JP2006265548A - Color development composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color development composition for forming a color development photosensitive resin composition comprising a dye which has improved dispersibility to a solvent, can form a color filter having excellent heat-resistance, and which also has excellent resolving power. <P>SOLUTION: The color development composition comprises at least a dye (A), a resin (B), and solvent (E), wherein the dye (A) and the resin (B) are so treated as to be dispersed in the solvent (E). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coloring composition used for forming a color filter.

It is known that a color filter used in an image sensor such as a CCD or CMOS is formed using a colored photosensitive resin composition formed using a colored composition containing a dye. However, since the coloring composition containing the dye does not have sufficient heat resistance, the heat resistance required for the color filter is not sufficient, and improvement has been required (for example, see Patent Documents 1 and 2).
In addition, dyes are known as solvents for colored photosensitive resin compositions, such as high boiling point solvents such as ethyl lactate and N, N-dimethylformamide, and low boiling point solvents such as propylene glycol monomethyl ether acetate. It is also known that the solubility of is not sufficient, and there is also a problem in dispersibility in a solvent (see, for example, Patent Document 1).

JP 2004-157455 A3 page 42 line 4 page 8 line JP 2004-246105 A2 page 35 line 3 page 3 line

  An object of the present invention is to form a colored photosensitive resin composition comprising a dye having excellent resolution and capable of forming a color filter with improved dispersibility in a solvent and good heat resistance. It is to provide a coloring composition.

  As a result of intensive studies to find a colored composition that can solve the above-described problems, the present inventors use a dye dispersed in a solvent together with a resin as a colorant for the colored composition. As a result, it has been found that the coloring composition can be used for a colored photosensitive resin composition that can form a pattern having good heat resistance without causing a problem of solubility of the dye in a solvent. The present invention has been completed.

That is, the present invention includes at least a dye (A), a resin (B), and a solvent (E), and a colored composition in which the dye (A) and the resin (B) are dispersed in the solvent (E). It is to provide.
The present invention also includes a colored photosensitive resin composition containing the colored composition, a pattern formed using the colored photosensitive resin composition, a color filter including the pattern, and the color filter. An image sensor is provided.

  By using the colored composition of the present invention, it is possible to provide a colored photosensitive resin composition capable of forming a pattern with good resolution and good heat resistance without causing a problem of solubility of a dye in a solvent. It becomes.

Examples of the dye (A) used in the colored composition of the present invention 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 D include an azo dye base, a xanthene dye base, an anthraquinone dye base, a triphenylmethane dye base, a cyanine dye base, a methine 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 alkoxyalkyl group having 2 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an aryl group having 6 to 21 carbon atoms, or a carbon number. 7 to 21 aralkyl groups are represented.
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 15 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.
Examples of the alkoxyalkyl group having 2 to 15 carbon atoms include a methoxymethylene group, a methoxyethylene group, an ethoxyethylene group, a butoxyethylene group, and a butoxybutylene group.
Examples of the alkenyl group having 2 to 15 carbon atoms include ethenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group and the like.
Examples of the aryl group having 6 to 21 carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 to 21 carbon atoms include phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentanyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group, naphthylbutyl group, and naphthylpenta. Nyl group etc. are mentioned.
Among them, 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- A butyl group, a tert-butyl group, a 2-ethylbutyl group, a 2-ethylpentyl group, a 2-ethylhexyl group, a 2-ethylheptyl group, and a 2-ethyloctyl group, more preferably an isopropyl group, a tert-butyl group, Examples include 2-ethylbutyl group, 2-ethylpentyl group, and 2-ethylhexyl group.
R ^{31 to} R ³⁴ are hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group, tert-butyl group, fluorine atom, chlorine atom, bromine atom, 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 can be used in combination, and the solubility in the solvent used for the colored composition and when forming a color filter pattern using the colored photosensitive resin composition containing the colored composition It is appropriately selected according to the light fading resistance and the spectral spectrum.

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), C.I. 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.

  If necessary, these dyes (A) can be treated with rosin, surface treatment with a derivative having an acidic group or basic group introduced, grafting onto the surface of the dye with a polymer compound, or removal of impurities. For example, cleaning treatment with an organic solvent or water, removal treatment with an ion exchange method of ionic impurities, or the like may be performed alone or in combination.

