JP2017226820A - Blue colored resin composition comprising naphthalocyanine, color filter, and solid-state image sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue colored resin composition which enables preparation of an optical filter layer that has a blue color filter function and a function of cutting near infrared light at a wavelength of 900 nm or more for a solid-state image sensor, and which has excellent dispersion stability and heat resistance.SOLUTION: The blue colored resin composition comprises an organic coloring pigment classified as Pigment Blue, an organic coloring pigment classified as Pigment Violet, a naphthalocyanine compound having a specific structure, and a photopolymerizable monomer. A thin film having a thickness of 0.8 μm obtained by using the above blue colored resin composition shows a transmittance of 60% or more at a wavelength of 450 nm, a transmittance of 15% or less at a wavelength of 700 nm, and a transmittance of 80% or less at a wavelength of 910 nm.SELECTED DRAWING: None

Description

  The present invention relates to a blue colored resin composition, a color filter composed of the blue colored resin composition, and a solid-state imaging device comprising the color filter. More specifically, the present invention relates to a blue colored resin composition used for producing a color filter that selectively transmits a blue light region and also has a near-infrared absorption function, and a color filter having a colored pattern formed using the same. It is related with the near-infrared cut off filter which has the function of.

  In general, a color filter is required to capture a color image with a solid-state image sensor (image sensor). Conventionally used blue color filter functions as a filter that transmits only the blue light region in the visible light region, but has a weak ability to cut light in the near infrared region, and transmits near infrared light. End up. Therefore, when only a conventional blue color filter is used for a solid-state imaging device using a silicon substrate having a spectral sensitivity over the visible light region to the near infrared light region near 1100 nm, the effect of near infrared light When the blue signal is mixed with the near-infrared light signal, a difference from the visibility of the human eye is produced.

  In order to solve this problem, a method has been proposed in which the near-infrared cut filter layer is used in combination with the color filter layer to eliminate the influence of near-infrared light, and only visible light is taken into the pixel for photoelectric conversion. Patent Document 1 describes a method of providing an inorganic multilayer film made of a low refractive material and a high refractive material as a near infrared cut filter layer below the color filter layer.

  On the other hand, thinning of the near-infrared cut filter and the color filter is required for the purpose of downsizing the solid-state imaging device and high color separation. In Patent Document 2 and Patent Document 3, there is a color filter having improved color separation properties by containing a pyrrolopyrrole compound or a squarylium compound as a near-infrared absorber in a red colored resin composition or a green colored resin composition. Have been described.

Further, for the purpose of improving the reliability of the solid-state imaging device, further higher heat resistance of color filters and near infrared cut filters is required. Patent Document 4 describes a color filter in which heat resistance is improved by using a specific dipyrromethene compound in combination with a blue colored resin composition and a phthalocyanine compound or squarylium compound as a near infrared absorber.
Patent Document 5 discloses (A) an ethylenically unsaturated compound, (B) an infrared-absorbing phthalocyanine dye having an absorption maximum at 750 nm to 1200 nm, (C) a photopolymerization initiator, and (D) a cationic compound. There is described a photopolymerizable composition in which the influence of polymerization inhibition by oxygen is suppressed, which includes a dye and (E) a visible light absorbing dye that is not sensitized to visible light.

International Publication 2014/041742 Pamphlet JP2015-163955A Japanese Patent Laying-Open No. 2015-163958 JP 2012-77153 A JP 2003-337410 A

  However, the near-infrared absorber used in Patent Documents 2 and 3 has a problem that the absorption wavelength is 900 nm or less, and the ability to cut the spectral sensitivity wavelength region of a silicon substrate of 900 nm or more is insufficient. Moreover, in patent document 4, since dye was used for the blue coloring resin composition, there existed a problem that the heat resistance of a color filter and the dispersion stability of the pigment dispersion liquid which added dye were inadequate. Further, in Patent Document 5, since a phthalocyanine compound is used, the color filter has insufficient heat resistance and light resistance.

An object of the present invention is to provide a blue colored resin composition excellent in dispersion stability, which can produce a blue thin film color filter for a solid-state imaging device having a function of a near infrared cut filter in a single development process. It is.
Another object of the present invention is to provide a blue colored resin composition capable of forming a color filter preferably having improved heat resistance or light resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors include an organic coloring pigment classified as pigment blue, an organic coloring pigment classified as pigment violet, a specific naphthalocyanine compound and a photopolymerizable monomer. The present inventors have found that the above problems can be solved by using a blue colored resin composition.

That is, various aspects of the present invention are as follows.
[1]. Organic color pigments classified as pigment blue, organic color pigments classified as pigment violet, the following general formula (1)

(In Formula (1), R _{1 to} R ₂₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom. Represents an aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, —OR ₂₅ or —SR ₂₆ , wherein R ₂₅ and R ₂₆ are each independently a hydrogen atom, Represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, M represents two hydrogen atoms, a metal atom, a metal Represents oxide or metal halide.)
A blue colored resin composition containing a naphthalocyanine compound represented by formula (1) and a photopolymerizable monomer, wherein the transmittance of a thin film having a thickness of 0.8 μm obtained using the blue colored resin composition is:
60% or more at a wavelength of 450 nm,
A blue colored resin composition that is 15% or less at a wavelength of 700 nm and 80% or less at a wavelength of 910 nm.
[2]. The blue colored resin composition according to [1] above, wherein a 0.8 μm-thick thin film obtained using the blue colored resin composition has a wavelength within a range of 505 to 515 nm at which the transmittance is 50%. A blue colored resin composition.
[3]. The blue colored resin composition according to [1] or [2] above, wherein the organic color pigment classified as pigment blue is any one of pigment blue 15: 4 and pigment blue 15: 6.
[4]. The blue colored resin composition according to any one of [1] to [3], wherein the organic coloring pigment classified as pigment violet is pigment violet 23.
[5]. The blue colored resin composition according to any one of [1] to [4], wherein the photopolymerizable monomer is an acrylate monomer.
[6]. The blue colored resin composition according to [5], wherein the photopolymerizable monomer is an alkylene oxide-modified acrylate monomer.
[7]. Furthermore, the blue colored resin composition according to [5] or [6], further including an aminoalkylphenone photopolymerization initiator or an oxime photopolymerization initiator.
[8]. A color filter comprising the blue colored resin composition according to any one of [1] to [7].
[9]. The color filter according to [8], wherein a step of applying a blue colored resin composition to a substrate, a step of pre-baking the blue colored resin composition applied to the substrate to obtain a thin film, and a mask on the thin film A color filter obtained through a step of irradiating radiation through a pattern and a step of developing a thin film irradiated with the radiation.
[10]. A solid-state imaging device comprising the color filter described in [8] or [9] above.

