JP2008020779A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new colored photosensitive resin composition which ensures less residues after development in the manufacture of a thin color filter, even if a pigment is contained at a high concentration. <P>SOLUTION: The colored photosensitive resin composition comprises (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and (E) a solvent, wherein the binder resin (B) is a resin, comprising a constitutional unit derived from (meth)acrylic acid, a constitutional unit derived from cyclohexyl (meth)acrylate and a constitutional unit, derived from a compound having at least one skeleton selected from among a group having a tricyclodecane skeleton and a dicyclopentadiene skeleton. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition.

  The colored photosensitive resin composition comprises a pigment, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, for producing a color filter used for an image sensor such as a CCD or CMOS, a liquid crystal display panel, It is used for manufacturing color filters used in display devices such as electroluminescence and plasma display panels.

  Among them, a color filter with a thin film thickness is particularly required for a color filter for an image sensor. However, when the film thickness is simply reduced, the color density is reduced when the color filter is formed using the same color filter forming material, so the pigment concentration in the color filter forming material needs to be increased. Thus, when a color filter is produced using a colored photosensitive resin composition having a high pigment concentration in the color filter forming material, there is a problem that a large amount of residue (residue) that cannot be removed during development remains. (For example, refer to Patent Document 1).

JP-A-8-271723

  An object of the present invention is to provide a new colored photosensitive resin composition that contains a small amount of residue after development in the production of a thin color filter, even if it contains a pigment at a high concentration.

  In order to find a colored photosensitive resin composition that can solve the above-described problems, the present inventors have conducted extensive studies on the composition of the colored photosensitive resin composition, and as a result, have selected a specific compound as a photopolymerizable compound. The present inventors have found that a colored photosensitive resin composition to be contained can solve the above problems, and have completed the present invention.

  That is, the present invention is a colored photosensitive resin composition containing (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. The binder resin (B) is at least one selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from cyclohexyl (meth) acrylate, and a tricyclodecane skeleton and a dicyclopentadiene skeleton. Provided is a colored photosensitive resin composition which is a resin comprising a structural unit derived from a compound having a skeleton.

  The present invention also provides a pattern formed using the colored photosensitive resin composition, a color filter including the pattern, an image sensor including the color filter, and a liquid crystal display device including the image sensor. I will provide a.

  When the colored photosensitive resin composition of the present invention is used, a residue after development is reduced, and a thin color filter can be formed with a sufficient color density.

  The colored photosensitive resin composition of the present invention contains (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. B) is a structural unit derived from (meth) acrylic acid, a structural unit derived from cyclohexyl (meth) acrylate, and a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton. Including derived structural units.

  The colored photosensitive resin composition of the present invention contains (B) a binder resin. The (B) binder resin is at least one selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from cyclohexyl (meth) acrylate, and a tricyclodecane skeleton and a dicyclopentadiene skeleton. Containing structural units derived from a compound having a skeleton. Here, in this specification, (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and (meth) acrylate is at least one selected from the group consisting of acrylate and methacrylate. Represents a species.

  Examples of the compound having a tricyclodecane skeleton include tricyclodecyl (meth) acrylate and tricyclodecyloxyethyl (meth) acrylate.

  Examples of the compound having a dicyclopentadiene skeleton include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. It is done.

Content of the structural unit derived | led-out from said (meth) acrylic acid is a molar fraction in all the structural units which comprise (B) binder resin, Preferably it is 10 or more and 40 mol%, More preferably, it is 13-38. The mol%, particularly preferably 15 to 35 mol%. When the content of the structural unit derived from meth (acrylic) acid is in the above range, the solubility during development when forming a pattern using a colored photosensitive resin composition containing a binder resin having the component is included. Is preferable, and there is a tendency that a residue hardly remains after development.
The content of the structural unit derived from the cyclohexyl (meth) acrylate is preferably 20 to 90 mol%, more preferably 30 to 80 mol in terms of mole fraction in all the structural units constituting the (B) binder resin. %, Particularly preferably 40 to 70 mol%. When the content of the structural unit derived from cyclohexyl (meth) acrylate is in the above range, the solubility is good during development and the residue tends to remain after development, which is preferable.
The content of the structural unit derived from the compound having at least one skeleton selected from the group consisting of the tricyclodecane skeleton and the dicyclopentadiene skeleton is the molar content in all the structural units constituting the binder resin (B). The ratio is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, particularly preferably 5 to 25 mol%, and particularly preferably 8 to 20 mol%.

