilane, dimethyljetoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N, Bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazanes of trimethylsilylimidazoles, butyltrichlorosilane, γ-chloropropylpropylmethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane Γ-glycidoxyprovir trimethoxysilane and other silanes, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobensimidazole, 2— Mention may be made of heterocyclic compounds such as lucaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, urea such as 1,1-dimethyleneurea, 1,3-dimethylurea, or thiourea compounds. it can.

[0052] 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 (i) component. It is.

[0053] Additives miscible with the dye-containing resist composition may be further added to the dye-containing resist composition of the present invention. For example, UV absorbers and antioxidants that enhance light stability, and compatibilizers that suppress dye precipitation include polyoxyethylene octyl ether compounds, polyoxyethylene lauryl ether compounds, polyoxyethylene alkyl ( 12 to 13 carbon atoms ether compound, polyoxyethylene secondary alkyl (12 to 14 carbon atoms) ether compound, polyoxyethylene alkyl (13 carbon atoms) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene Stearyl ether compounds, polyoxyethylene oleyl ether compounds, polyoxyethylene decyl ether compounds, polyoxyalkylene alkyls (11 carbon atoms! 15) ether compounds, polyoxyalkylene secondary alkyls (12 to 12 carbon atoms) 14) Alkyl ether compounds such as ether compounds and polyoxyalkylene cetyl ether compounds, alkyls such as polyoxyethylene lauryl amino ether compounds, polyoxyethylene stearyl amino ether compounds and polyoxyethylene oleylamino ether compounds Amino ether compound, polyoxyethylene lauric acid Alkylamide compounds such as amide ether compounds, polyoxyethylene stearic acid amide ether compounds, polyoxyethylene oleic acid amide ether compounds, lauric acid diethanolamide compounds, stearic acid diethanolamide compounds, oleic acid diethanolamide compounds, Polyoxyethylene polystilphenyl ether compound

Polysyl phenyl ether formamide condensates, polyoxyethylene monostyryl phenyl ether compounds, polyoxyethylene distyryl phenyl ether compounds, polyoxyethylene naphthyl ether compounds and other aryl phenyl ether compounds, glycerin monolaurate compounds, Glycerin monostearate compound, glycerin monooleate compound, glycerin fatty acid ester compound such as glycerol triolate compound, sorbitan monolaurate compound, sorbitan monopalmitate compound, sorbitan monostearate compound, sorbitan tristearate compound, sorbitan Sorbitanate compounds such as monooleate compounds, sorbitan trioleate compounds, polyoxyethylene dilaurate compounds, polyoxyesters Len laurate compound, polyoxyethylene stearate compound, polyoxyethylene distearate compound, polyoxyethylene dioleate compound, fatty acid ether ester compound such as polyoxyethylene oleate compound, polyoxyethylene castor oil ether compound, polyoxyethylene Vegetable oil ether ester compounds such as hardened castor oil ether compounds, polyoxyethylene sorbitan monolaurate compounds, polyoxyethylene sorbitan monostearate compounds, polyoxyethylene carbitan monooleate compounds, polyoxyethylene sulfitan trioleate compounds Carabitan ether ester compounds such as polyoxyalkylene butyl ether compounds, poly

14 to 15) Monool type polyether compound such as ether compound, polyoxyalkylene oleyl ether compound, diol type polyether compound such as polyoxyethylene polyoxypropylene condensate, trimethylolpropane tris (polyoxyalkylene) ether Compounds, polyol type polyether compounds such as polyoxyalkylene glyceryl ether compounds, methyl laurate compounds, methyl oleate compounds, isopyl pyrmyristate compounds, butyl stearate compounds, octyl palmitate compounds, Octyl stearate compound, Lauryl oleate compound, Isotridecyl stearate compound, Oleolelate compound, Dioleyl adipate compound, Trimethylolpropane Tridecanoate compound, Trimethylolpropane trilaurate compound, Pentaerythritol monorudiolate compound, Fatty acid alkyl ester compounds such as pentaerythritol monostearate compound and pentaerythritol distearate compound, alkyl sulfonate compounds, long-chain alkylbenzene sulfonate compounds, branched alkylbenzene sulfonate compounds, long-chain alkylbenzene sulfonate compounds, branched Alkylbenzene sulfonate compounds, branched alkyl diphenyl ether disulfonate compounds, mono

Compounds, sulfonic acid type compounds such as dioctylsulfosuccinate compounds, oleic acid sulfated oil compounds, castor sulfated compounds, octyl sulfate compounds, lauryl sulfate compounds, alkyl sulfate compounds, alkyl ether sulfate compounds, etc. Compounds, cellulose, cellulose derivatives, and sugar skeleton polymer compounds.

[0054] The proportion of the compatibilizer used is 0.001 to 100 parts by mass of resin (B) component 100 parts by mass.

20 parts by mass. 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, if the compatibilizer does not interfere with the pattern shape, it can be used in an amount of 20 parts by mass or more.

[0055] 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, 3-coumarin, atalidine, thiazine, phenothiazine , Anthracene, coronene, benzanthracene, perylene, merocyanine, ketocoumarin, fumarine, and borate. These can be used alone or in combination of two or more.

[0056] A method for producing a color filter using the dye-containing resist composition of the present invention is not particularly limited, and examples thereof include the following methods.