  The blue colored resin composition of the present invention is excellent in dispersion stability and can form a thin color filter, and the blue color filter having the function of a near infrared cut filter obtained using the blue colored resin composition is heat resistant. In addition, the absorption capacity of near infrared rays of 900 nm or more is also excellent. Further, in many cases, the blue color filter is also excellent in light resistance.

The blue colored resin composition of the present invention includes an organic colored pigment classified as pigment blue (hereinafter simply referred to as “blue pigment”) and an organic colored pigment classified as pigment violet (hereinafter simply referred to as “purple pigment”). Contain). As these organic pigments, those having spectral characteristics suitable for color filters are preferable.
Specific examples of blue pigments include Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 and 79 etc. are mentioned. Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, and the like are preferable.
Specific examples of the purple pigment include Pigment Violet 1, 1: 1, 2: 2, 2: 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Pigment Violet 23 and the like are preferable.

The content of the organic coloring pigment in the blue colored resin composition of the present invention is the total solid content in the blue colored resin composition (blue pigment, purple pigment as essential components, naphthalocyanine compound of the formula (1) and light 1 to 60 parts by mass, preferably 20 to 50 parts by mass with respect to 100 parts by mass of the polymerizable monomer and the optional components such as a dispersant, a dispersion aid, and a binder resin, all solid components except the solvent) is there. By setting the content of the organic coloring pigment in the blue colored resin composition within the above range, sufficient color purity can be obtained without causing problems of dispersion stability such as aggregation. In addition, the blending ratio of the blue pigment and the purple pigment in the blue colored resin composition of the present invention is a specific range in which the transmittance of a thin film having a thickness of 0.8 μm obtained using the blue colored resin composition of the present invention is described later. If it is in, it will not be specifically limited.
Moreover, the blue pigment and the violet pigment contained in the blue colored resin composition of the present invention are preferably as fine as possible. Considering handling properties and the like, the average primary particle size is preferably 100 nm or less, more preferably 5 to 80 nm, and even more preferably 5 to 50 nm. The average primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

  The blue colored resin composition of the present invention contains a naphthalocyanine compound represented by the formula (1).

In formula (1), R _{1 to} R ₂₄ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic ring having 4 to 20 carbon atoms. Group, -OR ₂₅ or -SR ₂₆ , the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms and the heterocyclic group having 4 to 20 carbon atoms have a substituent. May be. R ₂₅ and R ₂₆ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. .

Examples of the halogen atom represented by R _{1 to} R _{24 in} Formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} the formula (1) is not particularly limited as long as it is a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. The alkyl group may have a branch or may form a ring.
Specific examples of the alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} the formula (1) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso- Butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, isohexyl group, sec-hexyl group, n-heptyl group, iso-heptyl group, sec-heptyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 1-t-butyl-2-methylpropyl group, n-nonyl Group, 3,5,5-trimethylhexyl group, n-decyl group, n-dodecyl group, cyclohexyl group, cyclopentyl group, cyclohexylmethyl group, cyclohexylethyl Group, cyclopentylmethyl group and cyclopentylethyl group, and the like.
The alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. A linear or branched alkyl group having 1 to 8 carbon atoms is more preferred.

Examples of the substituent that the alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have, for example, an alkoxy group (the above-described alkyl group having 1 to 20 carbon atoms and oxygen) An alkoxy group having atoms bonded thereto), a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), amino group, cyano group, nitro group and the like, but are not limited thereto.
In the present specification, the phrase “having a substituent” in the alkyl group having 1 to 20 carbon atoms having a substituent is one or two of a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. It means that two or more hydrogen atoms are substituted with a substituent such as an alkoxy group, a halogen group, an amino group, a cyano group, a nitro group, etc., and the phrase “unsubstituted” It means that the hydrogen atom of the saturated aliphatic hydrocarbon group consisting of 1 to 20 is not substituted with a substituent such as an alkoxy group, a halogen group, an amino group, a cyano group, or a nitro group. In the present specification, “having a substituent” and “unsubstituted” are used in the same meaning as described herein.

The aryl group having 6 to 20 carbon atoms represented by R _{1 to} R _{24 in} the formula (1) is not particularly limited as long as it is a residue obtained by removing one hydrogen atom from an aromatic ring having 6 to 20 carbon atoms. Is not to be done. Specific examples thereof include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl. Group, trityl group, pyrenyl group and the like. A phenyl group is particularly preferred.
The aryl group having 6 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have a substituent. Examples of the substituent which may be included include the same substituents as those which the alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have.

The heterocyclic group having 4 to 20 carbon atoms represented by R _{1 to} R _{24 in} formula (1) is not particularly limited as long as it is a residue obtained by removing one hydrogen atom from a heterocyclic ring having 4 to 20 carbon atoms. Is not to be done. Specific examples thereof include pyridyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, pyrazolyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, Examples thereof include a triazinyl group, an indolyl group, an isoindolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group, an isoquinolyl group, a prynyl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, and a phenothiazinyl group. A pyridyl group is particularly preferred.
The heterocyclic group having 4 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have a substituent. Examples of the substituent which may be included include the same substituents as those which the alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ₂₅ and R ₂₆ in formula (1) include the same alkyl groups having 1 to 20 carbon atoms represented by R _{1 to} R ₂₄ in formula (1). It is done.
The alkyl group having 1 to 20 carbon atoms represented by R ₂₅ and R _{26 in} Formula (1) may have a substituent. Examples of the substituent which may be included include the same substituents as those which the alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ₂₅ and R ₂₆ in Formula (1) include the same aryl groups having 6 to 20 carbon atoms as represented by R _{1 to} R ₂₄ in Formula (1). It is done.
The aryl group having 6 to 20 carbon atoms represented by R ₂₅ and R _{26 in} Formula (1) may have a substituent. Examples of the substituent which may be included include the same substituents as those which the alkyl group having 1 to 20 carbon atoms represented by R _{1 to} R _{24 in} Formula (1) may have.