  A structural unit derived from a compound having at least one skeleton selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from cyclohexyl (meth) acrylate, a tricyclodecane skeleton, and a dicyclopentadiene skeleton Examples of the other monomer that leads to the constituent unit of the binder resin other than those include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, and carboxylic acid vinyl esters. , Unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, and macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain. . In addition, for example, a compound obtained by reacting (meth) acrylic acid contained in a structural unit with a compound having an unsaturated bond and an epoxy group in one molecule can be given.

  Specific examples of the binder resin include a component obtained by reacting glycidyl methacrylate with methacrylic acid / methacrylic acid / cyclohexyl methacrylate copolymer / tricyclodecanyl methacrylate copolymer, and glycidyl methacrylate with methacrylic acid / methacrylic acid. Constituents reacted with / cyclohexyl methacrylate copolymer / dicyclopentadienyl methacrylate copolymer, methacrylic acid / methacrylic acid reacted with glycidyl methacrylate / styrene copolymer / tricyclodecanyl methacrylate copolymer Coalescence is preferred.

  The acid value of (B) binder resin used by this invention becomes like this. Preferably it is 30-150, More preferably, it is 40-140, Most preferably, it is 50-130. When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. Is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration with an aqueous potassium hydroxide solution. .

  (B) Content of binder resin is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 10-40 mass%, More preferably, it is 12-35 mass%, Especially preferably. Is 14 to 32% by mass. (B) It is preferable that the content of the binder resin be in the above range because a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

  (B) The polystyrene-reduced weight average molecular weight of the binder resin is preferably 5,000 to 55,000, more preferably 6,000 to 45,000, and particularly preferably 7,000 to 35,000. . When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  The colored photosensitive resin composition of the present invention contains (A) a colorant. Examples of the colorant (A) include at least one selected from the group consisting of pigments and dyes.

Specific examples of the pigment include compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists). Specifically, for example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7. Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 209, 254, C.I. I. Pigment red violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. It is preferable to contain at least one pigment selected from the group consisting of CI Pigment Green 7 and 36.

Examples of the dye include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes.
Examples of the dye include C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only numbers are described. Other dye types and hues are also omitted) 14, 15, 23, 24 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. I. Solvent Red 45, 49, C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56, C.I. I. Solvent blue 35, 37, 59, 67 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. I. Acid Yellow 17, 29, 40, 76, C.I. I. Acid Red 91, 92, 97, 114, 138, 151, C.I. I. Acid Orange 51, 63, C.I. I. Acid Blue 80, 83, 90, C.I. I. Examples include dyes such as Acid Green 9, 16, 25, and 27.

  In addition, as the dye (A), for example, amine salts of acidic dyes represented by formulas (i) to (vii) and sulfonamide derivatives of acidic dyes represented by formulas (viii) to (ix) are also used. it can.

D- (SO ₃ ⁻ ) _m (C _n H _{2n + 1} N ⁺ H ₃ ) _m (i)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₂ N ⁺ H ₂ } _m (ii)
D− (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₃ N ⁺ H} _m (iii)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₄ N ⁺ } _m (iv)
D- (SO ₃ ⁻ ) _m (C _e H _{2e + 1} OC _f H _2f N ⁺ H ₃ ) _m (v)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) (PhCH ₂ ) ₂ N ⁺ H} _m (vi)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) Py ⁺ } _m (vii)
_{D - [{SO 2 NH (} C n H 2n + 1)} p] [(SO 3 L) q] (viii)
_{D - [{SO 2 NH (} C e H 2e + 1 OC f H 2f)} p] [(SO 3 L) q] (ix)