The resist composition of the present invention is prepared at a rotational speed to obtain a desired resist film thickness by a spinner method. Apply on recon wafer or glass substrate and perform soft beta (firing). The soft beta should be conducted for 30 seconds to 10 minutes in the temperature range of 50 to 150 ° C, as long as the solvent is evaporated. After that, exposure is performed through a mask at an exposure amount of about 10 to 3000 mj / cm ² . 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, heating (P EB (post exposure beta)) is preferably performed. By PEB, crosslinking with an acid or base generated by exposure further proceeds, and the difference in the solubility of the developing solution from the unexposed area is further widened to improve the resolution contrast. PEB should be in the temperature range of 50 to 170 ° C for 30 seconds! /, And preferably for 5 minutes! /.

Next, development is performed. The developing method can be carried out by a known method such as a paddle method, a dating method, or a spray method without any particular limitation. The development temperature is 20! /, And it is preferable to immerse in a developer solution preferably between 50 ° C for 10 seconds to 10 minutes.

As the developer, an organic solvent or an alkaline aqueous solution can be used. Specific examples include isopropyl alcohol, propylene glycol monomethyl ether, ethylamine aqueous solution, n-propylamine aqueous solution, jetylamine aqueous solution, diethyl n-propylamine aqueous solution, triethylamine aqueous solution, methyljetylamine aqueous solution, diethanolamine aqueous solution, triethanol. Examples thereof include an aqueous solution of amine, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium silicate, and an aqueous solution of sodium metasilicate.

[0058] Furthermore, it is preferable to add a surfactant to the developer in order to enhance the removability of the unexposed areas. Specific examples include polyoxyethylene octyl ether compounds, polyoxyethylene lauryl ether compounds, polyoxyethylene alkyl (12 or 13 carbon atoms) ether compounds, polyoxyethylene secondary alkyl (12 to 14 carbon atoms). Ether compounds, polyoxyethylene alkyl (13 carbon atoms) ether compounds, polyoxyethylene cetyl ether compounds, polyoxyethylene stearyl ether compounds, polyoxyethylene oleyl ether compounds, polyoxyethylene decyl ether compounds, polyoxyalkylenes Alkyl (11 carbon atoms! /, 15) etherification Compounds, polyoxyalkylene secondary alkyl (carbon atoms of 12 to 14) ether compounds, alkyl ether compounds such as polyoxyalkylene cetyl ether compounds, polyoxyethylene lauryl amino ether compounds, polyoxyethylene stearyl amino ethers Compounds, alkylamino ether compounds such as polyoxyethylene oleylamino ether compounds, polyoxyethylene lauric acid amide ether compounds, polyoxyethylene stearic acid amide ether compounds, polyoxyethylene oleic acid amide ether compounds, Alkylamide ether compounds such as lauric acid diethanolamide compound, stearic acid diethanolamide compound, oleic acid diethanolamide compound, polyoxyl ether compound, polyoxyalkylene Polystyryl phenyl ether formamide condensate, polyoxyethylene monostyryl phenyl ether compound, polyoxyethylene distyryl phenyl ether compound, polyoxyethylene naphthyl ether compound and other aryl phenyl ether compounds, glycerin monolaurate compound, glycerin mono Glycerin fatty acid ester compounds such as stearate compounds, glycerol monooleate compounds, glycerol trioleate compounds, sorbitan monolaurate compounds, sorbitan monopalmitate compounds, sorbitan monostearate compounds, sorbitan tristearate compounds, sorbitan monooleate Compounds, sorbitan acid ester compounds such as sorbitan triolate compounds, polyoxyethylene dilaurate compounds, polyoxy Tylene laurate compounds, polyoxyethylene stearate compounds, polyoxyethylene distearate compounds, polyoxyethylene diolate compounds, polyoxyethylene oleate compounds and other fatty acid ether ester compounds, polyoxyethylene castor oil ether compounds, Vegetable oil ether ester compounds such as reoxyethylene hydrogenated castor oil ether compounds

Sorbitan ether ester compounds such as polyoxyethylene sorbitan monolaurate compounds, polyoxyethylene sorbitan monostearate compounds, polyoxyethylene sorbitan monooleate compounds, polyoxyethylene sorbitan trioleate compounds,

Compounds, polyoxyalkylene alkyl (carbon atoms of 14! /, 15) ether compounds, monool-type polyether compounds such as polyoxyalkylene oleyl ether compounds Diol type polyether compounds such as polyoxyethylene polyoxypropylene condensate, polyol type polyether compounds such as trimethylolpropane tris (polyoxyalkylene) ether compound, polyoxyalkylene glyceryl ether compound, methyl laurate compound, methyl oleate compound, Isopropyl myristate compound, butyl stearate compound, octyl palmitate compound, octyl stearate compound, laurylololeate compound, isotridecyl stearate compound, oleyllate compound, dioleyl adipate compound, trimethylolpropane tridecanoate compound, trimethylo Propanetrilaurate compound, pentaerythritol diolate compound, pentaerythritol monostearate Fatty acid alkyl ester compounds, alkyl sulfonate compounds, long-chain alkyl benzene sulfonate compounds, branched alkyl benzene sulfonate compounds, long-chain alkyl benzene sulfonate compounds, branched alkyl benzene sulfonate compounds, branched alkyl diphenyl ethers Sulfonic acid type compounds such as disulfonate compound, monoisopropyl naphthalene sulfonate compound compound, dibutyl naphthalene sulfonate compound, dioctyl sulfosuccinate compound, oleic acid sulfated oil compound, castor sulfate compound, octyl sulfate compound, Sulfate ester compounds such as lauryl sulfate compounds, alkyl sulfate compounds, alkyl ether sulfate compounds Gera is.

[0059] 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 developability is too strong. In the case of the negative type, the unexposed area penetrates to the unexposed area. If the pattern surface is rough, the developability 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, developability cannot be obtained.

[0060] After development, there is water! / Is preferably rinsed with a general organic solvent. Thereafter, the 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.

