JP2008242325A - Color photosensitive resin composition and color filter array, solid-state image sensor and camera system using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color photosensitive resin composition with which a color filter array exhibiting favorable spectral characteristics can be formed. <P>SOLUTION: The color photosensitive resin composition contains a dyestuff expressed by formula (I), an alkali-soluble resin, a photosensitive compound, a curing agent and a solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored (colored) photosensitive resin composition useful for producing a color filter array formed on a solid-state imaging device (such as an image sensor) or a liquid crystal display device.

  As a color filter array for colorizing (coloring) a solid-state imaging device or a liquid crystal display device, for example, a red filter layer (R), a green filter layer (G), and a blue filter layer (B) are provided on the device. A color filter array formed adjacent to the same plane is known. The plane pattern of each filter layer (R, G, B) of the color filter array is appropriately set. For example, a Bayer pattern (mosaic pattern) or a band pattern is known. The filter layer has a combination of primary colors composed of red (R), green (G), and blue (B) as well as a combination of complementary colors composed of yellow (Y), magenta (M), and cyan (C). Sometimes adopted.

  Color filter arrays are often manufactured by a color resist method in which a colored photosensitive resin composition corresponding to each filter layer is prepared, and these are sequentially exposed, developed, and patterned. A pigment is frequently used as a dye contained in the product. However, since the pigment does not dissolve in the developer, it is disadvantageous for forming a fine pattern. Therefore, in recent years, the use of dyes has been proposed as a pigment that dissolves in a developer.

  For example, Patent Document 1 discloses a triarylmethane dye (dye) having an absorption maximum at a wavelength of 550 to 650 nm, specifically C.I. I. Acid Blue 7, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Solvent Blue 38, C.I. I. Acid Violet 17, C.I. I. Acid Violet 49, C.I. I. Acid Green 3 and the like have been introduced as dyes having excellent spectral characteristics in the field of solid-state imaging devices. In particular, C.I. I. Acid Blue 90 is a dye represented by the formula (II), and it has been confirmed in the examples that it has excellent spectral characteristics.

Many blue dyes are known, but their spectral characteristics are not known, and their suitability as a color filter array is unknown. For example, Patent Document 2 discloses a disperse dye composition containing a plurality of dyes in order to dye a hydrophobic fiber material, particularly a polyester fiber material called a new synthetic fiber, in blue. Patent Document 3 lists a plurality of pigments (dyes) as pigments of the cyan color material layer in the thermal transfer sheet. However, the target field of these documents is completely different from the color filter array. Further, there is no disclosure as to whether or not the listed blue dyes are excellent in spectral characteristics as pigments for color filter arrays.
Japanese Patent Laid-Open No. 2002-14222 JP-A-11-29716 JP 2003-205686 A

  By the way, in recent years, the pattern of the solid-state imaging device has been increasingly miniaturized, and accordingly, the filter pattern has to be miniaturized. In order to miniaturize the filter pattern, it is effective to further improve the spectral characteristics of the color filter array and make the color filter array itself thinner. The present invention has been made paying attention to the above-described circumstances, and an object thereof is to provide a colored photosensitive resin composition capable of forming a color filter array exhibiting further excellent spectral characteristics. “Good spectral characteristics” means that light in a predetermined wavelength range is sufficiently absorbed, but light in other wavelength ranges is transmitted satisfactorily.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a specific thiazole-triazolopyridine dye (hereinafter also referred to as “thiazole dye”) in which a thiazole ring is bonded to a triazolopyridine skeleton. Found that the spectral characteristics were superior to the triarylmethane dye described in Patent Document 1, and completed the present invention. That is, the colored photosensitive resin composition of the present invention is characterized in that it contains a thiazole dye represented by the formula (I).

In formula (I), X represents a nitrogen atom or CH.
R ¹¹ represents a hydrogen atom or a C _1-4 alkyl group.
R ¹² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group or a C _1-4 alkoxycarbonyl group.
R ¹³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents a C _1-8 alkyl group. However, when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom.
R ^{14 to} R ¹⁶ are each independently a hydrogen atom, an amino group or a C _1-20 alkyl group optionally substituted with a halogen atom, an amino group optionally substituted with a C _1-20 alkyl group, C _1-20 ether groups containing one or more oxygen atoms, _optionally substituted aromatic groups, or hydroxyl groups.
In the present invention, C _ab means that the carbon number is a or more and b or less.