[In formulas (i) to (ix), D represents a dye matrix.
m represents an integer of 1 or more and 20 or less.
n represents an integer of 1 or more and 20 or less.
e and f each independently represents an integer of 1 or more and 10 or less.
Ph represents a phenyl group.
Py represents a pyridine ring residue or a methylpyridine ring residue connected to C _n H _{2n + 1} by a nitrogen atom.
p represents an integer of 1 to 8.
q represents an integer of 0 or more and 8 or less.
L represents a hydrogen atom or a monovalent cation. ]

Specific examples of the dye base include an azo dye base, a xanthene dye base, an anthraquinone dye base, a triphenylmethane dye base, and a phthalocyanine dye base.
m preferably represents an integer of 1 to 10, more preferably an integer of 1 to 8.
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 8.
e and f each independently preferably represent an integer of 1 to 8, more preferably an integer of 1 to 6.
Py preferably represents a methylpyridine ring residue.
p preferably represents an integer of 1 to 6, more preferably an integer of 1 to 5.
q preferably represents an integer of 0 to 6, more preferably an integer of 0 to 5.
Examples of the monovalent cation in L include lithium ions, sodium ions, potassium ions, quaternary ammonium ions such as (C ₂ H ₅ ) ₃ HN ⁺ , and preferably sodium ions.

  Examples of the azo dye include dyes represented by formula (I) and dyes represented by formulas (11) to (13).

[In the formula (I), R ³⁰ represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an aryl group having 6 to 21 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms.
The alkyl group, alkenyl group, aryl group and aralkyl group may be unsubstituted or may have a substituent.
R ^{31 to} R ³⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ]

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. A linear alkyl group such as a group, n-decyl group, n-undecyl group, n-dodecyl group;
Isopropyl group, sec-butyl group, tert-butyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethylheptyl group, 2-ethyloctyl group, 2-ethylnonyl group, 2-ethyldecyl group Branched alkyl groups such as;
Examples thereof include cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.
The alkyl group may contain an oxygen atom in the form of an ether bond. Examples of the alkyl group containing an oxygen atom in the form of an ether bond include a methoxymethylene group, a methoxyethylene group, an ethoxyethylene group, a butoxyethylene group, and a butoxybutylene group.
R ³⁰ is preferably a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isopropyl group, sec-butyl group. Tert-butyl group, 2-ethylbutyl group, 2-ethylpentyl group, 2-ethylhexyl group, 2-ethylheptyl group, 2-ethyloctyl group, more preferably isopropyl group, tert-butyl group, 2- Examples include an ethylbutyl group, a 2-ethylpentyl group, and a 2-ethylhexyl group.
R ^{31 to} R ³⁴ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. And preferably include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a fluorine atom, and a chlorine atom.

  Of the dyes represented by formula (I), a preferred dye is specifically a compound represented by formula (14). Moreover, as a xanthene dye, the compound represented by Formula (15) is mentioned, for example. Moreover, as a copper phthalocyanine dye, the compound represented by Formula (16) etc. are mentioned, for example.

  These dyes that can be used in combination include the solubility in a solvent used for the colored composition, the light fading resistance and the spectral spectrum when forming a color filter pattern using a colored photosensitive resin composition containing the colored composition. It is suitably selected according to

For example, in order to form a red pixel using the colored photosensitive resin composition containing the colored composition of the present invention, a dye of formula (13), a dye of formula (14) and a dye of formula (15) are preferred. Can be selected.
In order to form a blue pixel, for example, preferably a dye of formula (16) I. Acid Blue 90 and C.I. I. A combination of Solvent Blue 67 can be selected.
In order to form a green pixel, for example, preferably C.I. I. Solvent Blue 67, C.I. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Solvent Yellow 82 and C.I. I. A combination of solvent yellow 162 can be selected.
The combination of the red, blue and green dyes is not limited to the above combination, and each dye can be appropriately combined according to the spectral spectrum of the target pixel.