R _{1 to} R ₂₄ in Formula (1) are preferably each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. R _{1 to} R ₂₄ are all hydrogen atoms, or R ₁ , R _{2 to} R ₅ , R ₇ , R _{8 to} R ₁₁ , R ₁₃ , R _{14 to} R ₁₇ , R _{19 and} R _{20 to} R _23. Is a hydrogen atom and R ₆ , R ₁₂ , R _{18 and} R ₂₄ are unsubstituted aryl groups having 6 to 20 carbon atoms, or R _{2 to} R ₅ , R ₆ , R _{8 to} R _11. , R ₁₂ , R _{14 to} R ₁₇ , R ₁₈ , R _{20 to} R _{23 and} R ₂₄ are hydrogen atoms, and R ₁ , R ₇ , R _{13 and} R ₁₉ are unsubstituted aryl having 6 to 20 carbon atoms More preferably, it is a group. R _{1 to} R ₂₄ are all hydrogen atoms, or R ₁ , R _{2 to} R ₅ , R ₇ , R _{8 to} R ₁₁ , R ₁₃ , R _{14 to} R ₁₇ , R _{19 and} R _{20 to} R _23. Is a hydrogen atom and R ₆ , R ₁₂ , R _{18 and} R ₂₄ are phenyl groups, or R _{2 to} R ₅ , R ₆ , R _{8 to} R ₁₁ , R ₁₂ , R _{14 to} R ₁₇ , R ₁₈ , R _{20 to} R _{23 and} R ₂₄ are more preferably hydrogen atoms, and R ₁ , R ₇ , R _{13 and} R ₁₉ are more preferably phenyl groups.

In formula (1), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. When M represents two hydrogen atoms, a structure in which the NMN portion in the formula (1) is shown as two NHs is formed.
Examples of the metal atom represented by M in Formula (1) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.
Examples of the metal oxide represented by M in the formula (1) include titanyl and vanadyl.
Examples of the metal halide represented by M in the formula (1) include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride.
M in the formula (1) is preferably copper, zinc, cobalt, nickel, iron, vanadium, titanium, indium chloride or tin (II) chloride. Copper, zinc, vanadium or titanium is more preferable, and vanadium is particularly preferable.

  The naphthalocyanine compound represented by Formula (1) can be used alone or in combination of two or more. The content of these naphthalocyanine compounds in the blue colored resin composition is usually 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total solid content. By making the content of the naphthalocyanine compound in the blue colored resin composition within the above range, the transmittance in the visible wavelength range is not reduced, the dispersion stability such as aggregation is not caused, and the infrared wavelength range A sufficient light-shielding property can be obtained.

The naphthalocyanine compound represented by the formula (1) preferably has a maximum absorption wavelength in the wavelength region of 750 to 1500 nm, and more preferably has a maximum absorption wavelength in the wavelength region of 780 to 1100 nm. By using a naphthalocyanine compound having a maximum absorption wavelength in the wavelength region, light in the target wavelength region is efficiently absorbed.
The maximum absorption wavelength in the present invention refers to the wavelength at which the absorbance is maximum in the wavelength region measured with an ultraviolet-visible near-infrared spectrophotometer.

  Further, when the naphthalocyanine compound represented by the formula (1) is present in the pigment dispersion in a state dissolved in an oil-soluble organic solvent or an aqueous medium, the heat resistance of the cured product of the colored resin composition containing the pigment dispersion May decrease. Therefore, the naphthalocyanine compound is preferably present in the pigment dispersion in a state of being dispersed in an oil-soluble organic solvent or an aqueous medium.

  Next, the manufacturing method of the compound represented by Formula (1) is demonstrated. The method for producing the compound represented by the formula (1) is not particularly limited, and a conventionally known method can be appropriately used. For example, in the presence of the corresponding metal compound, naphthalenedicarboxylic acid or It is known to synthesize naphthalocyanine having a metal at the center from its derivative (an acid anhydride, diamide, dinitrile, etc.) by direct cyclization (for example, Chemistry-A. European Journal, Vol. 9, 5123- 5134 (issued in 2003)). At this time, it is preferable that a catalyst (for example, ammonium molybdate) and urea coexist. Or after synthesizing the metal-free body of naphthalocyanine once using a lithium compound, it can also synthesize | combine using metal compounds, such as a vanadium compound, as mentioned later.

  The cyclization reaction can be performed in the absence of a solvent, but is preferably performed in an organic solvent. The organic solvent that can be used in the cyclization reaction is not particularly limited as long as it has low reactivity with naphthalenedicarboxylic acid or a derivative thereof as a starting material, but an inert solvent that does not exhibit reactivity is preferable. Examples of the organic solvent include inert solvents such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; methanol Alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 1-hexanol, 1-pentanol and 1-octanol; pyridine, N, N-dimethylformamide, N, N-dimethylacetamide And aprotic polar solvents such as N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide and sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene, benzonitrile and sulfolane are preferred. 1-octanol, dichlorobenzene, benzonitrile and sulfolane are more preferred. These solvents may be used alone or in combination of two or more.

  The amount of naphthalenedicarboxylic acid or its derivative and metal compound used for the cyclization reaction is not particularly limited as long as the reaction proceeds. For example, the naphthalenedicarboxylic acid or derivative thereof is usually used in the range of 1 to 500 parts by weight, preferably 10 to 350 parts by weight with respect to 100 parts by weight of the organic solvent, and with respect to 1 mole of the naphthalenedicarboxylic acid or derivative thereof. The metal compound is usually used in the range of 0.25 to 0.5 mol, preferably 0.25 to 0.4 mol. The conditions for the cyclization reaction are not particularly limited, but the reaction temperature is preferably in the range of 30 to 250 ° C, more preferably in the range of 80 to 200 ° C. The reaction time is preferably 1 to 30 hours. Further, the cyclization reaction may be performed in an air atmosphere, but is preferably performed in an inert gas atmosphere (for example, under circulation of nitrogen gas, helium gas, argon gas, etc.).

