JP6678003B2 - Coloring composition for solid-state imaging device and color filter - Google Patents

Description

    The present invention relates to a color filter for a solid-state imaging device mounted on a solid-state imaging device represented by a C-MOS (Complementary Metal Oxide Semiconductor), a CCD (Charge Coupled Device), and the like. The present invention relates to a solid-state imaging device provided with the color filter and a photosensitive coloring composition for a solid-state imaging device.

  2. Description of the Related Art A solid-state imaging device such as a C-MOS or CCD has a color filter having a filter segment of an additive primary color of B (blue), G (green), and R (red) on its light receiving element. Generally, color separation is performed. In recent years, the area per pixel has been decreasing due to the miniaturization of solid-state imaging devices and the increase in the number of pixels. As a result, it is required to reduce the thickness of the color filter mounted on the imaging device and increase the concentration of the coloring component.

  As a method for manufacturing a color filter, there are a dyeing method using a dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, an electrodeposition method, and the like. Among them, the dyeing method or the dyeing dispersion method has a disadvantage that heat resistance and light resistance are slightly inferior because the dye is a dye. Therefore, a pigment excellent in heat resistance and light resistance is used as a color material of a color filter, and a pigment dispersion method is often used as a manufacturing method in view of accuracy and stability of a forming method.

  In the pigment dispersion method, a color resist is prepared by mixing and blending a photosensitive agent and additives with a dispersion of pigment particles, which are pigments, in a transparent resin, and the color resist is coated on a substrate using a coating device such as a spin coater. This is a method of forming a coating film by using an aligner, a stepper or the like, selectively exposing through a mask, performing patterning by performing alkali development and thermosetting, and repeating this operation to produce a color filter.

  In recent years, there has been an increasing demand for color filters such as improvement in transmittance and color purity, coating uniformity when forming filter segments, sensitivity, developability, and pattern shape. Further, high definition and high color reproducibility are required, and a color filter having high transmittance, excellent color reproducibility, and excellent color separation is required.

  Therefore, in recent years, in order to achieve high transmittance of a color filter, and to realize a color filter excellent in color reproducibility and color separation, a pigment contained in a filter segment is often used after being finely treated. However, a variety of pigments (a so-called crude having a particle size of 10 to 100 μm produced by a chemical reaction, which is converted into a mixture of primary particles and secondary particles obtained by agglomerating them by a pigmentation treatment) are variously used. Even if the particles are refined by the refinement treatment method, the pigment whose primary particles or secondary particles have been refined is generally easily aggregated, and if the refinement is excessively advanced, a huge massive pigment solid is formed. I will. Further, the finely-divided pigment is dispersed in a pigment carrier containing a resin or the like, and a stable colored composition is obtained even if the secondary particles of the pigment are again stabilized as close to the primary particles as possible. It is very difficult.

  Therefore, for example, a pigment composition containing a pigment composed of fine particles often exhibits a high viscosity, which not only makes it difficult to take out and transport the product from a dispersing machine, but also causes gelation during storage in a bad case. It can wake up and even be difficult to use. Therefore, dispersibility is controlled by a structure-controlled one having a block type structure (Patent Document 1) or a comb-shaped structure (Patent Document 2), or a resin type dispersant such as a polyester dispersant having a specific structure (Patent Document 3). A colored composition having excellent storage stability and a high contrast ratio has been studied. However, even when these resin-type dispersants are used, the fineness of the pigment is advanced and the surface area is increased, so that the light resistance is deteriorated. Therefore, in a solid-state imaging device application requiring good color separation, the spectral change becomes large and the color separation deteriorates.

Therefore, although a composition for a color filter using a benzotriazole-based ultraviolet absorber to improve light resistance (see Patent Document 4) and the like have been disclosed, in recent years, achievement of high transmittance of a color filter has been achieved. In order to realize a color filter having excellent color reproducibility and color separation properties, a sufficient effect has not been obtained for a composition for a color filter, which is often used after finely treating a pigment. In addition, when an ultraviolet absorber is used, there has been a problem that adhesion is poor due to insufficient ultraviolet sensitivity at the time of exposure.

JP 2002-31713 A JP-A-11-1515 WO 2008/007776 pamphlet JP 2000-214580 A

  Therefore, an object of the present invention is to provide a photosensitive coloring composition for a solid-state imaging device that has excellent light resistance and good adhesion even when a finely divided pigment or dye is used as a coloring agent.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by including an ultraviolet absorber containing the benzotriazole-based unit of the present invention in the coloring composition, excellent in light resistance, and It was found that the adhesion was good.

  That is, the present invention contains a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E), The ultraviolet absorber (E) is a polymer containing a unit (e1) having a benzotriazole structure and a unit (e2) having no benzotriazole structure, and a weight ratio (e1 /) of (e1) to (e2). e2) is from 0.1 to 10.0, and relates to a photosensitive coloring composition for a solid-state imaging device.

Further, the present invention relates to the photosensitive coloring composition for a solid-state imaging device described above, wherein the unit having a benzotriazole structure includes a unit having a benzotriazole structure represented by the general formula (1).

General formula (1)


[In the general formula (1), R ¹ , R ⁴ and X represent a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, A heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R ³ represents an alkylene group, a cycloalkylene group which may contain a double bond, or an arylene group. ]

Further, in the present invention, R ^{1 in the} general formula (1) is a hydrogen atom or a methyl group, R ³ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁴ is a hydrogen atom or A hydrocarbon group having 1 to 18 carbon atoms, wherein X is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The present invention relates to the photosensitive coloring composition for a solid-state imaging device described above.

  Further, in the present invention, the ultraviolet absorbent (E), which is the benzotriazole-based organic compound, is contained in an amount of 0.5 to 6.0% by weight in a solid content of the entire coloring composition. The present invention relates to a photosensitive coloring composition for an imaging device.

  Further, the present invention relates to a color filter comprising a filter segment formed on a base material using the photosensitive coloring composition for a solid-state imaging device.

  The photosensitive coloring composition for a solid-state imaging device of the present invention can provide a high-quality color filter that maintains adhesion and has excellent light resistance.

Hereinafter, the present invention will be described in detail.
In the present application, when described as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, respectively, “acrylate and / or methacrylate”, The term “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide” is used.
In addition, “CI” described below means a color index (CI).

Hereinafter, each component constituting the photosensitive coloring composition for a solid-state imaging device of the present invention will be described in detail.