[0061] Necessary by repeating the above series of steps as many times as necessary, changing each color and pattern. A colored pattern in which various numbers of colors are combined can be obtained. Further, after pattern formation, or in order to completely react the functional group that can be polymerized or condensed remaining in the pattern, heating (post beta) may be performed or after all colored patterns are formed. 150! /, 30 ° C in the temperature range of 500 ° C! /, And preferably 2 hours! /.

[0062] The color filter produced using the dye-containing resist composition of the present invention can be suitably used for a liquid crystal display device, an LED (light emitting diode) display device, a solid-state imaging device, and the like. It is preferably used as a solid-state image sensor.

[0063] The present invention also provides a cyclohexagen-based oxime sulfonate compound represented by the formula [3].

In the above formula [3], R ¹ and R ² are each independently a halogen atom, a CN NO alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. Represents a haloalkyl group of 5 or a haloalkoxy group of 1 to 5 carbon atoms, and R ³ represents a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group of 1 to 10 carbon atoms, or an alkyl group of 1 to 5 carbon atoms. An alkoxy group, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, and when n represents 23 or 4, each R ³ may be the same as each other or In addition, when R ³ is adjacent to each other, the two adjacent R ³ are —CH CH —CH 2 O— —CH N (R ⁸ ) — —CH 2 CH 2 CH 2 CH 2 O— CH CH N (R ⁸ ) CH CH CH CH CH CH CH CH O— CH CH CH N (R ⁸ ) — CH CH CH CH CH

Form CH CH CH CH O— or one CH CH CH CH N (R ⁸ ) — to form a 4-, 5-, or 6-membered ring with the carbon atom to which each of the two R ³ bonds. R ⁴ may be an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, R ⁸ represents a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. R ⁸ represents a hydrogen atom or a carbon atom having 1 to 10 carbon atoms. Represents an alkyl group, and W represents a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 represents a haloalkoxy group, n is 1 2 3 Or represents an integer of 4.

Here, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, a phenyl group optionally substituted by W, W Specific examples of the naphthyl group optionally substituted with and the anthranyl group optionally substituted with W include the same groups as those described for R ¹ to R ⁴ above.

[0064] The present invention also provides a cyclohexadiene-based oxime compound represented by the formula [4] as an intermediate for producing the compound represented by the formula [3].

In the formula [4], R ¹ and R ² are each independently a halogen atom, a CN NO alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms. Represents a haloalkyl group of 5 or a haloalkoxy group of 1 to 5 carbon atoms, and R ³ represents a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group of 1 to 10 carbon atoms, or an alkyl group of 1 to 5 carbon atoms. An alkoxy group, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms, and when n represents 23 or 4, each R ³ may be the same as each other or In addition, when R ³ is adjacent to each other, the two adjacent R ³ are —CH CH —CH 2 O— —CH N (R ⁸ ) — —CH 2 CH 2 CH 2 CH 2 O— CH CH N (R ⁸ ) CH CH CH CH CH CH CH CH O— CH CH CH N (R ⁸ ) — CH CH CH CH CH

Form CH CH CH CH O— or one CH CH CH CH N (R ⁸ ) — to form a 4-, 5-, or 6-membered ring with the carbon atom to which each of the two R ³ bonds. However, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 2 3 or 4.

Specific examples of a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkoxy group having 1 to 5 carbon atoms, and a phenyl group optionally substituted by W Examples thereof include the same groups as those described for R ¹ to R ⁴ above.

[0065] The cyclohexadiene oxime sulfonate compound represented by the formula [3] can be produced by a production method including the following steps. [Formula 15] one ^R1 (f ^[pi basic acid ^{^{_{R 1 <>"R4S02CI R 1}}} ()" 2 R 2 CN bases R ² 0N

PAN NB A ^N OC SCHC

(In the formula, R ¹ to R ⁴ have the same meaning as above.)

[0066] That is, in the first step, an intermediate oxime compound (OC) is obtained by reacting a substituted phenylacetonitrile compound (PAN) and a nitrobenzene compound (NB) in the presence of a base, followed by acidification. . In the second step, OC is reacted with a sulfonyl chloride compound (SC) in the presence of a base to produce the desired cyclohexadiene oxime sulfonate compound (SCHC).

[0067] As specific examples of the substituted phenylacetonitrile compound (PAN) in the first step, 2, 6 difluorophenylacetonitrile, 2, 6 diclonal phenylacetonitrile, 2, 6 dibuphthyl phenylacetonitrile, 2 , 6 Jodophenylacetonitrile, 2, 6 Dicyanophenoxyacetonitrile, 2, 6 Dinitrophenylacetonitrile, 2, 6 Dimethylphenylacetonitorinole, 2, 6 Dimethoxyphenenoleacetonitrinole, 2, 6 Examples include 6-difluoromethoxyphenylacetonitrile, 2-fluoro-6-methylphenylacetonitrile, 2-chloro-6-methylphenylacetonitrile, 2-bromo-6-methylphenylacetonitrile, and the like. Of these, 2,6-dichlorophenylnitrile and 2,6 dimethylphenylnitrile are particularly preferred.

[0068] On the other hand, specific examples of the nitrobenzene compound (NB) include nitrobenzene, 2-chloronitrite benzene, 3 chloronitrobenzene, 2 cyanonitrobenzene, 3 cyanonitrobenzene, 2 methinorenitrobenzene, 3 methinorenitrobenzene, 2- (i —Propinole) Nitrobenzene, 3— (i Propinole) Nitrobenzene, 2 Methoxy nitrobenzene, 3 Methoxynitrate Mouth benzene, 2 Trifunoleolomethino nitrobenzene, 3 Trifunoleolomethino nitrobenzene, 2 Trifluoromethoxynitrobenzene 3 trifluoromethoxynitrobenzene and the like. Also, the 2nd and 3rd positions are joined together to form a ring with 2 to 5 carbon atoms (oxygen atom or As the group that may form a nitrogen atom), for example, a compound of the following formula can be applied.