The use ratio of the raw material when synthesizing the compound represented by the formula (1) using a metal compound of naphthalocyanine and a metal compound is 0.1% of the metal compound with respect to 1 mol of the metal compound of naphthalocyanine. It is preferable to use 10 to 10 mol, more preferably 0.5 to 5 mol, and still more preferably 1 to 3 mol. As the metal compound, inorganic and organic metal compounds can be used. Specific examples thereof include halides (for example, chlorinated products, brominated products), oxyhalides, sulfates, acetates, metal acetylacetonates, and the like. Preferred are halides and oxyhalides, and more preferred are oxyhalides.
The compound obtained by the above reaction may be subjected to crystallization, filtration, washing, drying and the like according to a conventionally known method.
By such an operation, the naphthalocyanine compound represented by the formula (1) can be obtained efficiently and with high purity.

  Specific examples of the compound represented by formula (1) are shown below, but the present invention is not limited thereto.

The blue colored resin composition of the present invention contains a photopolymerizable monomer.
The photopolymerizable monomer contained in the blue colored resin composition of the present invention is a compound having a polymerizable group that can be polymerized by light irradiation. The polymerizable group is not particularly limited as long as it is a group that contributes to polymerization, but an acrylate monomer is preferable in terms of the design of the photolithography method. Although there is no restriction | limiting in particular as an acrylate monomer, From the point of the favorable solubility with respect to a developing solution, and the fine pattern formation property, the acrylate monomer with a molecular weight of 2000 or less is more preferable. Alkylene oxide modified acrylate monomers are particularly preferred.
The “alkylene oxide-modified acrylate monomer” in the present invention is a weight average molecular weight (in terms of polystyrene; GPC) having an alkylene oxide structure (a structure in which an alkylene group and an oxygen atom are bonded) and an acrylate group or a methacrylate group in the structure. Means a compound having a value of 3000 or less.

Specific examples of the acrylate monomer include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M -452, M-450, M-408, M-403, M-400, M-402, M-404, M-406, M-405, M-460, M-510 (manufactured by Toagosei Co., Ltd.) , NK ester, A-9300, A-9300-1CL, A-GLY-3E, A-GLY-9E, A-GLY-20E, TMPT, A-TMM-3, A-TMM-3L, A-TMM- 3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, U-4HA, U-6HA, U-6LPA, UA-1100H, UA-53H, UA- 33H (new MURA CHEMICAL INDUSTRY CO., LTD.), Kayarad TMPTA, TPA-330, D-310, T-1420 (T), GPO-303, DPHA-40H, PET-30, DPEA-12, FM-700, DPHA, THE -330, RP-1040, DPCA-20, DPCA-30, DPCA-60, DPCA-120, CCR-129H, ZAR-1035, ZFR-1491H, ZCR-1569H, UXE-3000, UXE-3024 Etc.).
Specific examples of the alkylene oxide-modified acrylate monomer include Aronix M-310, M-321, M-350, M-360, M-313, M-315, M-460 (manufactured by Toa Gosei Co., Ltd.), NK Ester, A-9300, ATM-35E, A-GLY-3E, A-GLY-9E, A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.), Kayrad TPA-330, GPO-303, THE-330 RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  The content of the photopolymerizable monomer in the blue colored resin composition of the present invention is determined by exposing the colored resin composition film obtained by applying the colored resin composition of the present invention to a substrate and then removing the solvent as necessary. As long as a cured film can be formed by applying, the ratio can be set to any ratio without particular limitation. Specifically, it is usually 1 to 80 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition.

A thin film having a thickness of 0.8 μm obtained using the blue colored resin composition of the present invention exhibits a transmittance of 60% or more at a wavelength of 450 nm, 15% or less at a wavelength of 700 nm, and 80% or less at a wavelength of 910 nm. By having the transmittance characteristics described above, the thin film (blue color filter) made of the blue colored resin composition of the present invention is excellent in color separability from the red color filter and the green color filter. In addition, the transmittance | permeability in this invention means the value measured using the ultraviolet visible near-infrared spectrophotometer.
A 0.8 μm-thick thin film obtained using the blue colored resin composition of the present invention may exhibit a transmittance of 70% or more at a wavelength of 450 nm, 12% or less at a wavelength of 700 nm, and 70% or less at a wavelength of 910 nm. More preferably, the transmittance is 75% or more at a wavelength of 450 nm, 10% or less at a wavelength of 700 nm, and 60% or less at a wavelength of 910 nm.

In addition, a thin film having a thickness of 0.8 μm obtained using the blue colored resin composition of the present invention preferably has a wavelength with a transmittance of 50% within a range of 505 to 515 nm, and within a range of 508 to 512 nm. It is more preferable to have it at 510 nm.
When the thickness of the thin film is not 0.8 μm, the following calculation formula: Actual film thickness (μm) /0.8 (μm)
By multiplying the coefficient obtained in (1) with the measured value of transmittance, the transmittance of the thin film of 0.8 μm can be converted. Specifically, for example, when the transmittance of a thin film having a thickness of 1.6 μm is 25%, the transmittance converted into a thin film having a thickness of 0.8 μm is 1.6 μm / 0.8 μm × 25% = 50%.

The blue colored resin composition of the present invention may be used in combination with an oil-soluble organic solvent or an aqueous medium. The oil-soluble organic solvent or aqueous medium that can be used in combination is not particularly limited, but those that can maintain dispersion stability when the colored resin composition is produced are preferred.
Specific examples of the oil-soluble organic solvent include benzenes such as toluene and xylene, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate, propylene glycol monomethyl Propylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propionate such as methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate , Lactates such as methyl lactate, ethyl lactate, butyl lactate, diethylene glycol Diethylene glycols such as dimethyl ether, diethylene glycol monoethyl ether, acetates such as methyl acetate, ethyl acetate, butyl acetate, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, etc. Ketones, and alcohols such as methanol, ethanol, butanol, isopropyl alcohol, and benzyl alcohol. Since some of the organic solvents mentioned here are oil-soluble and water-based, they are listed in the following specific examples of the aqueous medium.

  Specific examples of the aqueous medium include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, Polyhydric alcohols such as polypropylene glycol, glycerin, trimethylolpropane, 1,3-pentanediol and 1,5-pentanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene Glycol monoethyl ether, triethylene glycol monobutyl ether and Glycol derivatives such as dipropylene glycol monomethyl ether; ethanolamine, diethanolamine, amines such as triethanolamine and morpholine; 2-pyrrolidone, NMP, 1,3-dimethyl - imidazolidinone.