<Colorant (A)>
The photosensitive coloring composition for a solid-state imaging device of the present invention contains a coloring agent (A) and can form a filter segment of each color constituting a color filter.
As the colorant (A), organic or inorganic pigments and dyes can be used alone or in combination of two or more. As the colorant, a substance having high coloring properties and high heat resistance is preferable, and usually an organic pigment is used.
The organic pigment may be finely divided by salt milling, acid pasting, or the like, and is more preferable in terms of the suitability of the color filter for contrast.

Hereinafter, specific examples of the coloring agent (A) that can be used in the photosensitive coloring composition for a solid-state imaging device of the present invention will be described.
The colorant (A) used for the red photosensitive coloring composition forming the red filter segment is C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, 279, Red pigments such as 280, 281, 282, 283, 284, 285, 286, or 287 are used. It is also possible to use basic dyes, acid dyes and salt-forming compounds of these dyes that exhibit red color.

The photosensitive coloring composition for a red solid-state imaging device includes C.I. I. Orange pigments such as CI Pigment Orange 43, 71 or 73 and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. In addition, orange and / or yellow basic dyes, acid dyes, and salt-forming compounds of these dyes can also be used.

The colorant (A) used in the photosensitive color composition for a color filter forming a green filter segment is C.I. I. Pigment Green 7, 10, 36, 37, 58 and the like.
In addition, a yellow pigment can be used in combination with the photosensitive coloring composition for a green solid-state imaging device. Yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221 can be mentioned. Further, a basic dye, an acid dye or a salt-forming compound of these dyes exhibiting yellow can be used in combination.

The coloring agent (A) used for the photosensitive coloring composition for a blue solid-state imaging device forming a blue filter segment is C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, or 64 or the like can be used. The photosensitive coloring composition for a blue solid-state imaging device includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 or other purple pigments can be used in combination. Further, a basic dye, an acid dye, and a salt-forming compound of these dyes exhibiting a purple color may be used in combination.

The colorant (A) is preferably contained in the range of 1 to 80% by weight, more preferably in the range of 2 to 70% by weight, based on 100% by weight of the solid content of the photosensitive coloring composition for a solid-state imaging device. It is. If the content of the coloring agent (A) is less than 1% by weight, the film thickness of the color filter becomes excessively large, which is not preferable. If it exceeds 80% by weight, a good dispersion state cannot be obtained, which is not preferable.

<Resin (B)>
The resin (B) disperses the colorant (A), and examples thereof include a thermoplastic resin and a thermosetting resin.
The resin (B) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali-developed colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. In addition, a photosensitive resin having an ethylenically unsaturated active double bond can be used to improve photosensitivity.

The weight average molecular weight (Mw) of the resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant (A) preferably. It is. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

In addition, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl group serving as a pigment adsorbing group and an alkali-soluble group during development, an aliphatic group and an aromatic group serving as an affinity group for a pigment carrier and a solvent. The balance is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.
The resin (B) is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the colorant (A) because of its good film-forming properties and various resistances. It is preferable to use it in an amount of 500 parts by weight or less because the properties can be exhibited.

(Thermoplastic resin)
As the thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (anhydride) maleic acid copolymer; Above all, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and high transparency.

(Photosensitive resin)
The photosensitive resin is not particularly limited as long as the resin has an ethylenically unsaturated double bond in a side chain.In particular, the main chain is preferably linear, and alkali-soluble to impart alkali developability. It is more preferable that the applied resin is used. In particular, the resin (B-1) having a specific structure has good adhesion to a substrate, a base, or the like, and can provide a coating film having low dielectric constant and dielectric loss tangent and excellent electric characteristics.

As the photosensitive resin, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl gly Diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, urethane acrylate Acrylates and methacrylates such as styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile Water of a polymer compound obtained by polymerizing a monomer / oligomer such as a monomer with a monomer / oligomer having an acid value such as (meth) acrylic acid A (meth) acrylic compound or a cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group with a reactive substituent such as a group, a carboxyl group or an amino group to obtain (meth) acryloyl A resin into which a photocrosslinkable group such as a group or styryl group is introduced is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted to a (meth) acryl compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate. Half-esterified ones can also be used.

[Photosensitive resin (B-1)]
Among the photosensitive resins, the following (b1), (b2) and (b3) are copolymerized to obtain a copolymer (b6), and the obtained copolymer (b6) and an unsaturated monobasic acid ( b4) to obtain a copolymer (b7), and further react the obtained copolymer (b7) with a polybasic anhydride (b5) to obtain a photosensitive resin (B-1). ), The adhesion to the base material or the base is improved, and a coating film having a low dielectric constant and a low dielectric loss tangent and having good electric properties can be obtained.
(B1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule (b2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule (b3); Compound (b4) having an ethylenically unsaturated bond other than (a2); unsaturated monobasic acid (b5); polybasic acid anhydride

(B1) Specific examples of the compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cycloheptyl ( (Meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadenyl (meth) acrylate, isobornyl (meth) acrylate , Pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, derivatives having substituents pinenyl (meth) acrylate and on the alicyclic ring. Examples of the substituent on the alicyclic ring of these monomers include an alkyl group, a hydroxyl group and a carboxyl group.

Among them, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate is preferred, and most preferred are isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate. These can be used alone or in combination of two or more.

(B2); Compounds having an epoxy group and an ethylenically unsaturated bond in one molecule include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-propylglycidyl (meth) acrylate, and β-methyl Glycidyl-α-ethyl acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) Examples include acrylate and glycidyl vinyl ether, and glycidyl (meth) acrylate is preferable.

(B3) Specific examples of the compound having an ethylenically unsaturated bond other than (a1) and (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl. Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as (meth) acrylate, aminoethyl (meth) acrylate;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
Examples include N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. These can be used alone or in combination.

(B4): As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl (meth) acrylic acid, alkoxyl, halogen, nitro, cyano And monocarboxylic acids such as substituted ones. Among them, (meth) acrylic acid is preferred.

(B5); Examples of polybasic anhydrides include dibasic anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride: anhydrous And polybasic acid anhydrides such as trimellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride or succinic anhydride is preferable.