  These dyes (A) are optionally treated by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the surface of dye particles with a polymer compound, or the like. A cleaning process using an organic solvent or water for removing water, a removing process using an ion exchange method for ionic impurities, or the like may be performed alone or in combination.

  (A) The colorant is a dispersion in which pigments and dyes are uniformly dispersed in the solution by containing a dispersant or a part or all of the binder resin (B) as necessary. Obtainable.

  Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and may be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink Chemical Co., Ltd.) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Inc.) Etc.

  When using a dispersing agent, the usage-amount is a mass fraction with respect to 100 mass% of coloring agents, Preferably it is 0.1-100 mass%, More preferably, it is 5-50 mass%. It is preferable that the amount of the dispersant used be in the above range because a uniform dispersion tends to be obtained.

  The content of the colorant (A) used in the colored photosensitive resin composition of the present invention is a mass fraction with respect to the solid content in the colored photosensitive resin composition, preferably 20 to 65% by mass, and more preferably. Is 25 to 60% by mass, more preferably 27 to 55% by mass, and particularly preferably 30 to 50% by mass. Here, the solid content in the present specification means (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator of the colored photosensitive resin composition, and further necessary. The total amount of components that are not liquid at room temperature among the components added according to the above.

  (A) When the content of the colorant is in the above range, the color density when a color filter is obtained is sufficient, and the binder resin can be contained in the composition in an amount more than necessary. Is preferable because a sufficient pattern can be formed.

  The colored photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. (C) The photopolymerizable compound is a compound that can be polymerized by active radicals, acids, etc. generated from (D) a photopolymerization initiator when irradiated with light, for example, polymerizable carbon-carbon unsaturated Examples thereof include compounds having a bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The (C) photopolymerizable compound may be used alone or in combination of two or more. (C) Content of a photopolymerizable compound is a mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably it is 5-50 mass%, More preferably, it is 10-45 mass%, Especially preferably, it is 15-40 mass%. (C) When the content of the photopolymerizable compound is in the above range, curing is sufficiently performed, the film thickness ratio before and after development is improved, and undercut is difficult to enter into the pattern, and the adhesion is good. It is preferable because it tends to become.

  The colored photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. Examples of the photopolymerization initiator (D) include triazine compounds, acetophenone compounds and biimidazole compounds, active radical generators, and acid generators.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

    Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- Examples include 1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenyl. Onium salts such as methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  (D) Content of photoinitiator is a mass fraction with respect to the total amount of (B) binder resin and (C) photopolymerizable compound, Preferably it is 0.1-20 mass%, More preferably Is 1 to 15% by mass. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved. On the other hand, the line width of the line and space pattern is resolved due to the sensitivity being too high. Is preferable because the line width tends not to be too large.

The colored photosensitive resin composition of the present invention may further contain (G) a photopolymerization initiation assistant. The (G) photopolymerization initiation assistant is a compound that is usually used in combination with the (D) photopolymerization initiator and is used to accelerate the polymerization of the photopolymerizable compound that has been polymerized by the photopolymerization initiator. is there.
Examples of the (G) photopolymerization initiation assistant include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone etc. are mentioned, Preferably 4,4'-bis (diethylamino) benzophenone is mentioned.

  Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  (G) The photopolymerization initiation assistant may be used alone or in combination of two or more. In addition, as the (G) photopolymerization initiation aid, commercially available products can be used, and as the commercially available (G) photopolymerization initiation aid, for example, EAB-F (Hodogaya Chemical Co., Ltd. And 4,4′-bis (diethylamino) benzophenone) and other organic amine compounds.

  Examples of the combination of (D) photopolymerization initiator / (G) photopolymerization initiation assistant in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketo / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) Examples include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, and preferably 2-methyl-2-morpholino- 1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When these (G) photopolymerization initiation assistants are used, the amount used is preferably 0.01 to 10 parts, more preferably 0.01 to 5 parts per part of (D) photopolymerization initiator. .

  Examples of the solvent (E) contained in the colored photosensitive resin composition of the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Over DOO, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.

  Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

  Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-methyl-4-hydroxy-2-pentanone, and cyclopentanone. And cyclohexanone.

  Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

  Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
These solvents may be used alone or in combination of two or more.

  Among the above solvents, a solvent containing propylene glycol monomethyl ether acetate is preferably used. (E) When the solvent contains propylene glycol monomethyl ether acetate, the content of propylene glycol monomethyl ether acetate is a mass fraction with respect to the solvent, preferably 50 to 97 mass%, more preferably 60 to 95 mass%. is there.

  (E) Content of a solvent is a mass fraction with respect to a coloring photosensitive resin composition, Preferably it is 70-90 mass%, More preferably, it is 75-88 mass%. (E) It is preferable for the content of the solvent to be in the above-mentioned range since the in-plane uniformity at the time of coating is good, and the color density when the color filter is formed is sufficient and the display characteristics are good.

  Further, a surfactant may be included. Examples of the surfactant include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.

  Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, it is a Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323. , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, under the product names Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck F142D, F171, F172, F173, F177, F183, F470, F475, and R30 ( Dainippon Ink & Chemicals, Inc.), F-Top EF301, EF303, EF351, EF352 (made by Shin-Akita Kasei), Surflon S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) ), E5844 (manufactured by Daikin Fine Chemical Laboratory), BM-1000, BM-1100 (manufactured by BM Chemie), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specific examples include Megafax R08, BL20, F475, F477, F443 (Dainippon Ink Chemical Co., Ltd.).
These surfactants may be used alone or in combination of two or more.

  The colored photosensitive resin composition of the present invention may contain an organic acid. Examples of the organic acid include organic acids disclosed in JP-A-5-343631. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, Methacrylic acid is mentioned, Preferably malonic acid, oxalic acid, fumaric acid, and phthalic acid are mentioned. By containing an organic acid, the residue tends to be even better, which is preferable.

  The colored photosensitive resin composition of the present invention further includes a filler, a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic amine compound, a curing agent, and the like. An agent may be contained.

  Examples of the filler include fine particles such as glass and alumina.

  Examples of the polymer compound other than the binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of the antioxidant include 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;
Benzophenone series such as 2-hydroxy-4-octyloxybenzophenone;
Benzoate systems such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;
And triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

By adding the organic amine compound, a residue is not generated on the unexposed substrate during development, and a pixel having excellent adhesion to the substrate can be provided.
Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n- Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, Dialkylamines such as di-n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkanediols such as 1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  Examples of the curing agent include a compound that can react with a carboxyl group in the binder resin by being heated to crosslink the binder resin, and a compound that can be polymerized alone to cure the colored pattern. . As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example, An oxetane compound is used preferably.

  Here, as the epoxy compound, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic epoxy resins , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, cycloaliphatic or aromatic epoxy compounds, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl Examples include isocyanurate.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored photosensitive resin composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples include ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), RIKACID HH, MH-700 (both manufactured by Shin Nippon Rika Co., Ltd.) and the like. It is done.

  The above curing agents may be used alone or in combination of two or more.

  As a method for preparing the colored photosensitive resin composition of the present invention, for example, a dispersion of a colorant is prepared by dispersing a colorant such as a pigment in the solvent (E) together with a dispersant. Furthermore, (B) binder resin, (C) photopolymerizable compound, (D) photopolymerization initiator and other additives as necessary dissolved in a solvent are dissolved, and the above-mentioned (A) colorant is dispersed. The method of mixing with a liquid and adding a solvent further as needed is mentioned.

  In addition, the colored photosensitive resin composition of the present invention is usually enclosed in a container and distributed and stored.

  A general method for producing a color filter for an image sensor using the colored photosensitive resin composition of the present invention is as follows. A step of applying and drying the colored photosensitive resin composition of the present invention on a substrate, a step of pattern exposure of the obtained dry coating film with an i-line stepper, a step of alkali development after exposure, and a step of heat treatment A color filter is obtained by sequentially performing the above steps for each color (3 colors or 4 colors) to form pixels.