  The colored photosensitive resin composition of the present invention contains an alkali-soluble resin, a photosensitive compound (particularly an oxime compound), a curing agent, and a solvent in addition to the thiazole dye represented by the formula (I). The present invention also includes a color filter array formed using the colored photosensitive resin composition, a solid-state image sensor including the color filter array, and a camera system including the solid-state image sensor.

  According to the present invention, since the thiazole dye represented by the formula (I) is used in the colored photosensitive resin composition, the spectral characteristics of the color filter array formed using the colored photosensitive resin composition are improved. Further improvements can be made.

The colored photosensitive resin composition of the present invention is characterized by containing a thiazole dye represented by formula (I) (hereinafter sometimes referred to as thiazole dye (I)). The thiazole dyes represented by the formula (I) may be used alone or in appropriate combination of several kinds. Preferred R ¹¹ in the formula (I) is a C _1-3 alkyl group, more preferably a methyl group. Preferred R ¹² is a cyano group, and preferred R ¹³ is an oxygen atom. R ¹⁴ is preferably a methyl group, an ethyl group, or a dialkylmethyl group (particularly a dilinear alkylmethyl group) having about 3 to 20 (preferably about 4 to 10) carbon atoms. Preferred R ¹⁵ is an amino group substituted with two C _1-10 alkyl groups (more preferably a C _3-6 alkyl group), particularly an N-diisopropylamino group, N, N-di-n-butylamino. Group, N, N-di-n-pentylamino group, N, N-di-n-hexylamino group. R ¹⁶ is preferably a hydrogen atom, a linear or branched C _1-8 alkyl group, a naphthyl group or a phenyl group, more preferably a hydrogen atom, a branched C _3-4 alkyl group (isopropyl group, Isopentyl group, tert-butyl group, etc.) or phenyl group.

  More specific examples of these thiazole dyes (I) include dyes represented by formulas (I-1) to (I-5).

  The thiazole dye (I) has excellent spectral characteristics and can be used alone as a blue dye in a blue filter layer, but has an absorption maximum at a wavelength of 600 to 700 nm for color adjustment, that is, to adjust spectral characteristics. You may use together a pigment | dye (dye). Examples of the dye having an absorption maximum at a wavelength of 600 to 700 nm include a copper phthalocyanine dye (hereinafter sometimes referred to as copper phthalocyanine dye (III)) represented by the formula (III).

[In the formula (III), R ^{30 to} R ³³ each independently represents a sulfonic acid group or a sulfonamide group represented by the formula (III-1).
R ³⁴ HN—SO ₂ − (III-1)
{In Formula (III-1), R ³⁴ represents a hydrogen atom, a C _2-20 alkyl group, a C _2-12 alkyl group substituted with a cyclohexyl group, a cyclohexyl group substituted with a C _1-4 alkyl group, C _2-12 C _2-12 alkyl group substituted with an alkoxyl group, a phenyl group substituted with a C _1-20 alkyl group, C _1-20 alkyl group substituted with a phenyl group, represented by formula (III-2) An alkylcarbonyloxyalkyl group, or an alkoxycarbonylalkyl group represented by the formula (III-3).
R ³⁵ —CO—O—R ³⁶ — (III-2)
R ³⁷ —O—CO—R ³⁸ − (III-3)
(In Formula (III-2) and Formula (III-3), R ³⁵ and R ³⁷ each independently represent a C _2-12 alkyl group, and R ³⁶ and R ³⁸ each independently represent C 2 _{2-12 represents an} alkylene group.)}
a, b, c and d each independently represent an integer of 0 to 2; ]

The copper phthalocyanine dye represented by the formula (III) can form a salt with a base, for example, when any of R ^{30 to} R ³³ is a sulfonic acid group. Examples of the salt form include metal salts with alkali metals such as sodium and potassium, and amine salts with amines such as trimethylamine, 2-ethylhexylamine and 1-amino-3-phenylbutane.

  Examples of the copper phthalocyanine dye (III) include C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 67, C.I. I. Acid Blue 249, C.I. I. Direct Blue 86 etc. are included. These copper phthalocyanine dyes (III) may be used alone or in combination of two or more. The content of the copper phthalocyanine dye (III) is preferably about 30 to 70% by mass, more preferably 40 to 60% by mass with respect to the total content of the thiazole dye (I) and the copper phthalocyanine dye (III). %.

  Moreover, the colored photosensitive resin composition of this invention may contain the pigment | dye (dye) which has an absorption maximum in wavelength 500-600 nm, in order to adjust spectral characteristics. Examples of the dye having an absorption maximum at a wavelength of 500 to 600 nm include a xanthene dye represented by the formula (IV) (hereinafter sometimes referred to as xanthene dye (IV)).