(Method for producing photosensitive resin (B-1))
The photosensitive resin (B-1) is obtained by copolymerizing (b1), (b2) and (b3) to obtain a copolymer (b6), and the obtained copolymer (b6) is mixed with an unsaturated monobasic. A copolymer obtained by reacting the acid (b4) with the acid (b4) to obtain a copolymer (b7), and further reacting the obtained copolymer (b7) with the polybasic anhydride (b5). .

First, (b1), (b2) and (b3) are copolymerized to obtain a copolymer (b6). This copolymerization is carried out under ordinary conditions. For example, a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube is 0.5 to 20 times by weight the total amount of (b1), (b2) and (b3). An amount of solvent is introduced, and the atmosphere in the flask is replaced with nitrogen from air. Then, after raising the temperature of the solvent to 40 to 140 ° C., based on the mass based on the predetermined amounts of (b1), (b2) and (b3) and the total amount of (b1), (b2) and (b3). A solution in which 0.1 to 10 parts by weight of a solvent and a polymerization initiator in an amount of 0 to 20 times the amount of (b1), (b2) and (b3) are added (dissolved by stirring at room temperature or under heating). Is dropped into the flask over a period of 0.1 to 8 hours from a dropping funnel, and further stirred at 40 to 140 ° C. for 1 to 10 hours.

In the above step, a part or all of the polymerization initiator may be charged into the flask, or a part or all of (b1), (b2) and (b3) may be charged into the flask. Further, in order to control the molecular weight and the molecular weight distribution, an α-methylstyrene dimer or a mercapto compound may be used as a chain transfer agent. The amount of the α-methylstyrene dimer or mercapto compound used is 0.005 to 5 parts by mass based on the total amount of (b1) to (b3). The above-mentioned polymerization conditions may be appropriately adjusted in the charging method and the reaction temperature in consideration of the production equipment, the calorific value due to the polymerization, and the like.

As the ratio of the constituent components derived from each, a molar fraction based on the total number of moles of the constituent components constituting the copolymer (b6) is 2 to 40 mol% of the structural unit derived from (b1), It is preferably from 2 to 95 mol% of the structural unit derived from (b2) and from 3 to 65 mol% of the structural unit derived from (b3), and from the balance between flexibility and heat resistance, from the structural unit derived from (b1). More preferably, it is 5 to 35 mol%, 5 to 80 mol% of the structural unit derived from (b2), and 15 to 50 mol% of the structural unit derived from (b3).

Next, (b4) is added to the copolymer (b6) to give the resin (B) light or thermosetting properties. The reaction between the copolymers (b6) and (b4) can be performed, for example, under the conditions described in JP-A-2001-89533. Specifically, the atmosphere in the flask is replaced with air from nitrogen, and as a reaction catalyst for the carboxyl group and the epoxy group, for example, trisdimethylaminomethylphenol is added on a mass basis with respect to the total amount of (b1) to (b4). 0.01 to 5%, and as a polymerization inhibitor, for example, 0.001 to 5% by mass of hydroquinone, based on the total amount of (b1) to (b4), The copolymer (b6) and (b4) can be reacted by reacting at a temperature of 130 ° C. for 1 to 10 hours. As in the case of the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

The amount of (b4) added is 5 to 100 mol%, preferably 10 to 95 mol%, based on the epoxy groups in the resin obtained by copolymerizing (b1) to (b3). It is preferable that the composition ratio of (b2) be within the above range, since sufficient photocurability and thermosetting properties can be obtained and reliability is excellent.

Next, the copolymer (b7) is reacted with (b5) to impart alkali solubility to the resin (B).
The reaction between the copolymers (b7) and (b5) can be performed, for example, under the conditions described in JP-A-2001-89533. Specifically, as a reaction catalyst, for example, triethylamine is put into a flask in an amount of 0.01 to 5% on a mass basis with respect to the total amount of (b1) to (b4), and at 60 to 130 ° C, By reacting for 1 to 10 hours, the above-mentioned copolymer (b7) and (b5) can be reacted. As in the case of the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization, and the like.

The amount of (b5) added is 5 to 100 mol%, preferably 10 to 95 mol%, based on the number of moles of alcoholic hydroxyl groups in the copolymer (b7).

The weight average molecular weight in terms of polystyrene of the photosensitive resin (B-1) is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. When the weight-average molecular weight of the photosensitive resin (B-1) is in the above range, coating properties are good, film loss hardly occurs during development, and developability of unexposed portions during development is good. There is a tendency and it is preferable.

The molecular weight distribution [weight average molecular weight / number average molecular weight] of the photosensitive resin (B-1) is preferably from 1.5 to 6.0, and more preferably from 1.8 to 4.0. It is preferable that the molecular weight distribution is in the above-mentioned range because the developability is excellent.

The content of the photosensitive resin used in the photosensitive coloring composition for a solid-state imaging device of the present invention is usually 5 to 90% by weight, preferably 10 to 70% by weight based on 100% by weight of the solid content of the photosensitive resin composition. It is. When the content of the photosensitive resin is in the above range, the solubility in a developing solution is excellent, a development residue is hardly generated, and the film thickness of an exposed portion is hardly reduced at the time of development.

Further, by using a photosensitive resin, the degree of photocuring crosslinking increases, the adhesion is good, and the cross-sectional shape is good.

(Thermosetting resin)
Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

<Photopolymerizable monomer (C)>
The photopolymerizable monomer (C) contained in the photosensitive coloring composition for a solid-state imaging device of the present invention is a monomer or oligomer which is cured by ultraviolet light or heat to produce a transparent resin, and these may be used alone or Two or more kinds can be used in combination.
The content of the photopolymerizable monomer (C) is preferably from 10 to 50% by weight based on the total solid content of 100% by weight of the coloring composition, and from the viewpoint of photocurability and developability, from 20 to 50%. More preferably, it is 40% by weight.

Examples of monomers and oligomers which are cured by ultraviolet light or heat to produce a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycine Di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO-modified phthalate Acid (meth) acrylate, PO-modified phthalic acid (meth) acrylate, acrylated siissocyanurate, bis (acryloxyneopene (Tyl glycol) adipate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane tri (meth) acrylate , Tripropylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, neopentyl glycol hydroxypivalate di (meth) acrylate, pentaerythritol tri (meth) acrylate, An agent having an EO-modified group such as dicyclopentanyl di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate Rate, acrylate having PO modifying group, esterified product of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; polycarboxylic acid and monohydroxyalkyl (meth) Examples thereof include an esterified product with an acrylate. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And a free carboxyl group-containing monoester of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid and benzene-1,3,5-tricarboxylic acid And carboxyl group-containing oligoesters of monohydroxy monoacrylates or monohydroxy monomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate; Various acrylates and methacrylates of acrylates having a group, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) ) Acrylamide, N-vinylformamide, acrylonitrile and the like, but are not necessarily limited thereto.