More specifically, the colored photosensitive resin composition of the present invention is dried on a suitable substrate by a spin coater or the like so that the film thickness when dried is generally 0.1 to 5 μm, preferably 0.2 to 2 μm. Then, it is left in an oven at 100 ° C. for 3 minutes to obtain a smooth coating film.
The substrate is not particularly limited, but is a glass plate, a plastic plate, an aluminum plate, a substrate for an electronic component such as a silicon wafer for an image sensor, a transparent resin plate, a resin film, a cathode ray tube display surface, a light receiving surface for imaging feeling, Wafers on which solid-state image sensors such as CCD, BBD, CID, and BASIS are formed, contact image sensors using thin film semiconductors, liquid crystal display surfaces, color electrophotographic photoreceptors, substrates for electrochromy (EC) display devices, etc. Is mentioned. Further, it is preferable to perform a high adhesion treatment to improve the adhesion to the color filter layer on the substrate. Specifically, after a thin coating with a silane coupling agent or the like is applied on the substrate in advance, a pattern of the colored photosensitive resin composition is formed, or the colored photosensitive resin composition is previously incorporated with a silane coupling agent. Also good.

  If there is a step on the substrate, apply the colored photosensitive resin composition of the present invention after coating the substrate with a planarizing film for eliminating the step and smoothing the coating surface. Can do. For example, a sensor unit of an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate according to the amount of received light, and a readout gate unit for outputting the generated electrons. However, if light hits the readout gate part, it causes noise and accurate data is not output.Therefore, a light shielding film layer is formed on the upper part of the readout gate part, and between the photodiode part without the light shielding film layer. There may be a level difference. When a color resist is applied on such a step and a color filter is directly formed, the optical path length becomes long, so that the image becomes dark and the light condensing property becomes inferior. In order to improve this, it is preferable to form a transparent flattening film between the CCD and the color filter in order to fill the step. Examples of the material for the planarizing film include a photosensitive resin composition as in the present invention, an acrylic-based, epoxy-based thermosetting resin, a photo-curable resin, and the like.

  After applying the colored photosensitive resin composition, in order to obtain a dry coating film by removing the solvent, drying under reduced pressure or pre-baking is usually performed. As a method for drying under reduced pressure, for example, there is a method in which the coated material is placed at a temperature of 50 to 120 ° C. at a pressure of 0.1 to 100 Torr. Examples of the pre-baking method include heat drying using high-temperature air and the like, and heat drying using a hot plate or the like (80 to 140 ° C., 50 to 200 seconds).

  In addition, post-baking is performed in order to sufficiently cure the pattern obtained after development to increase the mechanical strength and form a permanent film. For example, in the production of a three-color filter, the first formed pattern is then subjected twice to the application of a colored photosensitive resin composition of another color, exposure, and development. At this time, post-baking is performed so as not to cause pattern omission due to color mixing, exposure, and development with the applied colored photosensitive resin composition. This post-baking uses the same method as pre-baking, but is performed at a higher temperature and for a longer time than the pre-baking conditions. For example, it is performed at 100 to 250 ° C. for 1 to 60 minutes.

  There is no restriction | limiting in particular in the developing solution used for development of a coloring photosensitive resin composition, A conventionally well-known developing solution can be used. Among these, an organic alkaline aqueous solution of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) is preferable.

  Here, in the image sensor including the color filter of the present invention, for example, as described above, after the planarization film is formed on the sensor portion formed on the substrate and the color filter of the present invention is formed thereon, It can be manufactured by applying a lens material, patterning a lens pattern by a photolithography process and heat treatment, and then etching back the entire surface to form an on-chip lens.