[In the formula (IV), Z ⁻ represents BF ⁴⁻ , PF ⁶⁻ , X ⁻ or XO ⁴⁻ (wherein X represents a halogen atom).
R ⁴¹ and R ⁴³ each independently represents a hydrogen atom or a C _1-8 alkyl group.
^R42 represents a sulfonic acid group, a carboxylic acid group, an ester or salt thereof, or a sulfonamide group represented by the formula (IV-1).
R ⁴⁵ HN—SO ₂ − (IV-1)
{In Formula (IV-1), R ⁴⁵ represents a hydrogen atom, a C _2-20 alkyl group, a C _2-12 alkyl group substituted with a cyclohexyl group, a cyclohexyl group substituted with a C _1-4 alkyl group, C _2-12 C _2-12 alkyl group substituted with an alkoxyl group, C _1-20 alkyl phenyl group optionally substituted with a group, optionally C _1-20 alkyl group optionally substituted with a phenyl group, the formula ( An alkylcarbonyloxyalkyl group represented by IV-2) or an alkoxycarbonylalkyl group represented by formula (IV-3) is shown.
R ⁴⁶ —CO—O—R ⁴⁷ — (IV-2)
R ⁴⁸ —O—CO—R ⁴⁹ — (IV-3)
(In formula (IV-2) and formula (IV-3), R ⁴⁶ and R ⁴⁸ each independently represent a C _2-12 alkyl group, and R ⁴⁷ and R ⁴⁹ each independently represent C 2 _{2-12 represents an} alkylene group.)}
R ⁴⁰ and R ⁴⁴ each independently represent a hydrogen atom, a C _1-8 alkyl group, or a substituted phenyl group represented by the formula (IV-4).

{In Formula (IV-4), R ⁴⁰⁰ and R ⁴⁰² each independently represent a hydrogen atom or a C _1-3 alkyl group, and R ⁴⁰¹ represents a sulfonic acid group, a carboxylic acid group, an ester or a salt thereof. Or a sulfonamide group represented by formula (IV-1). }]

  As the xanthene dye (IV), C.I. I. Basic Red 1, C.I. I. Examples thereof include Acid Red 289 or a dye represented by Formula (IVa).

  The xanthene dye (IV) may be used alone or in combination of two or more. Further, xanthene dye (IV) and copper phthalocyanine dye (III) may be used in combination as a toning dye. The content of the xanthene dye is preferably about 10 to 70% by mass, more preferably about 20 to 50% by mass with respect to the total content of the thiazole dye (I) and the xanthene dye (IV). .

  The thiazole dye (I) used in the composition of the present invention can be obtained, for example, according to the method disclosed in JP-T-9-508403.

  The colored photosensitive resin composition of the present invention contains an alkali-soluble resin, a photosensitive compound, a curing agent, and a solvent in addition to the thiazole dye (I). The composition of the present invention is preferably a negative type, but may be a positive type.

  The photosensitive compound is properly used depending on whether the colored photosensitive resin composition is a positive composition or a negative composition. The photosensitive compound for the positive composition is generally called a photosensitive agent, and various known compounds can be used. More specifically, examples of the photosensitizer include an ester of a phenol compound and an o-naphthoquinone diazide sulfonic acid compound (such as o-naphthoquinone diazide-5-sulfonic acid, o-naphthoquinone diazide-4-sulfonic acid).

  Examples of the phenol compound include di, tri, tetra, or pentahydroxybenzophenone (such as 2,3,4,4'-tetrahydroxybenzophenone) and compounds represented by formulas (101) to (111).

  On the other hand, a photoacid generator can be used as the photosensitive compound for the negative composition. The kind of photoacid generator is not particularly limited, and various known photoacid generators [for example, iodonium salt compounds, sulfonium salt compounds, organic halogen compounds (haloalkyl-s-triazine compounds, etc.), sulfonate ester compounds, disulfones Compounds, diazomethanesulfonyl compounds, N-sulfonyloxyimide compounds, oxime compounds, and the like]. A preferred photoacid generator is an oxime compound.

  Examples of the oxime compounds include α- (4-toluenesulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- (camphorsulfonyloxyimino) -4. -Methoxybenzyl cyanide, α-trifluoromethanesulfonyloxyimino-4-methoxybenzyl cyanide, α- (1-hexanesulfonyloxyimino-4-methoxybenzyl cyanide, α-naphthalenesulfonyloxyimino-4-methoxybenzyl cyanide Nido, α- (4-toluenesulfonyloxyimino) -4-N-diethylanilyl cyanide, α- (4-toluenesulfonyloxyimino) -3,4-dimethoxybenzyl cyanide, α- (4-toluenesulfonyloxy) Imino) -4-thienyl Cyanides such as nido; α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, (5-tosyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, ( 5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-n-propyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, Acetonitriles such as (5-n-octyloxyimino-5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile.