<Photopolymerization initiator (D)>
The photosensitive coloring composition for a solid-state imaging device of the present invention is cured by irradiation with ultraviolet rays, and forms a filter segment by a photolithographic method. Adjust in the form of resist material.
Examples of the photopolymerization initiator (D) include oxime ester organic compounds. The content of the photopolymerization initiator (D) is preferably from 1 to 16% by weight from the viewpoint of adhesion and resolution, based on the solid content of the photosensitive coloring composition (100% by weight), More preferably, it is 2 to 13% by weight.

Among the photopolymerization initiators (D), oxime ester-based organic compounds are preferable from the viewpoint of adhesion and resolution. Examples of the oxime ester-based organic compound include 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime ), O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like.

Examples of the photopolymerization initiator that can be used in combination include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, and 1- (4-isopropylphenyl) -2-hydroxy-2. -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2 -Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Phenyl] -2-methyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (meth Ruthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Acetophenone compounds such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzyl dimethyl ketal. Benzoin compounds, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3 ′, 4,4′-tetra ( t-butyl par Benzophenone-based compounds such as (xoxycarbonyl) benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine-based compounds such as 6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)- Imidazole compounds such as 4,4 ', 5,5'-tetra (p-methylphenyl) biimidazole, and quinones such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone Compound, bis (2,4,6-trimethylbenzoyl) acyl phosphine oxide meter compounds such as triphenylphosphine oxide, borate-based compound, carbazole-based compounds.
These photopolymerization initiators can be used singly or as a mixture of two or more at any ratio as needed.

(Sensitizer)
In order to further enhance the reaction of the photopolymerization initiator, a sensitizer may be used in combination with the photosensitive coloring composition for a solid-state imaging device of the present invention. Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxanol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azulhenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, annulene derivative, spiropyran derivative, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives and the like.

Further examples include Shin Okawara et al., "Dye Handbook" (1986, Kodansha), Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadasaburo Ikemori et al., "Special Sensitizers described in "Functional Materials" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near infrared region can be contained.

Among the above sensitizers, specific examples of the sensitizer that can be used in combination include a thioxanthone derivative, a Michler's ketone derivative, and a carbazole derivative. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like can be mentioned.
These sensitizers can be used alone or in combination of two or more. The content of the sensitizer is preferably 0.1 to 60 parts by weight based on 100 parts by weight of the photopolymerization initiator (D).

<Ultraviolet absorber (E)>
The ultraviolet absorbent (E) in the present invention is an organic compound having an ultraviolet absorbing function, and is a polymer containing a unit (e1) having a benzotriazole structure and a unit (e2) having no benzotriazole structure. , (E1) and (e2) have a weight ratio (e1 / e2) of 0.1 to 10.0.

The ultraviolet absorber (E) in the present invention is obtained by polymerizing a monomer having a benzotriazole structure and a monomer having no benzotriazole structure.
The unit (e1) having a benzotriazole structure is derived from a monomer having a benzotriazole structure, and the unit (e2) having no benzotriazole structure is derived from a monomer having no benzotriazole structure.

Preferred specific examples of the unit (e1) having a benzotriazole structure include the general formula (1) and the general formula (2).
General formula (2)

In the unit having a benzotriazole structure represented by the general formula (2), the substituent represented by R ⁵ is a hydrogen atom or a methyl group, and the substituent represented by R ⁶ is a group having 1 to 1 carbon atoms. A linear or branched alkylene group of 6 or a linear or branched oxyalkylene group of 1 to 6 carbon atoms, and R ⁷ is a hydrogen atom or a hydrocarbon group of 1 to 18 carbon atoms. And Y is a benzotriazole composed of a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.

  The ultraviolet absorber containing the general formula (2) as a unit can be obtained by polymerizing a raw material monomer containing a monomer of the following general formula (4).

General formula (4)

In the monomer having a benzotriazole structure represented by the general formula (4), the substituent represented by R ⁵ is a hydrogen atom or a methyl group, and the substituent represented by R ⁶ is a carbon atom. A linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms, wherein R ⁷ is a hydrogen atom or a hydrocarbon having 1 to 18 carbon atoms A benzotriazole wherein Y is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group.

The monomer having the benzotriazole structure is not particularly limited, but a specific substance name is 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl). -2H-benzotriazol-5-yl] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] ethyl acrylate, 3- [ 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] propyl methacrylate, 3- [2- (6-hydroxybenzo [1,3] dioxol-5- Yl) -2H-benzotriazol-5-yl] propyl acrylate, 4- [2- (6-hydroxybenzo [1,3] dioxol-5) Yl) -2H-benzotriazol-5-yl] butyl methacrylate, 4- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] butyl acrylate, -[2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yloxy] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol- 5-yl) -2H-benzotriazol-5-yloxy] ethyl acrylate, 2- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl } Propanoyloxy] ethyl methacrylate, 2- [3- {2- (6-hydroxybenzo [1,3] dioxol-5) Yl) -2H-benzotriazol-5-yl} propanoyloxy] ethyl acrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5 -Yl} propanoyloxy] butyl methacrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] butyl acrylate 2- [3- {2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] ethyl methacrylate, 2- [3- {2- (6-Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanoyloxy] ethylac 2- (methacryloyloxy) ethyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5carboxylate, 2- (acryloyloxy) ethyl 2- (6-hydroxy Benzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate, 4- (methacryloyloxy) butyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H -Benzotriazole-5-carboxylate, 4- (acryloyloxy) butyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylate, and the like. . In addition, these monomers having a benzotriazole structure can be used alone or in combination of two or more.

General formula (1)

In the unit having a benzotriazole structure represented by the general formula (1), R ¹ , R ⁴ and X are a hydrogen atom or an alkenyl group, an alkyl group, or an alkyloxy group which may have a substituent. An aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, A phosphinoyl group, a carbamoyl group, or a sulfamoyl group, and R ³ is an alkylene group, a cycloalkylene group which may contain a double bond, or an arylene group.