The mixture of the dye (A), resin (B) and solvent (E) used in the coloring composition of the present invention is in a state where the dye is dispersed in the solution by performing a dispersion treatment such as using a medium such as beads. Obtained as a coloring composition.
The distributed processing can be performed as follows, for example. The resin (B) is dissolved in a solvent (E) such as propylene glycol monomethyl ether acetate to obtain a varnish, and after adding the dye (A) to the varnish, it is kneaded using a kneader such as a three-roller. To obtain a dye-containing varnish. Here, the content of the resin (B) can be the total amount of the resin used in the coloring composition or a part thereof.
Next, using a media mill such as zirconia beads, the dye-containing varnish, the resin (B), and propylene glycol monomethyl ether acetate are dispersed to obtain a colored composition.

As the resin (B), at least one polymer selected from the group consisting of an alkali-soluble resin (B1) and a dispersant (B2) is used.
Examples of the alkali-soluble resin (B1) include the same as the alkali-soluble resin (B1) described later.
Examples of the dispersant (B2) include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and may be used alone or in combination of two or more. .
When using a dispersing agent, the usage-amount is a mass fraction with respect to dye (A), Preferably it is 1 to 100 mass%, More preferably, it is 5 to 50 mass%. It is preferable that the amount of the dispersant used be in the above range because a colored composition having a uniform dispersion state tends to be obtained.
Here, in the process of obtaining the said coloring composition, resin (B) uses the whole quantity used when it is set as a colored photosensitive resin composition, or its one part. The resin (B) may be used alone or in combination of two or more.
Content of resin (B) is a mass fraction with respect to dye (A), Preferably they are 1 mass% or more and 100 mass% or less, More preferably, they are 5 mass% or more and 50 mass% or less. It is preferable that the content of the resin (B) is in the above range because a colored composition in which the dye is uniformly dispersed tends to be obtained.
The colored composition obtained as described above is preferable because it can provide a colored photosensitive resin composition that can form a pattern with good resolution and good adhesion and heat resistance.

The content of the dye (A) is a mass fraction with respect to the solid content of the colored photosensitive resin composition, preferably 20 mass% to 60 mass%, more preferably 25 mass% to 55 mass%. %, Particularly preferably 27% by mass or more and 55% by mass or less, more preferably 30% by mass or more and 50% by mass or less.
When the content of the dye (A) is in the above range, the color density when the color filter is obtained is sufficient, and the composition is alkali-soluble resin (B1), photopolymerizable compound (C), photopolymerization. Since a necessary amount of components such as the initiator (D) can be contained, it is preferable.

  The colored photosensitive resin composition of the present invention contains an alkali-soluble resin (B1). The alkali-soluble resin (B1) is preferably one that can be dissolved in the developer in the development step after exposure. The alkali-soluble resin (B1) preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is a mole fraction in the total structural units constituting the alkali-soluble resin (B1), preferably 16 mol% or more and 40 mol% or less, more preferably It is 18 mol% or more and 38 mol% or less. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility of the non-pixel portion is good during development, and the residue tends not to remain in the non-pixel portion after development. Yes, it is preferable.

  Examples of the other monomer that derives the constituent unit of the alkali-soluble resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, Saturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups at the ends of polymer molecular chains or Examples thereof include macromonomers having a monomethacryloyl group, units represented by the formula (II), and units represented by the formula (III).

[In Formula (II) and Formula (III), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

Specific examples of the alkali-soluble resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / Styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (II) (wherein, in formula (II), R ³ represents a methyl group, and R ⁴ represents hydrogen Represents a atom) / benzyl methacrylate copolymer, a constituent represented by the formula (II) (herein, in the formula (II), R ³ represents a methyl group, and R ⁴ represents a hydrogen atom). ) / Benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (III) (however, In formula (III), R ³ represents a methyl group, and R ⁴ represents a hydrogen atom.) / Styrene copolymer / Tricyclodecanyl methacrylate copolymer and the like are preferable.

The acid value of the alkali-soluble resin (B1) used in the present invention is preferably 50 to 150, preferably 60 to 135, particularly preferably 70 to 135. 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. .