  You may use these individually or in combination of 2 or more types. The amount of the oil-soluble organic solvent or aqueous medium used is usually 10000 parts by mass or less, preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the total solid content of the blue colored resin composition.

A photopolymerization initiator may be used in combination with the blue colored resin composition of the present invention. In combination with the photopolymerization initiator, a cured film can be easily formed by exposing the colored resin composition film obtained by applying the colored resin composition of the present invention to the substrate and then removing the solvent. This is a preferable aspect. The photopolymerization initiator that can be used in combination is not particularly limited, but an aminoalkylphenone photopolymerization initiator or an oxime photopolymerization initiator is preferable. Specific examples of the aminoalkylphenone photopolymerization initiator include methyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4, 4′-bis (dimethylaminobenzophenone), 4,4′-bis (ethylmethylamino) benzophenone, IRGACURE 369, 379, 379EG, 907, KAYACURE EPA (manufactured by Nippon Kayaku Co., Ltd.), EAB-F (Hodogaya) Chemical Industry Co., Ltd.). Specific examples of the oxime photopolymerization initiator include IRGACURE OXE-01, OXE-02, PAG103, PAG121, and PAG203 (manufactured by BASF).
The content of these photopolymerization initiators in the blue colored resin composition of the present invention is not particularly limited, but is usually 50 parts by mass or less, preferably 0.5 parts per 100 parts by mass of the total solid content of the colored resin composition. To 25 parts by mass.

A dispersant may be used in combination with the blue colored resin composition of the present invention. The combined use of the dispersant improves the dispersibility of the pigment. Examples of the dispersant include a dye-based dispersant, a resin-based dispersant, a surfactant, and the like that have good adsorptivity to the pigment.
As a method for using a dye-based dispersant, for example, a method of mixing a sulfonated organic pigment, a carboxyl oxide or a metal salt thereof with a pigment, a method of mixing a substituted aminomethyl derivative with a pigment, and the like are known as known techniques. Yes.
Examples of the resin dispersant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), and the like, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.), EFKA-46, EFKA -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Polymer dispersants such as Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco), Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.) , Addisper PB711, PB411, PB111, PB 14, PB821,822,824,881 (manufactured by Ajinomoto Fine-Techno), Solsperse 5000,13240,20000,24000,26000,28000,71000 (manufactured by Avecia) and the like. In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.
The content of these dispersants in the blue colored resin composition of the present invention is not particularly limited, but is usually 70 parts by mass or less, preferably 3 to 40 parts by mass with respect to 100 parts by mass of the total solid content.

  A binder resin may be used in combination with the blue colored resin composition of the present invention. The binder resin is desirably soluble in an alkaline developer used in the development processing step in terms of the design of the photolithography method used for producing the color filter of the present invention. Further, as the binder resin, those having sufficient curing characteristics with a photopolymerization initiator, a photopolymerizable monomer, etc. in order to form a good fine pattern are desirable.

  A known resin can be used as the binder resin. More preferably, the binder resin is an ethylenically unsaturated monomer having one or more carboxyl group or hydroxyl group-containing ethylenically unsaturated monomer or other copolymerizable aromatic hydrocarbon group or aliphatic hydrocarbon group listed below. A copolymer such as a saturated monomer is desirable. In addition, those having an epoxy group at the side chain or terminal, and epoxy acrylate resins to which acrylate is added can also be used. These monomers may be used alone or in combination of two or more.

  Specific examples of the carboxyl group-containing ethylenically unsaturated monomer that can be used in the present invention include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, and trivalent or higher unsaturated polycarboxylic acids (anhydrous) Products), 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, etc. it can. These can be used alone or in admixture of two or more.

  Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer that can be used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxy. Butyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate 5-hydroxyhexyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 5-hydroxy-3-methyl-pentyl (meth) acrylate, cyclohexane-1,4-dimethanol-mono (meth) acrylate Hydroxyl groups, such as rate, 2- (2-hydroxyethyloxy) ethyl (meth) acrylate, glycerin monomethacrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) monomethacrylate Examples include terminal polyalkylene glycol mono (meth) acrylate. These can be used alone or in admixture of two or more.

  Examples of the other copolymerizable ethylenically unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, and m-chloro. Aromatic vinyl compounds such as styrene, p-chlorostyrene, p-methoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, paracumylphenoxyethylene glycol (meta ) Acrylate, 2-hydroxy Unsaturated carboxylic acid esters such as 3-phenoxypropyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, o-phenylphenol (meth) acrylate hydroxyethylate, phenoxyethyl (meth) acrylate, cyclopentyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonorbornyl (meth) acrylate, isobornyl ( (Meth) acrylate, bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate , Dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.02,6] dec-8-yl = (meth) acrylate, tricyclo [5.2.1.02,6] dec-4-methyl = Alicyclic skeletons such as (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, tert-butylcyclohexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as mono (meth) acrylate and poly (ethylene glycol-propylene glycol) monomethacrylate, methoxypolyethylene glycol monomethacrylate, lauroxypolyethylene glycol mono ( Alkyl) -terminated polyalkylene glycol mono, such as acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polypropylene glycol monoacrylate, allyloxy polyethylene glycol-polypropylene glycol mono (meth) acrylate Unsaturated carboxylic acid aminoalkyl esters such as (meth) acrylates, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate , Glycidyl acrylate, glycidyl methacrylate, 3,4-epoxy Unsaturated carboxylic acid glycidyl esters such as cibutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, Carboxylic acid vinyl esters such as vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, etc. Vinyl cyanide compound, acrylamide, methacrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- 2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, unsaturated amides such as maleimide or unsaturated imides, aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, polystyrene, poly Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as methyl acrylate, polymethyl methacrylate, poly n-butyl acrylate, poly n-butyl methacrylate, and polysilicone. These can be used alone or in admixture of two or more.