  Moreover, a transparent protective film is formed on the color filter obtained above, and a transparent electrode such as an ITO film is further formed thereon. Next, the color filter substrate and a reflective electrode substrate on which a reflective electrode such as a metal vapor deposition film is formed are further subjected to a rubbing treatment for liquid crystal alignment provided on those substrates, and a liquid crystal alignment film, and They are bonded to each other through a spacer for maintaining the cell gap. In addition to the reflective electrode, a projection for light diffusion, a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, and the like are provided on the reflective electrode substrate, and a TFT liquid crystal display device, A TFD liquid crystal display device can be produced. When it has a backlight, it can arrange | position to the back surface of a liquid crystal display. The edge-light type uses acrylic resin with excellent light transmittance as the light guide plate, LED light sources are installed on its two sides or one side, the reflective part is processed on the back side of the light guide plate, and the reverse plate is processed A prism sheet, a diffusion plate, or the like can be disposed on the side. If it has a front light, it is placed in front of the liquid crystal display. A reflector and an LED light source can be disposed on the upper part of the light guide plate made of transparent resin or the like. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. Next, a liquid crystal display device can be manufactured by mounting an IC driver or the like.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

  The structure and the like of the binder resin used in Examples and Comparative Examples are shown in Formula (B1) and Formula (B2). In addition, a numerical value represents the mole fraction at the time of preparation.

Synthesis example 1
<Synthesis of Resin B1>
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 110 ° C., To a mixture of 67.2 g (0.40 mol) of cyclohexyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of tricyclodecyl methacrylate and 136 g of propylene glycol monomethyl ether acetate, A solution to which 3.6 g of isobutyronitrile was added was dropped into the flask from the dropping funnel over 2 hours, and stirring was further continued at 110 ° C. for 3 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 21.3 g of glycidyl methacrylate [0.15 mol, (30 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain Resin B1.

Synthesis example 2
<Synthesis of Resin B2>
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 110 ° C., A mixture of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of tricyclodecyl methacrylate and 136 g of propylene glycol monomethyl ether acetate was added to azobis. A solution to which 3.6 g of isobutyronitrile was added was dropped into the flask from the dropping funnel over 2 hours, and stirring was continued at 110 ° C. for 3 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 21.3 g of glycidyl methacrylate [0.15 mol, (30 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain Resin B2.

  The polystyrene equivalent weight average molecular weights of the obtained resins B1 and B2 were both 10,000.

About the measurement of the polystyrene conversion weight average molecular weight of said binder resin, it carried out on condition of the following using GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The components used in this example are as follows, and may be omitted below.
(A-1) Colorant: C.I. I. Pigment Red 254
(A-2) Colorant: C.I. I. Pigment Yellow 139
(B-1) Resin B1
(B-2) Resin B2
(C-1) Photopolymerizable compound: Dipentaerythritol hexaacrylate, succinic acid derivative CBZ-SA of dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical)
(D-1) Photopolymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine (E-1) solvent: propylene glycol monomethyl ether acetate (E-2) solvent: Ethyl 3-ethoxypropionate (F-1) Megafax F475 (manufactured by Dainippon Ink & Chemicals, Inc.)

Example 1
A colored photosensitive resin composition 1 was prepared with the composition shown in Table 1. Numerical values in Table 1 represent parts by mass.

[Pattern formation 1]
A glass resist (# 1737; manufactured by Corning) was spin-coated with Sumistres PR-1300Y-PG (manufactured by Sumitomo Chemical Co., Ltd.) and heated at 100 ° C. for 1 minute to remove volatile components. A 5 μm resin layer was formed. Next, this glass was heated at 230 ° C. for 15 minutes to cure the resin layer, thereby forming a support with a flattened film. On this support, the colored photosensitive resin composition 1 obtained above was applied by spin coating, and then the volatile components were volatilized at 100 ° C. for 3 minutes to form a colored photosensitive resin composition film. After cooling, the colored photosensitive resin composition film was exposed by irradiating i-line (wavelength 365 nm) through a photomask. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 150 mJ / cm ² . As the photomask, a photomask for forming linear color pixels having a line width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, and 100 μm was used. Next, a glass substrate after exposure [a colored photosensitive resin composition film is formed on the surface. ] Was developed by immersing in a developing solution (CIS DEVELOPER; ENF Technology Co., Ltd.) at 23 ° C. for 80 seconds, and washed with pure water to obtain a glass substrate on which a line and space pattern was formed.

[Evaluation 1]
The transmittance | permeability (550 nm) of the part which melt | dissolved the coating-film layer of the glass substrate obtained above was 100%, and there was no residue.