The ultraviolet absorber containing the general formula (1) as a unit can be obtained by polymerizing a raw material monomer containing the following general formula (5) as a monomer.

General formula (5)

The monomer having the above benzotriazole structure is not particularly limited, but a specific substance name is 2- [2-hydroxy-5- (methacryloyloxymethyl) phenyl] -2H-benzotriazole. 2- [2-hydroxy-5- (acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2- Hydroxy-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyl) Oxypropyl) phenyl] -2H-benzotriazole, -[2-hydroxy-5- (methacryloyloxybutyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxybutyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy- 5- (methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-butyl- 5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3-t-butyl-5- (acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy- 5- (methacryloyloxyethyl) phenyl] -5- Loro-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl]- 5-methoxy-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl ] -5-cyano-2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) ) Phenyl] -5-t-butyl-2H-benzotriazolate 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-t-butyl-2H-benzotriazole, 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -5-nitro -2H-benzotriazole, 2- [2-hydroxy-5- (acryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, 3- (2H-benzotriazol-2-yl) -4-4hydroxyphenethyl -Methacrylate, 2- [3- (2H-1,2,3-benzotriazol-2-yl) -4-hydroxyfell] ethyl methacrylate, 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-1,2,3-benzotriazol-5-yloxy] ethyl methacrylate and the like.
In particular, 3- (2H-benzotriazol-2-yl) -4-4hydroxyphenethyl-methacrylate, 2- [3- (2H-1,2,3-benzotriazol-2-yl) -4-hydroxyfel Ethyl methacrylate and 2- [2- (2-hydroxy-4-octyloxyphenyl) -2H-1,2,3-benzotriazol-5-yloxy] ethyl methacrylate are preferred from the viewpoint of light resistance.
In addition, these monomers having a benzotriazole structure can be used alone or in combination of two or more.

Further, as the unit (e1) having a benzotriazole structure, a unit represented by the following general formula (3) is also preferable.
General formula (3)

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxy group having 1 to 6 carbon atoms. Represents an alkylene group.)

The monomer having no benzotriazole structure to be copolymerized with the monomer having a benzotriazole structure is not particularly limited and can be appropriately selected and used. For example, methyl (meth) Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl ( Alkyl (meth) acrylates such as (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; Hydroxy group-containing unsaturated monomers such as hydroxyethyl (meth) acrylate, hydroxypropylethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate. Further, unsaturated monomers containing an oxide ring such as glycidyl (meth) acrylate and oxetane (meth) acrylate are exemplified. Further, nitrogen-containing unsaturated compounds such as (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (meth) acryloylmorpholine, vinylpyridine, vinylimidador, and N-vinylpyrrolidone Monomers. Further, there may be mentioned halogen-containing unsaturated monomers such as vinyl chloride and vinylidene chloride. Further, aromatic unsaturated monomers such as styrene and α-methylstyrene are exemplified. Further, unsaturated monomers containing a carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and maleic anhydride are exemplified. Further, sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid and styrene sulfonic acid are exemplified. Further, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate, 2- (meth) acryloyloxyethyl phenyl phosphate And the like.
Particularly, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and (meth) acrylic acid are preferable.

The weight ratio (e1 ′ / e2 ′) of the monomer (e1 ′) having a benzotriazole structure and the monomer (e2 ′) not having a benzotriazole structure when polymerizing the ultraviolet absorber (E) is , 0.1 to 10.0, more preferably 1.0 to 2.5.
Similarly, the weight ratio (e1 / e2) of the unit (e1) having a benzotriazole structure and the unit (e2) not having a benzotriazole structure in the ultraviolet absorber (E) which is a polymer of the above monomer is 0.1 to 10.0 is preferable, and 1.0 to 2.5 is more preferable.

  The method of mixing the monomer composition containing the monomer having the benzotriazole structure is not particularly limited. That is, the method for preparing the monomer composition is not particularly limited.

Examples of commercially available ultraviolet absorbers (E) containing units having a benzotriazole structure include UVA-101, 102, 103, 104, 5080, 5080 (OHV20), 55T, 55MHB, 7075, 7075 (OHV20) manufactured by Shin-Nakamura Chemical Co., Ltd. ), 73T, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., NCN-703S-30T, NCN-703S-30BK, NCI-905-20NPF manufactured by Nikko Chemical Laboratory.

The content of the ultraviolet absorber (E) having a benzotriazole structure is preferably 0.5 to 6.0% by weight, more preferably 1.5 to 3.0% by weight, based on the solid content of the coloring composition. When the content of the ultraviolet absorbent (E) is less than the above, the effect of the ultraviolet absorbent is small, and the light resistance is deteriorated. If the number is larger than the above, the sensitivity may be low and a problem such as pixel peeling may occur.

<Solvent>
In the photosensitive coloring composition for a solid-state imaging device of the present invention, a colorant is sufficiently dispersed and penetrated in a colorant carrier so that a dry film thickness on a substrate such as a glass substrate is 0.5 to 5 μm. A solvent can be included to facilitate application to form filter segments.

Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethyl Formamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobutyl Propyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl Ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl Sobuchiruketon, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among them, glycols such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate from the viewpoint of storage stability of the photosensitive coloring composition for a solid-state imaging device of the present invention. It is preferable to use acetates, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

The solvent can be used alone or in combination of two or more. Further, the solvent can adjust the photosensitive coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness. Therefore, the solvent is used in an amount of 800 to 4000 parts by weight based on 100 parts by weight of the coloring agent (A). It is preferable to use them.

<Method of producing photosensitive coloring composition for solid-state imaging device>
The photosensitive coloring composition for a solid-state imaging device of the present invention comprises a colorant (A) in a colorant carrier containing a resin (B) and a solvent, a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and a paint. A pigment dispersion is manufactured by finely dispersing using a variety of dispersing means such as a conditioner, and a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E) are dispersed into the pigment dispersion. And can be manufactured by mixing.

The pigment dispersion can also be produced by mixing colorants and the like separately dispersed in a colorant carrier.

The photosensitive coloring composition for a solid-state imaging device of the present invention is obtained by means of centrifugal separation, a sintered filter, a membrane filter, or the like, and has coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove coarse particles and mixed dust.

(Dispersion aid)
When dispersing the colorant (A) in the colorant carrier, a dispersing aid such as a dye derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersing agent is excellent in dispersing the colorant and has a large effect of preventing re-aggregation of the colorant after the dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersing agent is used. In this case, a color filter having a high spectral transmittance can be obtained.

Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone or triazine.
Among them, pigment derivatives are preferable, and the structure is a compound represented by the following general formula (4).
P-Ln General formula (4)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or phthalimidomethyl group optionally having a substituent n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine. Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthantrone, indanthrone, pyranthrone and biolanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; sulene pigments; metal complex pigments and the like.

Dye derivatives are described, for example, in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. And these can be used alone or as a mixture of two or more.
The amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more, based on 100 parts by weight of the colorant (A) from the viewpoint of improving dispersibility. is there. From the viewpoints of heat resistance and light resistance, it is preferably 40% by weight or less, and most preferably 35% by weight or less, based on 100 parts by weight of the coloring agent (A).

The resin type dispersant has a pigment affinity site having a property of adsorbing to the colorant, and a site compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant into the colorant carrier. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid alkylamine salt. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic esters, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group Such as oil-based dispersants, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resins, water-soluble polymer compounds, polyesters, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204 or BYK-. P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS, or BYKUMEN, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Lubrizol Japan, Ltd. , 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan Corporation 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines. These can be used alone or as a mixture of two or more, but are not necessarily limited thereto.

When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant (A). When the amount of the resin-type dispersant and the surfactant is less than 0.1 part by weight, the effect of the addition is difficult to obtain, and when the amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May be exerted.

<Other additive components>
(Polyfunctional thiol)
The photosensitive coloring composition for a solid-state imaging device of the present invention may further contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, such as hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, and ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimerca DOO -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine.
These polyfunctional thiols can be used alone or in combination of two or more.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 60 parts by weight, based on 100 parts by weight of the coloring agent (A).

(Leveling agent)
It is preferable to add a leveling agent to the photosensitive coloring composition for a solid-state imaging device of the present invention in order to improve the leveling property of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray and BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. Usually, the content of the leveling agent is preferably 0.003 to 0.5% by weight based on the total weight of the photosensitive coloring composition (100% by weight).

(Storage stabilizer)
The photosensitive coloring composition for a solid-state imaging device of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time of the composition. As the storage stabilizer, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, organic acids such as oxalic acid and its methyl ether, t-butyl pyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the coloring agent (A) contained in the photosensitive coloring composition.

(Adhesion improver)
Examples of the adhesion improver include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the coloring agent (A) contained in the photosensitive coloring composition.

<Color filter>
Next, a pixel color filter formed by using the photosensitive coloring composition for a solid-state imaging device of the present invention, and a method of manufacturing the color filter will be described.
The color filter of the present invention includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. The filter segment is formed on a substrate by applying the photosensitive coloring composition for a solid-state imaging device of the present invention by a spin coating method or a die coating method.

As a base material of the color filter, a glass plate such as soda lime glass, low alkali borosilicate glass, and alkali-free aluminoborosilicate glass having high transmittance with respect to visible light, and polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate may be used. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, a gas phase reaction method, and vacuum deposition. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after forming the panel.

If the BM is formed before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the BM, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Alternatively, a TFT can be formed in advance on the above-mentioned transparent substrate or reflective substrate and used as a driving substrate of a liquid crystal display device, and pixels can be formed thereon. By using a color filter in which filter segments are formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, the aperture ratio can be greatly increased, and high image quality and low power consumption of the color liquid crystal display device can be achieved. Can be.

<Production method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.

  Since the formation of the filter segment by the printing method can be performed by repeating the printing and drying of the coloring composition prepared as the printing ink, the patterning can be performed at low cost and excellent in mass productivity as a color filter manufacturing method. Further, fine patterns having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the composition be such that the ink does not dry and solidify on a printing plate or on a blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or extender.

  When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. According to the method, coating is performed so that the dry film thickness becomes 0.2 to 5 μm. The film dried as required is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove an uncured portion and form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  When having a filter segment other than at least one filter segment formed by the photosensitive coloring composition for a solid-state imaging device of the present invention, a normal red coloring composition, a green coloring composition, a blue coloring composition, or the like is used. Can be formed.

<Production method of color filter>
Hereinafter, the color filter of the present invention will be described in detail through a method of manufacturing the same (a method of manufacturing a color filter of the present invention).

  In the method for producing a color filter of the present invention, the colored composition for a solid-state imaging device of the present invention is applied to a substrate directly or via another layer (and then dried if necessary) to form a colored layer. It comprises a colored layer forming step, an exposing step of exposing the colored layer through a mask (for example, in a pattern), and a developing step of developing the exposed colored layer to form a pattern. If necessary, a step of curing the pattern by heating and / or exposure, or a post-baking step of performing a post-baking process on the developed colored layer may be provided. Through these steps, a colored pattern can be formed.

  The coloring composition of the present invention described above is used for forming a pattern of a color filter for a solid-state imaging device such as a CCD, and is particularly effective for forming a fine pattern. Specifically, it is effective for forming a pattern having a pattern size of 2.5 μm or less, and is particularly effective for forming a pattern having a pattern size of 2.0 μm or less. The pattern thickness is effective for forming a pattern having a thickness of 1.5 μm or less, and is particularly effective for forming a pattern having a thickness of 1.0 μm or less.

Hereinafter, the method for manufacturing the color filter of the present invention will be described in detail.
In the colored layer forming step, the colored composition is applied onto the substrate by a coating method such as spin coating, cast coating, roll coating, slit coating, and the like, and further dried as necessary to form a colored layer.
Examples of the substrate include a silicon substrate and the like, and a solid-state imaging device such as a CCD and a CMOS. These substrates may be formed with a black matrix for isolating each pixel. If necessary, an undercoat layer may be provided on the substrate for improving adhesion to a layer provided on the substrate, preventing diffusion of a substance, or flattening the surface of the substrate.

  In the exposing step, a specific pattern is exposed to the colored layer formed in the colored layer forming step through a mask. Ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used as radiation used in the exposure. Among them, the i-line is particularly preferable from the viewpoint of forming a finer pattern.

In the developing step, the exposed colored layer is developed with an alkali developer or the like.
As the alkali developer, any one can be used as long as it dissolves the unexposed portion of the colored photocurable composition of the present invention and does not dissolve the exposed portion (radiation irradiated portion). Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the organic solvents described in the section <Organic solvent>.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. , An alkaline compound such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene at a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. And an aqueous alkaline solution.
When a developer composed of an alkaline aqueous solution is used, it is generally preferable to wash with water after development.