  As the alkali-soluble resin, known alkali-soluble resins used for photoresist materials can be used, and among them, a resin having a phenolic hydroxyl group is preferable. Specifically, a novolac resin, a polyvinyl resin, or the like can be used. Examples of the novolak resin include p-cresol novolak resin, m-cresol novolak resin, novolak resin of p-cresol and m-cresol, and novolak resin having a repeating structure represented by the formula (201).

Examples of the polyvinyl resin include polymers of vinylphenol (p-vinylphenol (also referred to as p-hydroxystyrene)). This polymer may be a homopolymer or a copolymer (for example, a copolymer of styrene and p-vinylphenol). If necessary, the hydrogen atom of the hydroxyl group of vinylphenol may be substituted (masked) with an organic group (for example, a C _1-6 alkyl group). When the hydroxyl group is masked with an organic group, the amount of exposure when forming a pattern by a photolithography method can be reduced, and the pattern shape can be easily made into a preferable rectangle as a color filter.

  The novolak resin has a polystyrene equivalent weight average molecular weight of, for example, about 3,000 to 20,000, and the polyvinyl resin has a polystyrene equivalent weight average molecular weight of, for example, about 1,000 to 20,000, preferably 2,000 to 6, About 000.

  As a hardening | curing agent (crosslinking agent) used in the colored photosensitive resin composition of this invention, the compound which has a thermosetting effect can be used, for example, the melamine compound represented by Formula (301) can be used.

[In the formula (301), R ^{300 to} R ³⁰⁵ are each independently a hydrogen atom, a linear C _1-10 alkyl group (preferably a linear C _1-4 alkyl group) or a branched C _{3. -10} alkyl group (preferably isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc.). However, at least two of R ^{300 to} R ³⁰⁵ are not hydrogen atoms. ]

  Preferred melamine compounds include hexamethoxymethyl melamine (also referred to as hexamethoxymethylol melamine), hexaethoxymethyl melamine and the like.

  Content of pigment | dye, photosensitive compound, alkali-soluble resin, and hardening | curing agent in the coloring photosensitive resin composition of this invention (The quantity with respect to a total of 100 mass parts of pigment | dye, photosensitive compound, alkali-soluble resin (solid content), and hardening | curing agent) ) Are as follows.

  Dye: For example, about 5 to 80 parts by mass, preferably about 15 to 80 parts by mass, more preferably about 20 to 70 parts by mass, especially about 50 to 70 parts by mass. By setting the amount of the dye within the above range, the color density of the color filter can be sufficiently increased, and the film loss in the development process at the time of pattern formation can be reduced.

  Photosensitive compound: For example, about 0.001 to 50 parts by mass, preferably about 0.01 to 40 parts by mass, more preferably about 0.1 to 30 parts by mass, particularly about 0.1 to 10 parts by mass. By setting the amount of the photosensitive compound within the above range, the film loss in the development process at the time of pattern formation can be reduced, and the projection exposure time for forming a pattern by photolithography can be shortened.

  Alkali-soluble resin: about 1 to 75 parts by mass, preferably about 5 to 60 parts by mass, and more preferably about 10 to 50 parts by mass. If the amount of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient, the film is not easily reduced in the development process, and the exposure amount when forming a pattern by the photolithography method is preferably reduced.

  Curing agent: about 1 to 40 parts by mass, preferably about 5 to 30 parts by mass, more preferably about 10 to 25 parts by mass. When the amount of the curing agent is within the above range, the exposure amount when forming a pattern by a photolithography method can be reduced. Moreover, the shape of the pattern after development is good, and the mechanical strength of the pattern after heating and curing the pattern is sufficient. Further, since the film thickness of the pixel pattern does not occur in the development process, the color unevenness of the image hardly occurs.

  The solvent can be appropriately selected depending on the solubility (particularly the solubility of the dye) of the dye, photosensitive compound, alkali-soluble resin, and curing agent contained in the colored photosensitive resin composition. For example, solvents include ethylene glycols (methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, etc.), propylene glycols (propylene glycol monomethyl ether, propylene glycol monomethyl ether) Acetate), N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, N, N-dimethylformamide, ketones (4-hydroxy-4-methyl-2-pentanone, cyclohexanone, etc.), carboxylic acid esters (ethyl acetate, N-butyl acetate, ethyl pyruvate, ethyl lactate, n-butyl lactate, etc.). These solvents may be used alone or in combination.