[Chemical 16]

[0069] Among these, nitrobenzene, 2-chloronitrobenzene, 3-chloronitrobenzene, 2-methino nitrobenzene, 3-methino nitrobenzene, 2- (i-propinole) nitrobenzene, 3- (i -Propyl) nitrobenzene and the like are preferred. The amount used is 0.8 for PAN. : Booster preference.

[0070] As the base, alkali metal or alkaline earth metal hydroxides, carbonates, organic acid salts and the like can be used. Specifically, from the viewpoint of reactivity and economy, sodium hydroxide or lithium hydroxide Is preferred. The amount used is preferably 2 to 5 equivalents to PAN.

[0071] The reaction solvent is preferably an aliphatic alcohol having 1 to 5 carbon atoms such as methanol or ethanol.

The reaction temperature is preferably -20 to 150 ° C, particularly 0 to 100 ° C. After the reaction, water is added to the reaction solution, acidified with an inorganic or organic acid, extracted with ethyl acetate and concentrated, and the resulting crude product is purified by recrystallization or column chromatography to obtain the desired OC. In this case, hydrochloric acid or acetic acid is used as the inorganic acid or organic acid.

[0072] Next, as specific examples of SC in the second step, methanesulfurol chloride, ethanesulfonol chloride, _n -propylsulfurol chloride, i-propylsulfurol chloride, _n- butylsulfurol chloride N-Amylsulfuryl chloride, n-Hexylsulfuryl chloride, n-Heptylsulfuryl chloride, n-octylsulfuryl chloride, n-Noninoresnorephoninorechloride, n-Desinoresnorecho Ninorechloride, Phenollessrephoni Nolechloride, p-Tosylsulfoylolide, p-Ethylphenylsulfurolide, p- (n-Propinole) phenylsulfolucide, p- (n-Butinore) Phenylsulfo Yuruku mouthride, p- (n-amyl) phenylsulfuryl mouthride, trifluoromethylsulfoninorechloride, pentafanolorechinolesnorehoninorechloride, nofnoreo- _n -pro-pinolesnorehoninorechloride, Novoleo mouth i Propinoles Norehonino chloride, Novenoreol butylsulfurol mouthride, Perfluoro n Amylsulfurol mouthride, Pentafluorophenylsulfurol mouthride, 1 Naphthylsulfurol mouthride, 2-Na Examples include butylsulfurolide, 1-anthranylsulfurolide and the like. The amount used is preferably 1 to 1.2 equivalents to OC.

[0073] As the base, organic bases such as triethylamine, pyridine, 4-N, N dimethylaminopyridine (DMA P) can be used. The amount used is preferably 1 to 1.1 equivalent times the amount of SC.

[0074] Examples of the reaction solvent include the number of carbon atoms such as toluene, xylene, ethylbenzene, and cumene.

1! /, And 5 alkyl benzenes are preferred! /, ...

The reaction temperature is preferably -20 to 100 ° C, particularly 0 to 80 ° C. Upon completion of the reaction, concentration yields a brown solid, which is then recrystallized or purified by column chromatography using silica gel to produce the desired cyclohexadiene oxime sulfonate compound (SCHC). .

Each of the above reactions can be carried out batchwise or flow-through, and can be carried out at normal pressure or under pressure.

[0075] In this specification, "n" is normal, "i" is iso, "s" is secondary, "t" is tertiary, "c" is cyclo, "o" is ortho. , “M” represents meta, “p” represents para, “Me” represents a methyl group, “Et” represents an ethyl group, and “Pr” represents a propyl group.

Example

[0076] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

The measuring device and conditions for each physical property in the examples are as follows.

[1] [Mass Spectrometry (MASS)]

Model: LX—1000 (manufactured by JEOL Ltd.)

Detection method: Ionization method: DEP (EI +) m / z = 50! /, 1000 [2] [ ^: H NMR]

Model: Equipment: JNM—LA400 type FT—NMR system (manufactured by JEOL Ltd.) Measurement solvent: DMSO—d

6

[3] [ ¹³ C NMR]

6

[4] [Melting point (mp.)]

Measuring instrument: Automatic melting point measuring device, FP62 (Metler Toledo Co., Ltd.)

[5] UV—Vis spectrum

Equipment: UV—VIS—NIR SCANNING SPECTROPHOTOMETER (Self-recorded spectrophotometer) (manufactured by Shimadzu Corporation)

[6] UV irradiation equipment

Model: PLA600FA (Canon Co., Ltd.)

[7] Interferometric film thickness meter

Model: F20— EXR (Filmetritas Co., Ltd.)

[Example 1] [Synthesis of HDCC]

[Chemical 17]

A lOOmL four-necked reaction flask was charged with 8.4 g (200 mmol) of NaOH and 42 g of methanol and heated to dissolve. Subsequently, after adding 11.2 g (60 mmol) of 2,6-dichlorophenylacetonitrile (2, 6-DCPA) at 55 ° C., 6.15 g (50 mmol) of nitrobenzene (ΝΒ) was added dropwise. The mixture was further stirred at 55 ° C for 2 hours and then concentrated to distill off the solvent. The residue was dissolved by adding 50 mL of water and 50 mL of ethyl acetate, and then ice-cooled. Then, 18 g of acetic acid was added dropwise to make it acidic. Since a solid was formed, it was separated by filtration and washed with ethyl acetate and water, and then the organic layer and aqueous layer of the filtrate were separated. Concentration of the organic layer gave 13. lg of oil. This crude After purification by column chromatography (ethyl acetate / heptane = 1/3 to 1/1) using 140 g of silica gel, recrystallization from ethyl acetate gave 6.52 g (yield 44.8%) of yellow crystals.