  A polymer in which an unsaturated double bond is further introduced into the side chain of the copolymer is also useful. For example, an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate in the maleic anhydride portion of a copolymer with styrene, vinylphenol, acrylic acid, acrylic ester, acrylamide, or the like copolymerizable with maleic anhydride Acrylic acid is added to the hydroxyl group of a compound obtained by reacting an acrylate having an epoxy group, such as glycidyl methacrylate, and half-esterified, and a copolymer of acrylic acid, an acrylic ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. Examples thereof include reacted compounds. Also, urethane resin, polyamide, polyimide resin, polyester resin, commercially available ACA-200M (manufactured by Daicel), ORGA-3060 (manufactured by Osaka Organic Chemical), AX3-BNX02 (manufactured by Nippon Shokubai), UXE-3024 (Nippon Kayaku) Manufactured), UXE-3000 (manufactured by Nippon Kayaku), ZGA-287H (manufactured by Nippon Kayaku), TCR-1338H (manufactured by Nippon Kayaku), ZXR-1722H (manufactured by Nippon Kayaku), ZFR-1401H (manufactured by Nippon Kayaku) And ZCR-1642 (manufactured by Nippon Kayaku) can also be used.

  When producing the binder resin (copolymer) used in the present invention, a polymerization initiator is used. Specific examples of the polymerization initiator used when synthesizing the copolymer include α, α′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), Examples thereof include t-butyl peroctoate and di-t-butyl peroxide benzoylmethyl ethyl ketone peroxide. The ratio of the polymerization initiator used is usually 0.01 to 25 parts by mass with respect to the total of all monomers used for the synthesis of the copolymer. In addition, when synthesizing a copolymer, it is preferable to use an organic solvent described below, but use a solvent having sufficient dissolving power for the monofunctional monomer or polymerization initiator used. Can do. The reaction temperature when synthesizing the copolymer is preferably 50 to 120 ° C., particularly preferably 80 to 100 ° C. The reaction time is preferably 1 to 60 hours, more preferably 3 to 20 hours. The preferred acid value of the copolymer is 10 to 300 (mgKOH / g), and the preferred hydroxyl value is 10 to 200 (mgKOH / g). When the acid value or the hydroxyl value is 10 or more, developability can be appropriately maintained. The weight average molecular weight (Mw) of the copolymer is preferably 2000 to 400,000, and more preferably 3000 to 100,000. When the weight average molecular weight is 2000 or more and 400000 or less, sensitivity, developability and the like can be appropriately maintained.

  In this invention, the said binder resin can be used individually or in mixture of 2 or more types. The content of the binder resin in the present invention is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the colored resin composition. In this case, when the content of the binder resin is 0.5 parts by mass or more, alkali developability can be appropriately maintained, and problems such as background contamination and film residue in areas other than the area where pixels are formed can be obtained. The possibility of occurrence can be suppressed.

  In the blue colored resin composition of the present invention, various additives such as a surfactant, a thermal polymerization initiator, a polymerization inhibitor, and an ultraviolet absorber can be used in combination as necessary. The additive that can be used in combination is not particularly limited as long as the effect of the blue colored resin composition of the present invention is not impaired. As an additive, for example, when a dipyrromethene compound represented by the following general formula (a) is used in combination with a boron atom, a boron compound, a metal atom, or a dipyrromethene complex compound coordinated to a metal compound or a tautomer thereof, Since the storage stability at the time of setting it as a blue colored resin composition falls, it is not preferable.

In formula (a), R _{31 to} R ₃₆ each independently represents a hydrogen atom or a monovalent substituent, and R ₃₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The method for preparing the blue colored resin composition of the present invention includes an organic pigment classified as an essential component, pigment blue, an organic pigment classified as pigment violet, a naphthalocyanine compound represented by the above formula (1), and photopolymerization. There is no particular limitation as long as the water-soluble monomer and the optional oil-soluble organic solvent or aqueous medium, photopolymerization initiator, dispersant, and binder resin can be mixed uniformly. Examples of the preparation method include a method of mixing and dispersing using an apparatus such as a dissolver or a homomixer.
In addition, an organic pigment classified as pigment blue, an organic pigment classified as pigment violet, and a naphthalocyanine compound represented by the above formula (1), a dispersant and an oil-soluble organic solvent or an aqueous medium, Using a sand grinder, a pin mill, a slit mill or an ultrasonic disperser, a pigment dispersion was prepared by pre-dispersing with beads made of glass or zirconia having a particle diameter of 0.01 to 1 mm. A method of obtaining a blue colored resin composition by adding a photopolymerizable monomer and various optional components to the pigment dispersion later is one of preferred embodiments.
Furthermore, before carrying out the above-mentioned bead dispersion, a strong shearing force can be obtained using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. The kneading and dispersing treatment while giving the value is a preferred embodiment for obtaining a pigment dispersion.
The time for the kneading and dispersing treatment is not particularly limited, but generally 1 hour or more is preferable. For details on kneading and dispersing, see T.W. C. The description of “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) can be considered.
The blue colored resin composition obtained by the above method or the like can be subjected to a microfiltration treatment with a filter or the like for removing foreign substances and the like as necessary.

  Next, a typical method for preparing a color filter comprising the blue colored resin composition of the present invention will be described. First, the blue colored resin composition of the present invention is formed on a substrate such as a glass substrate or a silicon substrate by a spin coating method, a roll coating method, a slit and spin method, a die coating method, a bar coating method, or the like. It is applied to a thickness of 0.1 to 20 μm, more preferably 0.5 to 5 μm. If necessary, it is dried in a vacuum chamber at a temperature of 23 to 150 ° C. for 1 to 60 minutes, more preferably A film can be formed by drying under reduced pressure at a temperature of 60 to 120 ° C. for 1 to 10 minutes and further performing a pre-bake treatment with a hot plate or a clean oven. Next, after irradiating radiation (for example, an electron beam or ultraviolet rays, ultraviolet rays are preferable, ultraviolet rays are preferable) through a predetermined mask pattern by a general photolithography method, a surfactant aqueous solution, an alkaline aqueous solution, or a surfactant and an alkali are used. It can develop with the mixed aqueous solution of an agent. Development methods include a dip method, a spray method, a shower method, a paddle method, and an ultrasonic development method, and any of these methods may be combined. A post-baking process may be performed after removing unirradiated parts by development and rinsing with water. The post-bake treatment can be performed, for example, at a temperature of 130 to 300 ° C. for a time of 1 to 120 minutes, more preferably at a temperature of 150 to 250 ° C. for a time of 1 to 30 minutes. In this way, a color filter comprising the blue colored resin composition of the present invention can be obtained.