  The content of the solvent is, for example, about 65 to 95% by mass, preferably about 70 to 90% by mass with respect to the colored photosensitive resin composition. When the amount of the solvent is within the above range, the uniformity of the coating film becomes good.

  The colored photosensitive resin composition of the present invention may also contain a surfactant or the like as necessary. Surfactants include silicone surfactants [for example, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (above Toray Silicone Co., Ltd.) Manufactured), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (above made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above GE Toshiba Silicone) Surfactants having a siloxane bond, etc.]; fluorine-based surfactants [for example, Florard FC430, FC431 (the above is Sumitomo 3E) (Manufactured by Dainippon Ink & Chemicals, Inc.), EFTOP EF301, EF303, EF351, MegaFuck F142D, F171, F172, F173, F173, F177, F183, and R30 EF352 (Shin-Akita Kasei Co., Ltd.), Surflon S381, S382, SC101, SC105 (above Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM- 1000, a surfactant having a fluorocarbon chain such as BM-1100 (the above is manufactured by BM Chemie), etc .; a silicone-based surfactant having a fluorine atom [Megafac R08, BL20, F475, F477, F443 Siloxane bonds and fluoro such as (manufactured by Dainippon Ink & Chemicals, Inc.) A surfactant having a carbon chain, etc.]. These surfactants may be used alone or in combination of two or more.

  When using a surfactant, the amount used thereof is, for example, about 0.0005 mass% to 0.6 mass%, preferably about 0.001 mass% to 0.5 mass%, based on the colored photosensitive resin composition. It is. When the surfactant is used in the above range, the flatness during application of the colored photosensitive resin composition is further improved.

  When the colored photosensitive resin composition of the present invention is a negative composition, an amine compound may be further contained. By using an amine compound, it is possible to prevent the exposure amount when performing photolithography from greatly changing before and after storing the colored photosensitive resin composition for a long period of time. Further, by using an amine compound, it is possible to reduce the dimensional change of the resist pattern due to the deactivation of the photoacid generator when the substrate is left after exposure.

  Examples of amine compounds useful for exhibiting the former effect of stabilizing the exposure dose include 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, and 2-amino-2. -Amino alcohols such as methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 3-methyl-2-amino-1-butanol 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] non-5-ene, etc. And a compound having a diazabicyclo structure.

  Examples of amine compounds useful for exerting the latter dimensional stabilization effect include 4-nitroaniline, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4, 4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetraethyl-diphenylmethane, 8 -Quinolinol, benzimidazole, 2-hydroxybenzimidazole, 2-hydroxyquinazoline, 4-methoxybenzylidene-4'-n-butylaniline, salicylic acid amide, salicylanilide, 1,8-bis (N, N-dimethylamino) naphthalene 1,2-diazine (pyridazine), piperidine, p-a No-benzoic acid, N-acetylethylenediamine, 2-methyl-6-nitroaniline, 5-amino-2-methylphenol, 4-n-butoxyaniline, 3-ethoxy-n-propylamine, 4-methylcyclohexylamine, 4-tert-butylcyclohexylamine, monopyridines (imidazole, pyridine, 4-methylpyridine, 4-methylimidazole, 2-dimethylaminopyridine, 2-methylaminopyridine, 1,6-dimethylpyridine, etc.), bipyridines ( Bipyridine, 2,2′-dipyridylamine, di-2-pyridyl ketone, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,3-di (4-pyridyl) ) Propane, 1,2-bis (2-pyridyl) ethylene, 1,2-bis (4-pyridyl) ethyl 1,2-bis (4-pyridyloxy) ethane, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 1,2-bis (4-pyridyl) ethylene, 2,2'-dipicoly , Amines (tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n-octylammonium hydroxy) , Phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, choline, etc.).

  The content of the amine compound is, for example, about 0.01 to 10% by mass, preferably about 0.05 to 5% by mass, and more preferably 0.1 to 0% with respect to the solid content of the colored photosensitive resin composition. About 8% by mass.

  Further, the colored photosensitive resin composition of the present invention contains various additive components (epoxy resin, oxetane compound, ultraviolet absorber, antioxidant, chelating agent, etc.) to the extent that the effects of the present invention are not impaired. Also good.