[Pattern formation 2]
Also, a violet resist PR-1300Y-PG (manufactured by Sumitomo Chemical Co., Ltd.) is spin-coated on a silicon wafer, heated at 100 ° C. for 1 minute to remove volatile components, and a resin layer having a thickness of 0.5 μm is formed. Formed. Next, this silicon wafer was heated at 230 ° C. for 15 minutes to cure the resin layer, thereby forming a support with a flattened film. On this support, the previously obtained colored photosensitive resin composition 1 is applied by spin coating, and heated at 100 ° C. for 1 minute to remove volatile components and form a colored photosensitive resin composition layer. It was done. Next, the obtained colored photosensitive resin composition layer was subjected to i through a mask pattern (2 μm square pixels were formed in a checkered pattern) using an exposure machine (Nikon NSR i9C; manufactured by Nikon Corporation). After the irradiation of the line was performed in 30 steps at intervals of 10 msec over 20 to 310 msec, each exposed support was subjected to 23 ° C. in a developer (CIS DEVELOPER; manufactured by ENF Technology). Development was performed by immersion for 60 seconds. After development, washing with water and drying, a color filter having pixels formed in a checkered pattern having a line width of 2.0 μm and a thickness of 0.7 μm on the support was obtained.

[Evaluation 2]
When the cross section of the pattern was observed with a scanning electron microscope (S-4500; manufactured by Hitachi, Ltd.), there was almost no residue attached to the portion where the coating layer of the glass substrate was dissolved, and a pattern with good adhesion was obtained. It was.

Comparative Example 1
[Evaluation 1]
A colored photosensitive resin composition 2 was prepared with the composition shown in Table 1. The result of measuring the transmittance (550 nm) of the portion where the coating layer of the glass substrate was dissolved in the same manner as in Example 1 except that the colored photosensitive resin composition 2 was used instead of the colored photosensitive resin composition 1. 98.4% and a residue was observed.

[Evaluation 2]
When the cross section of the pattern was observed in the same manner as in Example 1, adhesion of the residue was observed at the portion where the coating layer of the glass substrate was dissolved.

The colored photosensitive resin composition of the present invention can form a color filter, and the obtained color filter can be used for an image sensor or a liquid crystal display device.

Claims (11)

  A colored photosensitive resin composition comprising (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the binder resin ( B) is derived from a compound having at least one skeleton selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from cyclohexyl (meth) acrylate, and a tricyclodecane skeleton and a dicyclopentadiene skeleton. A colored photosensitive resin composition, which is a resin comprising a structural unit to be removed.   The colored photosensitive resin according to claim 1, wherein the content of the structural unit derived from (meth) acrylic acid is 10 to 40 mol% with respect to the total number of moles of the structural unit constituting the binder resin (B). Composition.   3. The colored photosensitive composition according to claim 1, wherein the content of the structural unit derived from cyclohexyl (meth) acrylate is 20 to 90 mol% with respect to the total number of moles of the structural unit constituting the binder resin (B). Resin composition.   The content of the structural unit derived from the compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton is based on the total number of moles of the structural units constituting the binder resin (B). The colored photosensitive resin composition according to claim 1, which is 1 to 40 mol%.   The binder resin (B) is a resin obtained by reacting a compound derived from (meth) acrylic acid contained in a structural unit with a compound having an unsaturated bond and an epoxy group in one molecule. The colored photosensitive resin composition in any one of -4.   The colored photosensitive resin composition according to claim 1, wherein the binder resin (B) has a polystyrene equivalent weight average molecular weight of 5,000 to 55,000.   (A) Content of a coloring agent is 35-55 mass% in mass fraction with respect to solid content of a colored photosensitive resin composition, The colored photosensitive resin composition in any one of Claims 1-6. .   The pattern formed using the colored photosensitive resin composition of Claims 1-7.   A color filter comprising the pattern according to claim 8.   An image sensor comprising the color filter according to claim 9. A liquid crystal display device comprising the color filter according to claim 9.