This crystal was confirmed to be (4-hydroxyiminocyclohexa 2,5 dimethylidene) 2,6 dichlorophenyl nitrile (HDCC) from the following analysis results.

— NMR confirmed that it was a mixture of two isomers (one to one).

MASS (FAB, m / e (%)): 291.96 ([M + H] +, 39), 289.97 (46), 23 9.06 (79), 237.06 (72), 190.20 (100), 177.20 (87)

: H NMR (DMSO-d, δ ppm): 6.35 (d, .1 = 10.1Hz, 0.5H), 6.43 (

6

dd, J = 1.83Hz, J = 10.08Hz, 0.5H), 6.70 (d, J = 9.78Hz, 0.5

1 2

H), 6.91 (dd, J = 1.83Hz, J = 9.32Hz, 0.5H), 7.27 (dd, J = 1.8

1 2 1

3Hz, J ₂ = 10.08Hz, 1H), 7.36 (dd, = 1.07Hz,] = 7.63Hz, 1H), 7.39 (dd, J = 1.83Hz, J = 9.77Hz, 1H), 7.44 (d, J = 0.54Hz, 1H

1 2

), 7.46 (t, J = l.07Hz, 1H), 7.48 (s, 1H)

13

C NMR (DMSO-d, δ ppm): 107.01, 107.04, 116.30, 116.3

6

6, 119.58, 119.79, 127.51, 128.09, 128.31, 128.54, 129.69, 129.96, 130.00, 130.20, 131.41, 135.92, 135.98, 1 45.03, 145.06, 150.64, 150.72.

mp.176 .

[Example 2] [Synthesis of TCDC]

[Chemical 18]

HDCC p-TSC

The operation was performed under a yellow fluorescent lamp below TCDC.

Charge a 50 mL four-necked reaction flask with HDCCl.0g (3.44 mmol) and 15 mL of toluene, and stir the magnetic stirrer at 17 ° C. When (3.44 mmol) was added, a red precipitate formed. While stirring as it was, 4 dimethylolaminoviridine (DMAP) O.63 g (5.16 mmol) was added dropwise. Since it became a cloudy slurry and stirring became worse, ImL of toluene was added. After stirring for 2 hours, transfer the reaction mixture to a round bottom flask while washing the reaction mixture with chloroform, and concentrate at 40 ° C to obtain 2.59 g of a brown solid.

This crude product was purified by column chromatography (hexane / chloroform = 1 / ;! ~ 2/3 ~ 1/2 ~ 0/1) using 60 g of silica gel, and then the fraction was purified at 40 ° C. After concentrating with, and dried under reduced pressure at 17 ° C for 2 hours, 1.555 g (100% yield) of amorphous solid was obtained. This solid had a purity of 98.8% according to analysis by liquid column chromatography. From the following analysis results, (4-p-toluenesulfonyloxyiminocyclohexa-2,5-gertylidene) 2,6 dichloro It was confirmed that it was oral phenylacetonitrile (TCDC).

^: H NMR confirmed that it was a mixture of two isomers (1 to 1).

MASS (FAB, m / e (%)): 469 ([M + Na + H] ⁺ , 71), 467 (100), 44 7 ([M + H] +, 30), 445 (41), 413 (9)

^: H NMR (DMSO-d, δ ppm): 2.46 (s, 3H), 6.86 (dd, J = 9.99Hz

6 1

, J = 16.2Hz, 0.5H), 7.12 (dd, = 9.99Hz, J = 16.2Hz, 0.5H), 7.26 (s, 0.5H), 7.32—7.52 (m, 7.5H), 7.89 (d, J = 8.37Hz, 2H)

¹³ C NMR (DMSO-d, δ ppm): 21.842, 111.638, 115.415, 119.

6

553, 111.976, 128.192, 128.546, 128.587, 128.892, 128.9 33, 129.673, 129.969, 130.710, 131.689, 131.738, 131.79 6, 132.553, 135.474, 135.531, 143.446, 145.552, 153.978, 154.043.

[Example 3] Synthesis of PCDC

[Chemical 19]

HDCC "" ^PSC PCDC and below were operated under a yellow fluorescent lamp.

In a 50 mL four-necked reaction flask, charge HDCC3.Og (10.3 mmol) and 25 mL of toluene, and add dropwise n-propylsulfurolide ride · 47 g (10.3 mmol) under magnetic stirring at 10 ° C. As a result, 20 mL of toluene was added again. 4-N, N-dimethylaminopyridine (DMAP) l.89 g (15.5 mmol) was added dropwise with stirring after heating to 20 ° C. Once the slurry had thinned, the slurry became thicker while generating heat (20 to 24 ° C), and particulate matter was formed. When stirring was continued as it was, the granular material became smaller, and stirring was stopped after 2 hours and 30 minutes. The reaction solution was concentrated to obtain 6.73 g of a solid.

This crude product was purified by column chromatography (hexane / chloroform = 1 / ;! ~ 2/3 ~ 1/2 ~ 0/1) using 100 g of silica gel, and the fraction was concentrated at 40 ° C. After drying for 1 hour under reduced pressure, 3.72 g (yield 91%) of one-spot reddish brown solid was obtained by two-dimensional TLC.