  Said colored photosensitive resin composition can be prepared by mixing each component in a solvent. The prepared colored photosensitive resin composition is usually filtered through a filter having a pore size of about 0.2 μm or less. The uniformity at the time of apply | coating colored photosensitive resin composition improves by filtration.

  The colored photosensitive resin composition of the present invention can be made into a color filter array by a photolithography method in the same manner as a normal photosensitive composition. In the photolithography method, for example, a film made of the colored photosensitive resin composition of the present invention is formed on a support, the film is exposed and then developed, and the film is cured by means such as heating as necessary. A pixel may be formed. The above-described series of steps is repeated for each color, thereby forming a color filter array.

  As the support, known materials can be used. For example, a silicon wafer on which an image sensor such as a solid coupling element is formed, a transparent glass plate, a quartz plate, or the like can be used.

  The method for forming a film on the support is also not particularly limited, and usual methods such as spin coating method, roll coating method, bar coating method, die coating method, dip method, casting coating method, roll coating method, slit & spin coating method, etc. The coating method can be appropriately employed. After coating the colored photosensitive resin composition of the present invention on a support, a film can be formed by removing volatile components such as a solvent by heating (for example, heating at 70 to 120 ° C.).

  When exposing the film, the film is irradiated with light through a mask pattern corresponding to the target pattern. As the light beam, for example, g-line or i-line can be used, and an exposure machine such as a g-line stepper or i-line stepper may be used for these. The amount of light irradiation in the irradiation region is appropriately selected depending on the type and content of the photosensitive compound, the type and content of the curing agent, and the polystyrene-equivalent weight average molecular weight, monomer ratio, and content of the alkali-soluble resin. . Moreover, you may heat the film produced in this way. By heating, the curing agent is cured and the mechanical strength of the coating is improved. The heating temperature in the case of heating is, for example, about 80 to 150 ° C.

  In the development, as in the case of using an ordinary photosensitive composition, the support provided with the film may be brought into contact with an ordinary developer. Although there is no restriction | limiting in particular as a developing solution, For example, alkaline aqueous solution etc. are used and you may mix surfactant as needed. The target pixel can be formed by shaking off the developer and then washing with water to remove the developer. In some cases, the developer is shaken off, rinsed with a rinse solution, and then washed with water. By this rinsing, the residue of the colored photosensitive composition remaining on the support during development can be removed.

  The developed pixel may be irradiated with ultraviolet rays as necessary. The remaining photosensitizer can be decomposed by ultraviolet irradiation. Further, the pixel may be heated after washing with water. By heating, the mechanical strength of the pixel can be improved. The heating temperature is usually about 160 to 220 ° C. When the heating temperature is in the above range, the curing with the curing agent proceeds sufficiently without the pigment being decomposed.

  The thickness of the color filter array obtained as described above is, for example, about 0.4 to 2.0 μm. The vertical and horizontal lengths of each pixel can be set independently in the range of about 1.0 to 20 μm.

  The color filter array of the present invention can be formed on an element such as a solid-state image sensor (CCD or the like) or a liquid crystal display element, and is useful for colorizing them. A typical example of forming the color filter array of the present invention on a CCD and a camera system using these will be described in more detail with reference to the drawings.

CCD image sensor:
FIG. 1 is a partially enlarged schematic sectional view showing an example of a CCD image sensor in which a color filter array of the present invention is formed, and FIGS. 2 to 7 are parts showing a procedure for forming a color filter in the CCD image sensor of FIG. It is an expansion schematic sectional drawing.

  In the illustrated CCD image sensor, a photodiode 2 is formed by ion-implanting N-type impurities such as P and As into a part of the surface of the P-type impurity region in the silicon substrate 1 and then performing heat treatment. Further, a vertical charge transfer portion 3 made of an impurity diffusion layer having an N-type impurity concentration higher than that of the photodiode 2 is formed on a surface of the silicon substrate 1 that is different from the photodiode formation site. The vertical charge transfer unit 3 can be formed by ion implantation of an N-type impurity such as P or As and then heat treatment. The vertical charge transfer unit 3 transfers charges generated when the photodiode 2 receives incident light. Acts as a layer (CCD).

  In the CCD image sensor of the illustrated example, the impurity region of the silicon substrate 1 is a P-type impurity layer, and the photodiode 2 and the vertical charge transfer unit 3 are N-type impurity layers. However, the impurity region of the silicon substrate 1 is an N-type impurity layer, The photodiode 2 and the vertical charge transfer unit 3 can also be implemented as a P-type impurity layer.