  Content of alkali-soluble resin (B1) is a mass fraction with respect to solid content of a coloring photosensitive resin composition including the carry-in from a coloring composition, Preferably it is 15-35 mass%, More preferably Is 18 to 33% by mass, particularly preferably 21 to 31% by mass. When the content of the alkali-soluble resin (B1) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved, which is preferable.

Alkali-soluble resin having a component represented by formula (I), for example, methacrylic acid / component represented by formula (IV) (wherein, in formula (II), R ³ represents a methyl group, R ⁴ represents a hydrogen atom.) / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer is represented by the formula (IV). (Wherein, in formula (IV), R ⁵ represents a hydrogen atom).

Methacrylic acid / constituent component represented by formula (III) (in this case, in formula (III), R ³ represents a methyl group and R ⁴ represents a hydrogen atom) / tricyclodecanyl methacrylate copolymer The coalescence can be obtained by reacting glycidyl methacrylate with a monomethacrylate copolymer having a benzyl methacrylate, methacrylic acid, or tricyclodecane skeleton.

  The polystyrene-converted weight average molecular weight of the alkali-soluble resin (B1) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. is there. 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 photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light, and is, 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 photopolymerizable compounds (C) may be used alone or in combination of two or more.
Content of a photopolymerizable compound (C) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 5 to 90 mass%, More preferably, it is 10 to 80 mass%. More preferably, it is 20 mass% or more and 70 mass% or less. When the content of the photopolymerizable compound (C) is in the above range, curing is sufficiently performed, the film thickness ratio before and after the development is improved, the pattern is less likely to be undercut, and the adhesion is improved. It is preferable because of its tendency.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include acetophenone compounds, active radical generators, and acid generators.
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 (t-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 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 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- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium 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.

  Content of a photoinitiator (D) is a mass fraction with respect to the total amount of alkali-soluble resin (B1) and a photopolymerizable compound (C), Preferably it is 0.1 to 20 mass%. More preferably, it is 1 mass% or more and 15 mass% or less. When the content of the photopolymerization initiator is in the above range, the sensitivity is increased and the exposure time is shortened, so that the productivity of the color filter is improved, while the sensitivity becomes too high, and the line and space pattern is increased. This is preferable because the line width does not tend to be too large at the minimum line width to be resolved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (G). The photopolymerization initiation assistant (G) is a compound that is usually used in combination with the photopolymerization initiator (D), and is used to accelerate the polymerization of the photopolymerizable compound that has been polymerized by the photopolymerization initiator. is there.
Examples of the photopolymerization initiation aid (G) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
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 (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  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.

  The photopolymerization initiation assistant (G) may be used alone or in combination of two or more. Moreover, as a photoinitiation adjuvant (G), a commercially available thing can also be used, and as a commercially available photoinitiation assistant (G), for example, EAB-F (made by Hodogaya Chemical Co., Ltd.) Etc.

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (G) 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-hydroxycyclohexylphenyl Ton / 4,4′-bis (diethylamino) benzophenone, oligomer of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4,4′-bis (diethylamino) ) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When these photopolymerization initiation assistants (G) are used, the amount used is preferably 0.01 mol or more and 10 mol or less, more preferably 0.01 mol, per mol of the photopolymerization initiator (D). It is 5 mol or less.

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 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 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 aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.
Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
Examples of 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-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-metho Methyl cypropionate, 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 amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
Among the above solvents, a solvent containing propylene glycol monomethyl ether acetate is preferably used. The content of propylene glycol monomethyl ether acetate in the solvent is preferably 50 to 100% by mass, more preferably 55 to 97% by mass, and particularly preferably 60 to 95% by mass.
These solvents may be used alone or in combination of two or more.
The content of the solvent (E) in the colored composition or colored photosensitive resin composition of the present invention is a mass fraction with respect to the colored composition or colored photosensitive resin composition, preferably 70% by mass or more and 90% by mass. Hereinafter, it is 75 to 88 mass% more preferably. When the content of the solvent (E) is in the above-mentioned range, it is preferable because 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.

The colored photosensitive resin composition of the present invention may further contain a surfactant. Examples of the surfactant include at least one selected from the group consisting of 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, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: 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, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F183, R183 (large) Nippon Ink Chemical Co., Ltd.), Ftop (trade name) EF301, EF303, EF351, EF352, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: 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. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.
When the surfactant is contained, the content thereof is a mass fraction with respect to the colored photosensitive resin composition, preferably 0.0005% by mass to 0.6% by mass, and more preferably 0.001% by mass. % Or more and 0.5% by mass. When the content of the surfactant is in the above range, the flatness during application tends to be good, which is preferable.