From the results of the following analysis, it was confirmed that this solid was (4-n-propylsulfonyloxyiminocyclohexa-2,5-diethylidene) -2,6-dichlorophenylacetonitrile (PCDC).

^: H NMR confirmed a mixture of two isomers (0.4 vs. 0.6).

^: H NMR (DMSO-d, δ ppm): 1.10 (t, J = 7.29Hz, 3H), 1.89— 1.99

6

(m, 2H), 3.35-3.42 (m, 2H), 6.55 (t, J = 8. 10Hz, 1H), 6.78 (dd, J = 1.89Hz, J = 10.3Hz, 0.4H), 6.98 (dd, J = 1.89Hz, J = 10

1 2 1 2

.3Hz, 0.6H), 7.16 (dd, J = 1.89Hz, J = 10.3Hz, 0.6H), 7.2

1 2

7 (s, 0.4H), 7.36-7.62 (m, 4H)

13

C NMR (DMSO-d, δ ppm): 12.890, 17.152, 51.067, 51.116

6

112.140, 115.332, 119.389, 119.619, 128.225, 128.27 4, 128. 554, 128. 587, 130. 348, 131. 080, 131. 812, 131. 870, 132. 890, 135. 400, 135. 441, 143. 315, 143. 339, 154. 26 [ [Example 4] Evaluation of colorability of photoacid generator by exposure and heating

In a 50 mL eggplant-shaped flask, VP8000 (manufactured by Nippon Soda Co., Ltd., the component is polybutanol. Weight average molecular weight 8000 (polystyrene equivalent)) 5 g, TCDC synthesized in Example 2 0.25 g, interface As an activator, Megafac R-30 (Dainippon Ink Chemical Co., Ltd.) (0.012 g) was added, and 4 hydroxy-4-methyl-2-pentanone (30 g) was added as a solvent and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. The composition was filtered using a 0.2 Hm PTFE (polytetrafluoroethylene) filter, and the composition was applied onto a glass substrate using a spin coater. The film was baked on a hot plate (soft beta) at 110 ° C for 1 minute to form a coating film with a thickness of 1.02 ίη (measured with an interference film thickness meter).

This coating film was irradiated with ultraviolet rays having an irradiation dose of 600 mj / cm ² at 365 nm by an ultraviolet irradiation device. Subsequently, PEB was performed on a hot plate at 120 ° C for 1 minute. Thereafter, post-beta was performed on a hot plate at 200 ° C. for 5 minutes, and the transmittance (transmittance at 400 nm) of the glass substrate on which the resist was formed was measured with a spectrophotometer.

[0081] [Example 5] Evaluation of colorability of photoacid generator by exposure and heating

In a 50 mL eggplant-shaped flask, 5 g of VP8000 (manufactured by Nippon Soda Co., Ltd., component polypolyphenol. Weight average molecular weight 8000 (polystyrene equivalent)), 0.25 g of PCDC synthesized in Example 3, interface As an activator, Megafac R-30 (Dainippon Ink Chemical Co., Ltd.) (0.012 g) was added, and 4 hydroxy-4-methyl-2-pentanone (30 g) was added as a solvent and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. The composition was filtered using a 0.2 m PTFE filter, and the composition was applied onto a glass substrate using a spin coater. The film was baked on a hot plate at 110 ° C for 1 minute (soft beta) to form a coating film with a thickness of 1.02 ^ m (measured with an interference film thickness meter).

This coating film was irradiated with ultraviolet rays having an irradiation dose of 600 mj / cm ² at 365 nm by an ultraviolet irradiation device. Subsequently, PEB was performed on a hot plate at 120 ° C for 1 minute. After that, post-beta was performed on a hot plate at 200 ° C for 5 minutes, and the resist was deposited on the film. The transmittance of the glass substrate (transmittance at 400 nm) was measured with a spectrophotometer.

[Example 6]

Marker Linker CHM (manufactured by Maruzen Petrochemical Co., Ltd., a component in a 50 mL eggplant-shaped flask, the component is a polymer consisting of a ratio of p-Buhlphenol / hydroxyethyl methacrylate = 50 parts by mass / 50 parts by mass. 5 g of average molecular weight 10000 (polystyrene equivalent)), 0.25 g of PCDC synthesized in Example 3, and Mega-F R-30 (manufactured by Dainippon Ink & Chemicals, Inc.) as a surfactant are put in 0 · 012 g. As a solvent, 30 g of 4-hydroxy-1,4-methylol-2-pentanone was added and stirred at room temperature. There was no insoluble material in the reaction solution, and the solution was uniform. The composition was filtered using a 0.2 m PTFE filter, and the composition was applied onto a glass substrate using a spin coater. The film was baked (soft beta) on a hot plate at 110 ° C for 1 minute to form a coating film with a thickness of 1.02 ίη (measured with an interference film thickness meter).

[0083] [Comparative Example 1] Evaluation of colorability of photoacid generator by exposure and heating

In a 50 mL eggplant-shaped flask, VP8000 (manufactured by Nippon Soda Co., Ltd., the component is polybutanol. Weight average molecular weight 8000 (polystyrene conversion)) 5 g, CGI1325 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.25 g of thiophenoxime sulfonate photoacid generator) and 0.012 g of MegaFac R-30 (Dainippon Ink Chemical Co., Ltd.) as the surfactant were added, and 4-hydroxy-4-methyl-2 as the solvent. 30 g of pentanone was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. The composition was filtered using a 0.2 m PTFE filter, and the composition was applied onto a glass substrate using a spin coater. The film was baked on a hot plate at 110 ° C for 1 minute (soft beta) to form a coating film with a thickness of 1.02 and im (measured with an interference film thickness meter).