An insulating film 5a such as SiO ₂ is formed on the silicon substrate 1, the photodiode 2 and the vertical charge transfer portion 3, and poly-Si or the like is formed above the vertical charge transfer portion 3 via the insulating film 5a. A vertical charge transfer electrode 4 is formed. The vertical charge transfer electrode 4 serves as a transfer gate for transferring the charge generated in the photodiode 2 to the vertical charge transfer unit 3 and transfers the charge transferred to the vertical charge transfer unit 3 in the vertical direction of the chip. To serve as a transfer electrode.

A light shielding film 6 is formed above and on the side surface of the vertical charge transfer electrode 4 via an insulating film 5b such as SiO ₂ . The light shielding film 6 is made of metal such as tungsten, tungsten silicide, or Al, Al silicide, for example, and plays a role of preventing incident light from entering the vertical charge transfer electrode 4 and the vertical charge transfer unit 3. Further, on the side surface of the light shielding film 6, an overhanging portion may be provided on the light shielding film 6 above the photodiode 2 to prevent the incident light from leaking into the vertical charge transfer portion 3.

  Above the light shielding film 6, for example, a BPSG film 7 is formed so as to protrude downward with respect to the photodiode 2, and a P-SiN film 8 is further laminated thereon. The BPSG film 7 and the P-SiN film 8 are laminated so that their interfaces are curved downward above the photodiode 2, and serve as an intra-layer lens for efficiently guiding incident light to the photodiode 2. Fulfill. A planarizing film layer 9 is formed on the surface of the P-SiN film 8 for the purpose of planarizing uneven portions other than the surface or the pixel region.

  Further, a color filter array 10 is formed on the planarizing film layer 9. The formation of the color filter array 10 may be performed in accordance with the above-described photolithography method, but will be described with reference to FIGS. In the illustrated example, a negative type colored photosensitive resin composition will be described as an example, but a positive type may be used.

  In order to form a color filter array, first, a colored photosensitive resin composition of the first color (blue photosensitive resin composition 10B in the illustrated example) is applied on the planarizing film layer 9 ( 2), the pattern is projected and exposed through the photomask 13 (see FIG. 3). By this exposure, the resin composition in the exposed region 14 becomes insoluble in the developer. The resin composition in the unexposed area 15 is soluble in the developer and dissolves in the developer to form a pattern. Thereafter, the remaining insolubilized resin composition in the exposed region is heat-cured to form a desired blue pixel pattern 10B (FIG. 4).

  Next, the same process is repeated for the other color pixel patterns (in the illustrated example, the green pixel pattern 10G and the red pixel pattern 10R) to form the three color pixel patterns on the same plane of the image sensor formation substrate. (FIG. 5).

  A flattening film 11 is formed on the surface of the color filter array 10 formed as described above for the purpose of flattening the irregularities (FIG. 6). Further, on the upper surface of the flattening film 11, the photodiode 2 is formed. By forming the microlens 12 for efficiently collecting incident light (FIG. 7), a CCD image sensor and a camera system using the same are formed.

Camera system:
FIG. 8 is a configuration diagram showing an example of a camera system in which a solid-state image sensor (image sensor) is incorporated. In this camera system, incident light enters the image sensor 42 via the lens 41. The above-described on-chip lens 12 and the color filter array 10 are formed on the light incident surface side of the image sensor 42, and a signal corresponding to each color of incident light is output. The signal from the image sensor 42 is signal-processed by the signal processing circuit 43 and output to the camera.

In the illustrated camera system, the image sensor 42 is driven by a device drive circuit 45. The operation of the device driving circuit 45 can be controlled by sending mode signals such as a still image mode and a moving image mode from the mode setting unit 44.
The present invention can be applied not only to a CCD image sensor but also to an amplifying solid-state imaging device such as a CMOS image sensor, a camera system using the same, and a liquid crystal display device.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and both are included in the technical scope of the present invention.

Synthesis example 1
Poly (p-hydroxystyrene) [trade name “Marcalinker M” (manufactured by Maruzen Petrochemical Co., Ltd.), weight average molecular weight (catalog value) 4,100, dispersity (catalog value) 1.98] 36.0 mass And 144 parts by mass of acetone were added to a reaction vessel and dissolved by stirring. Thereto were added 20.7 parts by mass of anhydrous potassium carbonate and 9.35 parts by mass of ethyl iodide, and the temperature was raised to start refluxing. After refluxing was continued for 15 hours, 72 parts by mass of methyl isobutyl ketone was added, the organic layer was washed with 92.8 parts by mass of a 2% by mass oxalic acid aqueous solution, then 96 parts by mass of methyl isobutyl ketone was added, and 64. The organic layer was washed with 7 parts by mass. The organic layer after washing was concentrated to 78.3 parts by mass, 187.9 parts by mass of propylene glycol monomethyl ether acetate was added, and the mixture was further concentrated to 117.4 parts by mass. The solid content of this concentrate was 30.6% by mass. Further, according to ¹ H-NMR measurement, 19.5% of the hydroxyl groups of poly (p-hydroxystyrene) were ethyl etherified in the resin after the reaction. This resin is referred to as Resin A.