  The colored photosensitive resin composition of the present invention further includes a filler, a polymer compound other than the resin (B), an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amino compound, You may contain additives, such as a hardening | curing agent.

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

  Examples of the polymer compound other than the alkali-soluble 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-t-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.

Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid are listed.

Examples of the organic amine compound include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, and n-heptylamine. Monoalkylamines such as n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-butylamine, disec-butylamine, di-t-butylamine, di dialkylamines such as 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, tri-i-propylamine, tri-n-butylamine, tri trialkylamines such as i-butylamine, trisec-butylamine, tri-t-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, di-i-propanolamine, di-n-butanolamine, dii-butanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, 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, pi-propylaniline, pn-butylaniline, pt-butylaniline, Aromatic amines such as 1-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 an alkali-soluble resin by being heated to crosslink the alkali-soluble resin, a compound that can be polymerized alone to cure a colored pattern, and the like. Can be mentioned. Examples of the compound include an epoxy compound and an oxetane compound, and an oxetane compound is preferably used.

  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 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. . 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 (all manufactured by Shin Nippon Rika Co., Ltd.), and the like.

  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 dye (A) is dispersed by coexisting a dispersant in a solvent (E) to prepare a dye (A) dispersion, The alkali-soluble resin (B1), the photopolymerizable compound (C), the photopolymerization initiator (D) and other additives as necessary are dissolved, mixed with the dye (A) dispersion, and if necessary, a solvent. And the like.

  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 steps described above for each color (3 colors or 4 colors) to produce a cured film.
More specifically, the colored photosensitive resin composition of the present invention is generally dried at a thickness of 0.1 to 5 μm, preferably 0. It coats so that it may become 2-2 micrometers, and it heats, for example for 3 minutes with heating apparatuses, such as 100 degreeC oven, and obtains a smooth coating film.

  The substrate is not particularly limited, but is a glass plate, a plastic plate, an aluminum plate, a base material for electronic parts such as a silicon wafer for an image sensor, and further a transparent resin plate, a resin film, a cathode ray tube display surface, a light receiving surface of the image pickup tube. , CCD, BBD, CID, wafers with solid-state image sensors such as BASIS, contact image sensors using thin film semiconductors, liquid crystal display surfaces, color electrophotographic photoreceptors, electrochromic (EC) display substrates Etc.

  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, an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate in accordance with the amount of received light and a read gate unit for outputting the generated electrons. If light hits the gate part, it causes noise and accurate data is not output.Therefore, a light shielding film layer is formed on the top of the readout gate part, and there is a step between the photodiode part without the light shielding film layer. It may have occurred. 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 flattening film include a photosensitive resin composition as in the present invention, and an acrylic or epoxy thermosetting resin.
After applying the photosensitive resin composition, pre-baking is usually performed to evaporate the solvent and obtain a dry coating film. Examples of the pre-baking method include reduced-pressure drying, indirect heating drying using high-temperature air, direct heating drying using a hot plate or the like (80 to 140 ° C., 50 to 200 seconds), and the like. 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, when a three-color filter is manufactured, the first formed pattern is then subjected to application, exposure, and development of another color resist solution twice. At this time, post-baking is performed so as not to cause pattern omission due to color mixing with the applied resist solution, exposure, and development. 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, in the case of heating by an oven, it is heated at 120 to 250 ° C. for 1 to 60 minutes, and in the case of heating by a hot plate, it is heated at 100 to 250 ° C. for 2 to 60 minutes.
Although the light source for exposure is not particularly limited, i-line of a mercury lamp can be cited as a light source that has a remarkable effect on the pattern forming property. The feature of the present invention is particularly remarkable in the production of a color filter for an image sensor in which i-line, which is one of the line spectrum of a mercury lamp, is used from an appropriate aspect of the process. Of course, it can be used.
There is no restriction | limiting in particular in the developing solution used for image development of a curable composition, A conventionally well-known developing solution can be used. Among them, an organic alkaline developer of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) is preferable for achieving the object of the present invention.