This coating film was irradiated with ultraviolet rays having an irradiation dose of 600 mj / cm ² at 365 nm by an ultraviolet irradiation device. Subsequently, PEB was performed on a hot plate at 120 ° C for 1 minute. afterwards Post-beta was performed on a hot plate at 200 ° C for 5 minutes, and the transmittance (transmittance at 400 nm) of the glass substrate on which this resist was formed was measured with a spectrophotometer.

[Chemical 20]

CG1 1325

[0084] [Comparative Example 2] Evaluation of colorability of photoacid generator by exposure and heating

In a 50 mL eggplant-shaped flask, VP8000 (manufactured by Nippon Soda Co., Ltd., the component is polybutanol. Weight average molecular weight 8000 (polystyrene conversion)) 5 g, CGI1397 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.25 g of thiophenoxime sulfonate photoacid generator) and 0.012 g of MegaFac R-30 (Dainippon Ink Chemical Co., Ltd.) as the surfactant were added, and 4-hydroxy-4-methyl-2 as the solvent. —Pentanone (30 g) was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. The composition was filtered using a 0.2 m PTFE filter, and the composition was applied onto a glass substrate using a spin coater. The film was baked on a hot plate at 110 ° C for 1 minute (soft beta) to form a coating film with a thickness of 1.02 and im (measured with an interference film thickness meter).

[Chemical 21]

CG1 1397

[0085] Table 1 shows the transmittance results of the resists produced in Examples 4 to 6 and Comparative Examples 1 and 2. [table 1]

Transmittance at 4 0 0 nm

Example 4 9 1%

Example 5 8 3%

Example 6 8 8%

Comparative Example 1 7 2%

Comparative Example 2 4 2% As shown in Table 1, the resist (Examples 4 to 6) prepared using the photoacid generator of the cyclohexagen-based oxime sulfonate compound of the present invention is shown in Table 2002. — Photoacid of the present invention having higher post-beta transmittance than a resist (Comparative Examples 4 to 6) prepared using a photoacid generator comprising a thiophenoxime sulfonate compound described in Japanese Patent No. 508774. It can be seen that the generator is less colored by exposure and heating. Next, the effect of producing a color filter using the dye-containing resist composition of the present invention will be shown.

[Example 7]

In a 50 mL eggplant-shaped flask, VP8000 (manufactured by Nippon Soda Co., Ltd., the component is polybutanol. Weight average molecular weight 8000 (polystyrene equivalent)) is 1.54 g, dye formula [21] is 1.9 g, As a solvent, 23.756 g of propylene glycol monomethyl ether was added and stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform.

Thereafter, 0 · 38 g of the crosslinkable compound Cymel 303 (manufactured by Nippon Cytec Industries Co., Ltd.), 0 · 2 g of TCDC synthesized in Example 2, and MegaFac R— 3 0 as a surfactant (Dainippon Ink Chemical Co., Ltd.) 0.013 g) was added, and the mixture was further stirred at room temperature. No insoluble matter was found in the reaction solution, and the solution was uniform. This composition was filtered using a 0.2111 PTFE filter, and the composition was applied onto a glass substrate using a spin coater. Firing was performed on a hot plate at 110 ° C for 1 minute (soft beta) to form a coating film with a thickness of 1.02 111 (measured with an interference film thickness meter).

Moreover, this composition was apply | coated using the spin coater on the silicon substrate with an acryl. 1 Baked on a hot plate for 1 minute at 10 ° C (soft beta) to form a coating film with a thickness of 1.02 m. This coating film was irradiated with ultraviolet rays having an irradiation dose of 600 mJ / cm ² at 365 nm by an ultraviolet irradiation device. Subsequently, PEB was performed on a hot plate at 120 ° C for 1 minute. Thereafter, the film thickness was measured using an interference type film thickness meter.

This film was statically developed at room temperature for 40 seconds using a developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the film thickness was measured again using an interference film thickness meter.

The film thickness before and after development was compared, and the remaining film ratio after development was calculated.

[Comparative Example 3]

Then, 0 · 38g of cross-linkable compound Cymel 303 (Nippon Cytec Industries Co., Ltd.), 0.2g of CGI1397, and MegaFac R-30 (manufactured by Dainippon Ink & Chemicals, Inc.) as a surfactant are used. . 013 g was added and further stirred at room temperature. There was no insoluble matter in the reaction solution, and the solution was uniform. The composition was filtered using a 0.2 m PTFE filter, and the composition was applied onto a glass substrate using a spin coater. The film was baked (soft beta) on a hot plate at 110 ° C for 1 minute to form a coating film with a thickness of 1.02 πι (measured with an interference film thickness meter).

Moreover, this composition was apply | coated using the spin coater on the silicon substrate with an acryl. 1 Baked on a hot plate for 1 minute at 10 ° C (soft beta) to form a coating film with a thickness of 1.02 m. The UV irradiation device applied this coating film with a dose of 300mj / c at 365nm. Irradiated with ultraviolet rays of m ² . Next, PEB was performed on a hot plate at 120 ° C for 1 minute. Thereafter, the film thickness was measured using an interference type film thickness meter.

This film was statically developed at room temperature for 30 seconds using a developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the film thickness was measured again using an interference film thickness meter.

Table 2 shows the transmittance of the resists produced in Example 7 and Comparative Example 3.

[Table 2]

As shown in Table 2, the resist (Example 7) prepared using the dye-containing resist composition of the present invention is a thiophenoxime sulfonate compound described in JP-T-2002-508774. The dye-containing resist composition of the present invention, which has higher post-beta transmittance, is more effective for color filters than a resist prepared using a dye-containing resist composition containing I understand.