As the alkali developer, it is preferable to use an alkaline aqueous solution in which the alkali concentration is adjusted to preferably pH 11 to 13, more preferably pH 11.5 to 12.5. When the alkali concentration is within the above range, the roughness and peeling of the pattern can be more effectively suppressed, the residual film ratio can be further improved, and the reduction of the development speed and the generation of the development residue can be further reduced. It can be suppressed effectively.
In the development step, it is preferable to carry out a development treatment using a developer composed of such an alkaline aqueous solution. The developing method includes, for example, a dip method, a spray method, a paddle method and the like, and the temperature is preferably 15 to 40 ° C.

  In the method for manufacturing a color filter of the present invention, it is preferable that a post-baking process is performed in a post-baking step in order to sufficiently cure the developed coating film. The heating temperature in the post-baking step is preferably from 100 to 300C, more preferably from 150 to 250C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

The color filter of the present invention is used for manufacturing a solid-state imaging device, and is suitable for an image sensor such as a CCD, particularly a high-resolution CCD device or a CMOS device having more than one million pixels. The color filter of the present invention is more preferably used, for example, as a color filter disposed between a light receiving unit of each pixel constituting a CCD and a microlens for condensing light.
Above all, it is more preferable to use as a color filter having a pattern size of 2.5 μm or less (more preferably 2.0 μm or less), and a pattern film having a pattern size of 2.5 μm or less (more preferably 2.0 μm or less). It is optimal to use as a color filter having a thickness of 1.5 μm or less (more preferably 1.0 μm or less).

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

The polymerization average molecular weight (Mw) of the resin was measured using a TSKgel column (manufactured by Tosoh Corporation), GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and polystyrene measured using THF as a developing solvent. It is a converted weight average molecular weight (Mw).

First, a method for producing the resin solution, the finely divided pigment, and the pigment dispersion used in Examples and Comparative Examples will be described.

<Method for producing resin solution>
(Preparation of resin solution (B1))
70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Acetate was added to obtain a resin solution (B1).

(Preparation of resin solution (B2))
560 parts of cyclohexanone is placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, and 45.5 parts of n-butyl methacrylate are dropped from a dropping tube. A mixture of 0 parts, 47.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to conduct a polymerization reaction.
After the completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 55 parts of cyclohexanone was added. A polymer solution was obtained.
Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate and 120.0 parts of cyclohexanone was added to 338 parts of the obtained copolymer solution at 70 ° C. for 3 hours. And dropped.
After cooling to room temperature, about 2 g of the resin solution was sampled, dried by heating at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Thus, a resin solution (B2) was obtained. The weight average molecular weight of the obtained photosensitive resin was 12,000.

(Preparation of resin solution (B3))
100 parts of propylene glycol monomethyl ether acetate is placed in a reaction vessel, and heated to 120 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, A polymerization reaction was carried out by dropping a mixture of 41.0 parts of nil methacrylate and 1.0 part of azobisisobutyronitrile over 2.5 hours.
Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours, and the solid content acid value = 0. The reaction was terminated when the pH reached 0.8, and a resin solution having a weight average molecular weight of about 12,000 was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 40%, and the resin solution (B3) solution was added. Prepared.

<Production method of micronized pigment>
(Production example 1 of micronized pigment)
100 parts of a diketopyrrolopyrrole-based red pigment PR254 (“Irgafor Red B-CF” manufactured by BASF), 1000 parts of ground salt, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and heated at 70 ° C. For 8 hours. The mixture was poured into 2,000 parts of warm water, stirred for about 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. After drying, 100 parts of a finely divided pigment (PR-1) was obtained.

(Production example 2 of micronized pigment)
100 parts of anthraquinone red pigment PR177 (“Chromophthal Red A2B” manufactured by BASF), 800 parts of ground salt, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. . The mixture was poured into 4000 parts of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. After drying, 100 parts of a finely divided pigment (PR-2) was obtained.

(Production example 3 of micronized pigment)
100 parts of a metal complex yellow pigment PY150 ("E4GN" manufactured by LANXESS), 1500 parts of ground salt, and 180 parts of diethylene glycol were charged into a 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. The kneaded material was poured into 5000 parts of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent. After drying for an hour, 95 parts of a finely divided pigment (PY-1) was obtained.

(Production example 4 of micronized pigment)
250 parts of yellow pigment (CI Pigment Yellow 139, “Pariotor Yellow D1819” manufactured by BASF), 700 parts of sodium chloride, maleic acid resin (“Marquid No. 3002” manufactured by Arakawa Chemical Co., acid value: 100) 107 Parts and 160 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, the mixture was poured into about 3 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water to remove sodium chloride and the solvent. It was dried in a hot air oven at a temperature of about 24 hours for about 24 hours to obtain 95 parts of a finely divided pigment (PY-2).

<Production method of pigment dispersion>
After uniformly stirring and mixing a mixture having the composition (parts by weight) shown in Table 1, the mixture was dispersed with an Eiger mill for 2 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 5 μm filter to obtain a pigment dispersion (DR- 1, 2, DY-1, 2) were produced.

Resin-type dispersant: "SOLSPERSE-20000" manufactured by Lubrizol Japan

[Examples 1 to 14, Comparative Examples 1 to 11]
<Preparation of photosensitive coloring composition for solid-state imaging device>
The mixture of the composition (parts by weight) and the ultraviolet absorber shown in Tables 2 to 5 were uniformly stirred and mixed, and then filtered through a 1 μm filter, followed by photosensitive coloring for solid-state imaging devices of Examples 1 to 14 and Comparative Examples 1 to 11. A composition was made. In this specification, Examples 8 to 11 are reference examples.

Table 3 shows the ultraviolet absorbers in Table 2.

Table 4 shows the composition of the UV absorber manufactured by Shin-Nakamura Chemical Co., Ltd. in Table 3.

Table 5 shows the compositions of the other ultraviolet absorbers in Table 3.