  A color filter can be obtained by repeating the pattern formed through the above steps for each different hue, and the color filter is preferably used as a component of the image sensor.

  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.

<Synthesis of Resin (B1)>
333 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, after the temperature of the solution in the flask was raised to 100 ° C., 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 70.5 g of benzyl methacrylate (0 .40 mol), 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were added dropwise to the flask using a dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours.
After the stirring was completed, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was changed to air. Then, 35.5 g of glycidyl methacrylate [0.25 mol (based on methacrylic acid used in this reaction)] 50 mol% in terms of mole fraction)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, the reaction was continued for 6 hours at 110 ° C., and the solid content, acid value of 80 mg KOH / g Resin B1 was obtained.
Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually a potassium hydroxide aqueous solution having a known concentration. It is calculated | required by titrating using.
The obtained resin B1 had a weight-average molecular weight in terms of polystyrene measured by GPC method of 9,000.

About the measurement of the polystyrene conversion weight average molecular weight of said alkali-soluble 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 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): C.I. I. Solvent Yellow 162

(A-2): C.I. I. Solvent Orange 56

(A-3): C.I. I. Acid Red 289

(A-4): C.I. I. Acid Green 16

<Preparation of colored composition (A-11)>
Propylene glycol monomethyl ether acetate: Dye (A-1) / (A-2) / (A-3) = 31/33/36: 200 g in three rolls in 260 g of varnish in which resin B1: 60 g was dissolved in 200 g Kneading and dispersing, then using a media mill with an internal volume of 1 L (using 0.5 mm zirconia beads with an internal volume of 80 vol%), the resin-treated dye slurry: 460 g, resin B 1: 20 g and propylene glycol monomethyl ether acetate : 520 g was dispersed to obtain a colored composition (A-11).

<Preparation of colored composition (A-12)>
Internal volume: Using a 1 L media mill (using 0.5 mm zirconia beads with an internal volume of 80% by volume), dye (A-1) / (A-2) / (A-3) = 31/33/36: 200 g, Resin B 1: 80 g and propylene glycol monomethyl ether acetate: 720 g were dispersed to obtain a colored composition (A-12).

<Preparation of colored composition (A-13)>
Propylene glycol monomethyl ether acetate: Dye (A-1) / (A-4) = 52/48: 200 g was kneaded and dispersed with three rolls in 260 g of varnish in which resin B1: 60 g was dissolved in 200 g, and then the contents Product: Using a 1 L media mill (using 0.5 mm zirconia beads with an internal volume of 80% by volume), the resin-treated dye slurry: 460 g, resin B 1:20 g, and propylene glycol monomethyl ether acetate: 520 g are dispersed and colored. A composition (A-13) was obtained.

<Preparation of colored composition (A-14)>
Internal volume: Using a 1 L media mill (using 0.5 mm zirconia beads with an internal volume of 80% by volume), dye (A-1) / (A-4) = 52/48: 200 g, resin B1: 80 g and propylene Glycol monomethyl ether acetate: 720 g was dispersed to obtain a colored composition (A-14).

<Preparation of colored composition (A-15)>
Internal volume: Using a 1 L media mill (using 0.5 mm zirconia beads with an internal volume of 80% by volume), dye (A-1) / (A-4) = 52/48: 200 g, polyester polymer dispersion Agent (Solsperse 24000GR (manufactured by Avicia)): 60 g and propylene glycol monomethyl ether acetate: 740 g were dispersed to obtain a colored composition (A-15).

(B-1) Resin B1
(C-1) Photopolymerizable compound: Dipentaerythritol hexaacrylate (D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (G- 1) Photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (E-1) Solvent: Propylene glycol monomethyl ether acetate (E-2) Solvent: Ethyl 3-ethoxypropionate (H-1) polyether Modified silicone oil SH8400 (Toray Silicone Co., Ltd.)