Table 3 shows the remaining film ratio of the color filters manufactured in Example 7 and Comparative Example 3.

[Table 3]

As shown in Table 3, the residual film ratio of the color filter prepared in Example 7 is higher than the residual film ratio of the color filter manufactured in Comparative Example 3. However, it turns out that it is highly sensitive.

Industrial applicability

Corresponding to the thinning of the color filter, it is possible to provide a dye-containing resist composition having a high dye concentration for expressing a desired spectral spectrum.

In addition, by suppressing the coloration that has been a problem with conventional photoacid generators, Toll reproducibility, high heat resistance, light resistance

Claims

Claim [1] Formula [1]

[Chemical 1]

(Where

R ° and R ⁷ are each independently a hydrogen atom, a halogen atom, CN NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Or a haloalkoxy group having 1 to 5 carbon atoms,

R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

n represents an integer of 1, 2, 3 or 4. )

A dye-containing resist composition comprising a photoacid generator comprising a cyclohexagen-based oxime sulfonate compound represented by the formula:

[2] The R ⁵ to R ⁷ forces are all hydrogen atoms, and R ¹ and R ² are each independently a halogen atom, CN, NO, an alkyl group having 1 to 10 carbon atoms, or a carbon atom number. The dye-containing resist composition according to claim 1, which is an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms.

[3] The dye-containing resist composition according to [2], wherein R ¹ and R ² are halogen atoms.

4. The dye-containing resist composition according to claim 3, wherein the halogen atom is a chlorine atom.

5. The dye-containing resist composition according to any one of claims 1 to 4, wherein R ³ is a hydrogen atom.

[6] A photoacid generator (A), a resin (B), a crosslinkable compound (C), a dye (D), and a solvent (E) comprising a cyclohexadiene oxime sulfonate compound represented by the formula [1] And a dye-containing resist composition.

[7] The dye (D) has the formula [2]

[Chemical 2]

7. The dye-containing resist composition according to claim 6, comprising a cationic compound represented by the formula: wherein R ⁹ to R ¹² each independently represents a hydrogen atom or an organic group.

[8] The dye-containing resist composition according to [7], wherein the dye (D) contains an anion compound which is a counter ion of the cationic compound represented by the formula [2].

[9] The dye-containing resist composition according to [8], wherein the anionic compound is a compound having a phthalocyanine structure.

10. The anionic compound according to claim 8, wherein the anionic compound is a compound having a pyrazole azo structure. A dye-containing resist composition.

[11] The dye-containing resist composition according to [8], wherein the anionic compound is a compound having a pyrazole azo structure and a metal complex structure.

12. The dye-containing resist composition according to claim 8, wherein the anionic compound is a compound having a xanthene structure.

[13] A method for producing a color filter comprising the steps of applying the dye-containing resist composition according to any one of claims 1 to 12 on a substrate, drying, exposing and developing.

14. A liquid crystal display device comprising a color filter produced by the method of claim 13.

15. An LED (light emitting diode) display device comprising a color filter manufactured by the method of claim 13.

[16] A solid-state imaging device comprising a color filter manufactured by the method of claim 13.

[17] Equation [3]

[Chemical 3]

R ³ represents a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or the number of carbon atoms. When 1 represents a haloalkoxy group of 1 to 5 and n represents 2 3 or 4, each R ³ may be the same as or different from each other, and when R ³ is adjacent The two adjacent R ³ groups are — CH CH —CH O— — CH N (R ⁸ ) — — CH CH CH —CH CH O— CH CH N (R CH CH CH CH —CH CH CH O— — CH CH CH N (R ⁸ ) CH CH CH CH CH C By forming H CH CH CH O— or one CH CH CH CH N (R ⁸ ) —, a 4-membered ring, 5-membered ring or 6-membered ring is formed with the carbon atom to which each of the two R ³ bonds. May

R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

W is a halogen atom, CN, NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or a haloalkoxy group having 1 to 5 carbon atoms. Represents

n represents an integer of 1, 2, 3 or 4. )

A cyclohexadiene oxime sulfonate compound represented by the formula:

18. The cyclohexadiene oxime sulfonate compound according to claim 17, wherein R ¹ and R ² are each independently a halogen atom.

[19] The cyclohexadiene oxime sulfonate compound according to [18], wherein the halogen atom is a chlorine atom.

[20] The cyclohexacene oxime sulfonate compound according to any one of [17] to [19], wherein R ³ is a hydrogen atom.

[21] Equation [4]

[Chemical 4]

(Wherein R ¹ and R ² are each independently a halogen atom, CN, NO, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Or a haloalkoxy group having 1 to 5 carbon atoms,

R ³ is a hydrogen atom, a halogen atom, a nitro group, a CN group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or the number of carbon atoms When 1 represents a haloalkoxy group of 1 to 5 and n represents 2 3 or 4, each R ³ may be the same or different from each other, and when R ³ is adjacent The two adjacent R ³ groups are — CH CH —CH O— — CH N (R ⁸ ) — —CH CH CH CH CH O—CH CH N (R ⁸ ) CH CH CH CH CH CH CH O— CH By forming CH CH N (R ⁸ ) —CH CH CH CH CH CH CH CH CH CH O— or one CH CH CH CH N (R ⁸ ) — together with the carbon atom to which each of the two R ³ bonds May form 4-, 5-, or 6-membered rings

R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

n represents an integer of 1 2 3 or 4. )

A cyclohexadiene oxime compound represented by:

[22] A photoacid generator comprising a cyclohexadiene oxime sulfonate compound represented by the formula [3].

[23] A photoacid generator for i-line comprising a cyclohexadiene oxime sulfonate compound represented by the above formula [3].