Example 1
26 parts by mass of the dye represented by formula (I-1) as the dye, and 4 parts by mass of α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile as the photosensitive compound (photoacid generator). Further, 53.45 parts by mass of resin A as an alkali-soluble resin, 0.15 parts by mass of 2-amino-2-methyl-1-propanol as an amine compound, and 16.4 of hexamethoxymethylol melamine as a curing agent After mixing 480 parts by mass of 4-hydroxy-4-methyl-2-pentanone as a solvent and 120 parts by mass of propylene glycol monomethyl ether as a solvent, the mixture is filtered through a membrane filter having a pore size of 0.2 μm and colored blue. The photosensitive resin composition 1 was obtained.

  Next, a colored photosensitive resin composition 1 is applied onto a quartz wafer so as to have a film thickness of 0.70 μm by spin coating, and the coating is formed by heating at 100 ° C. for 1 minute to remove volatile components. Formed. Subsequently, ultraviolet rays were irradiated and heated at 200 ° C. for 3 minutes to obtain a blue filter 1.

Comparative Example 1
By using the dye represented by the formula (II) (CI Acid Blue 90) instead of the dye (I-1) in the same procedure as in Example 1, a blue colored photosensitive composition is used. 2 and filter 2 were obtained. However, in Comparative Example 1, the dye (II) was used in an amount of 24 parts by mass in order to match the light transmittances of the blue filters 1 and 2 at a wavelength of 630 nm.

Spectroscopic evaluation The light transmittance at wavelengths of 450 nm and 630 nm of the filters obtained in Example 1 and Comparative Example 1 was measured. The results are shown in Table 1 below.

  From the results of Table 1, the blue filter 1 of the present invention containing the dye (I-1) has a higher light transmittance at a wavelength of 450 nm than the blue filter 2 containing the dye (II), and color reproduction as a light receiving element. It turns out that it is excellent in property.

  The colored photosensitive resin composition of the present invention can be used to produce a color filter array formed on an element in order to color a solid-state imaging element (such as an image sensor) or a liquid crystal display element.

FIG. 1 is a partially enlarged schematic sectional view showing an example of a CCD image sensor. FIG. 2 is a first view showing a manufacturing method of the image sensor of FIG. FIG. 3 is a second view showing a method for manufacturing the image sensor of FIG. FIG. 4 is a third view showing a method of manufacturing the image sensor of FIG. FIG. 5 is a fourth view showing a manufacturing method of the image sensor of FIG. FIG. 6 is a fifth view showing the method of manufacturing the image sensor shown in FIG. FIG. 7 is a sixth view showing a method of manufacturing the image sensor of FIG. FIG. 8 is a block diagram showing an example of a camera system.

Explanation of symbols

10 color filter array 10B Blue filter layer (blue pixel pattern)
10G green filter layer (green pixel pattern)
10R Red filter layer (red pixel pattern)

Claims (5)

A colored photosensitive resin composition comprising a dye represented by formula (I), an alkali-soluble resin, a photosensitive compound, a curing agent, and a solvent.
[In the formula (I), X represents a nitrogen atom or CH.
R ¹¹ represents a hydrogen atom or a C _1-4 alkyl group.
R ¹² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group or a C _1-4 alkoxycarbonyl group.
R ¹³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents a C _1-8 alkyl group. However, when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom.
R ^{14 to} R ¹⁶ are each independently a hydrogen atom, an amino group or a C _1-20 alkyl group optionally substituted with a halogen atom, an amino group optionally substituted with a C _1-20 alkyl group, C _1-20 ether groups containing one or more oxygen atoms, _optionally substituted aromatic groups, or hydroxyl groups. ]   The colored photosensitive resin composition according to claim 1, wherein the photosensitive compound contains an oxime compound.   A color filter array formed using the colored photosensitive resin composition according to claim 1.   A solid-state imaging device comprising the color filter array according to claim 3.   A camera system comprising the solid-state imaging device according to claim 4.