Example 1
[Preparation of colored photosensitive resin composition 1]
The following components were mixed to obtain a colored photosensitive resin composition 1.
(A-11) 44.100 parts by mass (B-1) 1.144 parts by mass (C-1) 4.344 parts by mass (D-1) 1.043 parts by mass (G-1) 0.348 parts by mass (E-1) 35.820 parts by mass (E-2) 7.900 parts by mass (H-1) 0.011 parts by mass

[Formation of pattern]
A silicon wafer is spin-coated with Sumistres PR-1300Y-PG (manufactured by Sumitomo Chemical Co., Ltd.), then heated at 100 ° C. for 1 minute to remove volatile components, and a flattened film forming material having a thickness of 0.5 μm A layer was formed. Next, the wafer was heated at 230 ° C. for 15 minutes to cure the planarization film forming material layer and form a support. The previously obtained colored photosensitive resin composition 1 is applied onto this support (silicon wafer with a flattened film) by spin coating, and heated at 100 ° C. for 3 minutes to volatilize the volatile components, thereby coloring the photosensitive resin. A composition layer was formed.
Next, the obtained colored photosensitive resin composition layer is formed with a pattern [2 μm square pixels in a pine pattern using an exposure machine (Nikon NSR i9C; manufactured by Nikon Corporation). I-line irradiation through a mask having [10] to 300 msec, stepwise exposure to 30 locations at 10 msec intervals], and then the substrate in a developer [0.05 mass% TMAH aqueous solution] at 23 ° C. for 60 seconds. Dipped and developed. After development, it was washed with water and dried to obtain a checkered pattern having a line width of 2.0 μm and a thickness of 2.0 μm.
Separately, on the glass substrate (# 1737; manufactured by Corning), the colored photosensitive resin composition 1 obtained above was applied by spin coating, and then dried at 100 ° C. for 1 minute to volatilize the volatile components. A layer of a colored photosensitive resin composition was formed. After cooling, this colored photosensitive resin composition layer was exposed by irradiating with i-line (wavelength 365 nm) without passing through a photomask to obtain a colored film formed on the entire surface of the substrate. As an i-line light source, an ultra-high pressure mercury lamp was used, and the irradiation light amount was 150 mJ / cm ² . The chromaticity of the obtained colored film was measured using a chromaticity meter (OSP-SP-200; manufactured by OLYMPUS).

[Evaluation]
(1) Evaluation of foreign matter Using a scanning electron microscope (S-4100; manufactured by Hitachi, Ltd.), the obtained substrate was observed. did. The results are shown in Table 1.
(2) Shape evaluation When the cross section of the pattern was confirmed with a scanning electron microscope, the trapezoidal shape of the cross section had a good taper shape with an angle between the base and the side in contact with the base of about 80 to 90 °, and the resolution was 2 μm or less. The thing was set to (circle) and the others were set to x. The results are shown in Table 1. In addition, it can be said that what can form a pattern has favorable adhesiveness at least.
(3) Surface roughness When the pattern surface is observed with a microscope (Nanopics; manufactured by Seiko Instruments Inc.), the average roughness (surface roughness refers to the unevenness of the coating film surface) is 3 nm or less. Otherwise, it was set as x. The results are shown in Table 1.
(4) Evaluation of heat resistance After the colored film was formed, heat treatment was performed at 150 ° C. for 2 minutes. After the heat treatment, the chromaticity was measured in the same manner as described above. The chromaticity immediately after the formation of the colored film was compared with the chromaticity after the heat treatment, and the color difference between them was 3 or less, and the others were x. The results are shown in Table 1.

Comparative Example 1
[Preparation of colored photosensitive resin composition 2]
The following components were mixed, but the dye (A) did not dissolve. Further, the dispersion was insufficient, and an aggregate of dyes was obtained, and a uniform colored photosensitive resin composition was not obtained.
(A-3) 3.780 parts by mass (A-2) 3.465 parts by mass (A-1) 3.255 parts by mass (B-1) 4.521 parts by mass (C-1) 4.521 parts by mass (D-1) 1.085 parts by mass (G-1) 0.362 parts by mass (E-1) 71.100 parts by mass (E-2) 7.900 parts by mass (H-1) 0.011 parts by mass

Comparative Example 2
[Preparation of colored photosensitive resin composition 3]
The following components were mixed to obtain a colored photosensitive resin composition 3. A pattern was formed in the same manner as in Example 1, but no pattern remained.
(A-3) 3.780 parts by mass (A-2) 3.465 parts by mass (A-1) 3.255 parts by mass (B-1) 1.144 parts by mass (C-1) 4.344 parts by mass (D-1) 1.043 parts by mass (G-1) 0.348 parts by mass Ethyl lactate 46.800 parts by mass N, N-dimethylformamide 31.200 parts by mass (H-1) 0.011 parts by mass

Example 2
[Preparation of colored photosensitive resin composition 4]
A colored photosensitive resin composition 4 was obtained in the same manner as in Comparative Example 2 except that (A-11) in the colored photosensitive resin composition 3 was replaced with (A-12).