  In the above, polyoxyalkylene alkyl ether or the like can be used as the surfactant. Moreover, as an alkaline agent, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. are used. In the present invention, it is preferable to use an aqueous solution containing both an alkali agent and a surfactant. Development is usually carried out at a processing temperature of 10 to 50 ° C., preferably 20 to 40 ° C., for a processing time of usually 30 to 600 seconds, preferably 30 to 120 seconds.

  The color filter made of the blue colored resin composition of the present invention has both a thin blue color filter function suitable for a solid-state imaging device used in a digital camera and the like, and a near infrared cut function. The solid-state imaging device of the present invention comprising the color filter is provided with a filter having the functions of both a blue color filter and a near-infrared cut filter formed in a single development step, and is lightweight. , Has excellent image quality with reduced noise.

  The color filter comprising the blue colored resin composition of the present invention has both the blue color filter function and the near-infrared cut function, and therefore preferably does not need to have a conventional two-layer structure in a solid-state imaging device. It can be a thinned single layer. However, in one embodiment, the color filter of the present invention can be used as an alternative to one of such conventional two-layer structures.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. In the examples, “part” means “part by mass” unless otherwise specified.
In addition, the mass spectrum in an Example is LC-MS (Agilent 6100; Agilent Technologies Co., Ltd.), and a maximum absorption wavelength is an ultraviolet visible near-infrared spectrophotometer (UV-3150; Shimadzu Corporation Corp.), respectively. It was measured.

Synthesis Example 1 (Synthesis of vanadyl 2,3-naphthalocyanine (compound represented by No. 2 in the above specific example))
In a 2000 mL four-necked flask, put 70 parts of 2,3-naphthalenedicarboxylic anhydride, 125 parts of urea, 1.8 parts of ammonium molybdate, 15.3 parts of vanadium trichloride (V) and 450 mL of sulfolane, After stirring at room temperature for 10 minutes, the mixture was heated and stirred at an internal temperature of 195 to 205 ° C. for 6 hours. The reaction solution was cooled to room temperature, 400 mL of pure water was added, and the precipitated solid was collected by filtration. This solid was placed in a 1000 mL four-necked flask, 500 mL of N, N-dimethylformamide (abbreviated as DMF) was added and suspended, and the mixture was heated and stirred at 100 ° C. for 1 hour. Thereafter, the internal temperature was cooled to 50 ° C., and the solid was collected by filtration. The obtained solid was dried and No. of the above specific example. 68.8 parts of the compound represented by 2 were obtained. The measurement results of mass spectrum and maximum absorption wavelength of the obtained compound were as follows.
Mass spectrum M + = 779
Maximum absorption wavelength 792nm (N-methyl-2-pyrrolidone)

Synthesis Example 2 (Synthesis of titanyl 2,3-naphthalocyanine (compound represented by No. 3 in the above specific example))
In a 500 mL four-necked flask, put 25 parts of 2,3-naphthalenedicarboxylic anhydride, 38 parts of urea, 0.2 part of ammonium molybdate, 8.4 parts of titanium (IV) chloride and 200 mL of sulfolane at room temperature. After stirring for 10 minutes, the mixture was heated and stirred at an internal temperature of 195 to 205 ° C. for 6 hours. The reaction solution was cooled to room temperature, 100 mL of pure water was added, and the precipitated solid was collected by filtration. This solid was placed in a 500 mL four-necked flask, and further 150 mL of N, N-dimethylformamide (abbreviation DMF) was added and suspended, followed by heating and stirring at 100 ° C. for 1 hour. Thereafter, the internal temperature was cooled to 50 ° C., and the solid was collected by filtration. The obtained solid was dried and No. of the above specific example. 19.1 parts of the compound represented by 3 were obtained. The measurement results of mass spectrum and maximum absorption wavelength of the obtained compound were as follows.
Mass spectrum M + = 776
Maximum absorption wavelength 791 nm (N-methyl-2-pyrrolidone)

Synthesis Example 3 (Synthesis of vanadyl-1-phenyl-2,3-naphthalocyanine (compound represented by No. 10 in the above specific example))
In a 500 mL four-necked flask, 10 parts of 1-phenyl-2,3-naphthalenedicarboxylic anhydride, 13 parts of urea, 0.2 part of ammonium molybdate, 1.6 parts of vanadium trichloride (V) and 100 mL of sulfolane The mixture was stirred at room temperature for 10 minutes and then heated and stirred at an internal temperature of 195 to 205 ° C. for 6 hours. The reaction solution was cooled to room temperature, 100 mL of pure water was added, and the precipitated solid was collected by filtration. This solid was placed in a 500 mL four-necked flask, and further 150 mL of N, N-dimethylformamide (abbreviation DMF) was added and suspended, followed by heating and stirring at 100 ° C. for 1 hour. Thereafter, the internal temperature was cooled to 50 ° C., and the solid was collected by filtration. The obtained solid was dried and No. of the above specific example. 9.9 parts of the compound represented by 10 were obtained. The measurement results of mass spectrum and maximum absorption wavelength of the obtained compound were as follows.
Mass spectrum M + = 1084
Maximum absorption wavelength 808nm (N-methyl-2-pyrrolidone)

Synthesis Example 4 (Synthesis of zinc 2,3-naphthalocyanine (compound represented by No. 5 in the above specific example))
In a 500 mL four-necked flask, put 18 parts of 2,3-dicyanonaphthalene, 9.4 parts of zinc (II) chloride and 150 mL of quinoline and stir at room temperature for 10 minutes, then at an internal temperature of 195 to 205 ° C. for 2 hours. Stir with heating. The reaction solution was cooled to room temperature, 200 mL of pure water was added, and the precipitated solid was collected by filtration. This solid was placed in a 300 mL four-necked flask, 100 mL of N, N-dimethylformamide (abbreviation DMF) was further added and suspended, and the mixture was heated and stirred at 100 ° C. for 1 hour. Thereafter, the internal temperature was cooled to 50 ° C., and the solid was collected by filtration. The obtained solid was dried and No. of the above specific example. 5.2 parts of the compound represented by 5 were obtained. The measurement results of mass spectrum and maximum absorption wavelength of the obtained compound were as follows.
Mass spectrum M + = 778
Maximum absorption wavelength 759 nm (N-methyl-2-pyrrolidone)