The abbreviations in Tables 2 to 5 are shown below.
<Photopolymerizable monomer (C)>
Photopolymerizable monomer C-1: dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer C-2: Trimethylolpropane EO-modified triacrylate (acrylic monomer having an EO-modified group "Aronix M-350" manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer C-3: trimethylolpropane PO-modified triacrylate ("Aronix M-321" manufactured by Toagosei Co., Ltd.)
Photopolymerizable monomer C-4: polybasic acid-modified acrylic oligomer ("Aronix M-520" manufactured by Toagosei Co., Ltd.)
<Photopolymerizable initiator (D)>
Photopolymerization initiator D-1: (oxime ester organic compound) 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE manufactured by Ciba Japan) −01)
Photopolymerization initiator (D2): 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by Ciba Japan) Irgacure 379 ")
Photopolymerization initiator D-3 :: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Japan)
<Sensitizer>
4,4'-bis (diethylamino) benzophenone ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.)
<Polyfunctional thiol>
Trimethylolethane tris (3-mercaptobutyrate) ("TEMB" manufactured by Showa Denko KK)
<Solvent>
Solvent: propylene glycol monomethyl ether acetate

<Evaluation>
[Adhesion evaluation]
The obtained photosensitive coloring composition for a solid-state imaging device is coated on a 6-inch silicon wafer by a spin coating method using a flattening film resist solution (HL-18s, manufactured by Nippon Steel Chemical Co., Ltd.) to form a pre-bake. Heat treatment was performed on a hot plate at 100 ° C. for 6 minutes. Further, the coating film was cured in an oven at 230 ° C. for 1 hour to form a 1.0 μm flattening film, thereby obtaining a wafer with a flattening film. Next, the obtained resist material was applied on a silicon wafer with a flattening film by a spin coater, and as a prebake, a heat treatment was performed on a hot plate at 100 ° C. for 1 minute. The thickness after prebaking was adjusted to 0.9 μm. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), pattern exposure was performed at a light exposure of 150 mJ / cm ² through a photomask for forming a 1.0 μm square pixel at a wavelength of 365 nm. Was done. The exposed coating film was subjected to paddle development with an organic alkali developer for 1 minute. After the paddle development, the substrate was rinsed with pure water by a spin shower for 20 seconds, and further rinsed with pure water for 20 seconds. Thereafter, water droplets remaining on the wafer were blown off by high-pressure air, and the substrate was dried naturally to form a square pixel pattern.
Thereafter, the substrate was dried by heating at 230 ° C. for 60 minutes to prepare an evaluation substrate.
The adhesion of this coating film was visually evaluated in three stages based on the following criteria.
: No pattern peeling is observed at all. パ タ ー ン: Pattern peeling is slightly observed. ×: Pattern peeling is observed.

[Light resistance evaluation]
After spectroscopy was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus), an accelerated exposure test at 470 W / m 2 was performed for 200 hours using a xenon lamp having a spectral distribution equivalent to sunlight. . The change in transmittance at 530 nm after light irradiation was calculated. Each sample was evaluated according to the following criteria.
：: Difference in transmittance at 530 nm before and after the test is less than 1.5% Δ: Difference in transmittance at 530 nm before and after the test is 1.5 or more and less than 5.0 ×: Difference in transmittance at 530 nm before and after the test is 5 .0 or more

Tables 6 and 7 show the spectral changes of Example 1 and Comparative Example 1 before and after the light resistance test. Table 8 shows a list of transmittance differences at 530 nm before and after the light resistance test.

As shown in Table 8, in Examples 1 to 14, the coloring composition containing the ultraviolet absorbent (E) containing a unit having a benzotriazole structure had good adhesion. In particular, as in Examples 1 to 7 and 9 to 12, the coloring composition in which the content of the ultraviolet absorber (E) is 0.5% by weight to 3.0% by weight based on the total solid content has particularly high adhesion. It was good.

Further, as in Examples 1 to 14, the coloring composition containing the ultraviolet absorbent (E) containing a unit having a benzotriazole structure had good light fastness. In particular, Examples 2 to 4 and 6 to 8 in which (e1 / e2) is 1.0 to 2.5 and the content of the ultraviolet absorber (E) is 1.5% by weight or more based on the total solid content. , 13-14, the change in transmittance at 530 nm was less than 1.5%, and the light resistance was particularly good. A coloring composition containing no ultraviolet absorber as in Comparative Example 1, a coloring composition formed from an ultraviolet absorber other than benzotriazole as in Comparative Examples 2 and 3, and a benzotriazole as in Comparative Examples 4 to 10. The change in transmittance at 530 nm of the coloring composition formed from the ultraviolet absorber containing the simple substance exceeded 5.0%. Further, as for the coloring composition containing 6.0% by weight of benzotriazole alone as in Comparative Example 11, the change in transmittance at 530 nm was Δ, but the adhesion was poor.

As described above, by including a fixed amount of an ultraviolet absorber containing a unit having a benzotriazole structure in a coloring composition, it is possible to obtain a high-quality color filter having good adhesion and no discoloration due to light irradiation. Can be.

Thereby, a coloring composition containing a fixed amount of an ultraviolet absorber containing a unit having a benzotriazole structure in the coloring composition is excellent in light resistance and adhesion, and can provide a high-quality color filter.

Claims (5)

A colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E);
The ultraviolet absorber (E) is a polymer containing a unit (e1) having a benzotriazole structure and a unit (e2) having no benzotriazole structure, and a weight ratio (e1 /) of (e1) to (e2). e2) is 1.0 to 10.0, wherein the photosensitive coloring composition for a solid-state imaging device is characterized in that: The photosensitive coloring composition for a solid-state imaging device according to claim 1, wherein the unit (e1) having a benzotriazole structure includes a unit having a benzotriazole structure represented by the general formula (1).
General formula (1)

[In the general formula (1), R ¹ , R ⁴ and X represent a hydrogen atom or an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, which may have a substituent, A heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R ³ represents an alkylene group, a cycloalkylene group which may contain a double bond, or an arylene group. R ^{1 in the} general formula (1) is a hydrogen atom or a methyl group, R ³ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁴ is a hydrogen atom or a 1 to 18 carbon atoms. X is a hydrocarbon group, wherein X is a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. The photosensitive coloring composition for a solid-state imaging device according to claim 2.   4. The solid-state imaging device according to claim 1, wherein the ultraviolet absorber (E) is contained in an amount of 0.5 to 6.0% by weight in a solid content of the entire coloring composition. 5. Photosensitive coloring composition.   A color filter, comprising: a filter segment formed on a substrate using the photosensitive coloring composition for a solid-state imaging device according to claim 1.