[Formation and evaluation of patterns]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 4. The results are shown in Table 1.

Comparative Example 3
[Preparation of colored photosensitive resin composition 5]
The following components were mixed, but the dye (A) did not dissolve. Further, the dispersion was insufficient, and an aggregate of dyes was obtained, and a uniform colored photosensitive resin composition was not obtained.
(A-4) 3.420 parts by mass (A-1) 6.580 parts by mass (B-1) 4.306 parts by mass (C-1) 4.306 parts by mass (D-1) 1.033 parts by mass (G-1) 0.344 parts by mass (E-1) 80.000 parts by mass (H-1) 0.010 parts by mass

Comparative Example 4
[Preparation of colored photosensitive resin composition 6]
The following components were mixed to obtain a colored photosensitive resin composition 6. A pattern was formed in the same manner as in Example 1, but no pattern remained.
(A-4) 3.420 parts by mass (A-1) 6.580 parts by mass (B-1) 4.306 parts by mass (C-1) 4.306 parts by mass (D-1) 1.033 parts by mass (G-1) 0.344 parts by mass ethyl lactate 48.000 parts by mass N, N-dimethylformamide 32.000 parts by mass (H-1) 0.010 parts by mass

[Formation and evaluation of patterns]
Evaluation was performed in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 6. The results are shown in Table 2.

Example 3
[Preparation of colored photosensitive resin composition 7]
The following components were mixed to obtain a colored photosensitive resin composition 7.
(A-13) 50.000 parts by mass (B-1) 0.306 parts by mass (C-1) 4.306 parts by mass (D-1) 1.033 parts by mass (G-1) 0.344 parts by mass (E-1) 44.000 parts by mass (H-1) 0.010 parts by mass

[Formation and evaluation of patterns]
Evaluation was carried out in the same manner as in Example 2 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 7.

Example 4
[Preparation of colored photosensitive resin composition 8]
A colored photosensitive resin composition 8 was obtained in the same manner as in Example 3 except that (A-13) in the colored photosensitive resin composition 7 was replaced with (A-14).

Example 5
[Preparation of colored photosensitive resin composition 9]
The following components were mixed to obtain a colored photosensitive resin composition 9.
(A-15) 50.000 parts by mass (B-1) 1.306 parts by mass (C-1) 4.306 parts by mass (D-1) 1.033 parts by mass (G-1) 0.344 parts by mass (E-1) 43.000 parts by mass (H-1) 0.010 parts by mass

[Formation and evaluation of patterns]
Evaluation was carried out in the same manner as in Example 1 except that the colored photosensitive resin composition 1 of Example 1 was replaced with the colored photosensitive resin composition 9.

The colored composition of the present invention is used for a colored photosensitive resin composition for forming a pixel of a color filter for a display device such as an LCD as well as a colored photosensitive resin composition for forming a color filter for an image sensor such as a CCD or CMOS. be able to.

Claims (9)

  A coloring composition comprising at least a dye (A), a resin (B) and a solvent (E), wherein the dye (A) and the resin (B) are dispersed in the solvent (E).   The colored composition according to claim 1, wherein the resin (B) is at least one polymer selected from the group consisting of an alkali-soluble resin (B1) and a dispersant (B2).   The coloring composition according to claim 1 or 2, wherein the solvent (E) contains propylene glycol monomethyl ether acetate.   The colored photosensitive resin composition containing the coloring composition in any one of Claims 1-3.   The colored photosensitive resin composition according to claim 4, comprising an alkali-soluble resin (B1), a photopolymerizable compound (C), and a photopolymerization initiator (D).   The colored photosensitive resin composition according to claim 4 or 5, wherein the content of the dye (A) is 20% by mass to 60% by mass with respect to the solid content of the colored photosensitive resin composition.   The pattern formed using the colored photosensitive resin composition in any one of Claims 4-6.   A color filter comprising the pattern according to claim 7. An image sensor comprising the color filter according to claim 8.