Synthesis Example 5 (Synthesis of magnesium 2,3-naphthalocyanine (compound represented by No. 41 in the above specific example))
In a 2000 mL four-necked flask, 18 parts of 2,3-dicyanonaphthalene, 9.4 parts of magnesium (II) acetate tetrahydrate and 500 mL of isoamyl alcohol were added and stirred for 10 minutes at room temperature. Stir with heating for hours. The reaction solution was cooled to room temperature, 500 mL of pure water was added, and the precipitated solid was collected by filtration. This solid was placed in a 300 mL four-necked flask, 100 mL of N, N-dimethylformamide (abbreviation DMF) was further added and suspended, and the mixture was heated and stirred at 100 ° C. for 1 hour. Thereafter, the internal temperature was cooled to 50 ° C., and the solid was collected by filtration. The obtained solid was dried and No. of the above specific example. This gave 5.5 parts of the compound represented by 41. The measurement results of mass spectrum and maximum absorption wavelength of the obtained compound were as follows.
Mass spectrum M + = 737
Maximum absorption wavelength 750 nm (N-methyl-2-pyrrolidone)

Formulation Example 1 (Preparation of pigment dispersion 1)
Each component is C.I. I. Pigment Blue 15: 6 / Pigment Violet 23 / Specific Example No. obtained in Synthesis Example 1 After mixing at a composition ratio of compound represented by 2 / Disperbyk-2001 / Solsperse 5000 / PGMEA = 11.4 / 2.9 / 0.75 / 6.0 / 1.0 / 78.0 (mass ratio) The pigment dispersion 1 was obtained by dispersing with 0.3 mm zirconia beads. Pigment dispersion liquid 1 had good dispersion stability because no precipitate was formed even when stored at 23 ° C. for 1 week.

Formulation Example 2 (Preparation of Pigment Dispersion Liquid 2)
Compound No. obtained in Synthesis Example 1 Compound No. 2 obtained in Synthesis Example 2 instead of Compound No. 3 was prepared in the same manner as in Example 1 except that No. 3 was used. 3. A pigment dispersion 2 containing Pigment Blue and Pigment Violet was obtained. Pigment dispersion liquid 2 had good dispersion stability because no precipitate was formed even when stored at 23 ° C. for 1 week.

Formulation Example 3 (Preparation of pigment dispersion 3)
Compound No. obtained in Synthesis Example 1 Compound No. 2 obtained in Synthesis Example 3 instead of Compound No. 10 was prepared in the same manner as in Example 1 except that Compound No. 10 was used. 10. A pigment dispersion 3 containing Pigment Blue and Pigment Violet was obtained. Pigment dispersion liquid 3 had good dispersion stability because no precipitate was formed even when stored at 23 ° C. for 1 week.

Formulation Example 4 (Preparation of pigment dispersion 4)
Compound No. obtained in Synthesis Example 1 Compound No. 2 obtained in Synthesis Example 4 instead of Compound No. 5 was prepared in the same manner as in Example 1 except that No. 5 was used. 5. A pigment dispersion 4 containing Pigment Blue and Pigment Violet was obtained. Pigment dispersion 4 did not produce a precipitate even when stored at 23 ° C. for 1 week, and the dispersion stability was good.

Formulation Example 5 (Preparation of pigment dispersion 5)
Compound No. obtained in Synthesis Example 1 Compound No. 2 obtained in Synthesis Example 5 instead of Compound No. 41 was prepared in the same manner as in Example 1 except that 41 was used. 41, pigment dispersion 5 containing Pigment Blue and Pigment Violet was obtained. Pigment dispersion 5 had no dispersion when stored at 23 ° C. for 1 week, and the dispersion stability was good.

Synthesis Example 6 (Synthesis of binder resin (copolymer (A)))
A 500 mL four-necked flask is charged with 160 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 33 parts of benzyl methacrylate and 1 part of α, α′-azobis (isobutyronitrile), and nitrogen gas is added to the flask for 30 minutes while stirring. Let it flow. Then, it heated up to 80 degreeC and stirred for 4 hours as it was at 80 to 85 degreeC. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, and the solid content was taken out and dried to obtain a copolymer (A). The resulting copolymer (A) had a polystyrene equivalent weight average molecular weight of 18,000 and an acid value of 152.

Example 1 (Preparation of the blue colored resin composition of the present invention)
3.0 parts of the copolymer (A) obtained in Synthesis Example 6 as a binder resin, 6.0 parts of Kayarad RP1040 (manufactured by Nippon Kayaku) as a photopolymerizable monomer, and Irgacure 907 (BASF) as a photopolymerization initiator 1.0 part), 1.0 part of Irgacure OXE-02 (manufactured by BASF), 50 parts of pigment dispersion 1 obtained in Formulation Example 1 as a pigment dispersion and propylene glycol monomethyl ether acetate as a solvent 39 parts were mixed and the blue colored resin composition 1 of this invention was obtained. Even when the blue colored resin composition 1 was stored at 23 ° C. for one week, no thickening or precipitation occurred, and the stability was good.

Example 2 (Preparation of the blue colored resin composition of the present invention)
The blue colored resin composition 2 of the present invention was obtained in the same manner as in Example 1 except that the pigment dispersion 2 obtained in Formulation Example 2 was used instead of the pigment dispersion 1 obtained in Formulation Example 1. It was. The blue colored resin composition 2 did not cause thickening or precipitation even when stored at 23 ° C. for one week, and had good stability.

Example 3 (Preparation of the blue colored resin composition of the present invention)
The blue colored resin composition 3 of the present invention was obtained in the same manner as in Example 1 except that the pigment dispersion 3 obtained in Formulation Example 3 was used instead of the pigment dispersion 1 obtained in Formulation Example 1. It was. The blue colored resin composition 3 did not increase in viscosity or precipitate even when stored at 23 ° C. for one week, and the stability was good.

Example 4 (Preparation of the blue colored resin composition of the present invention)
The blue colored resin composition 4 of the present invention was obtained in the same manner as in Example 1 except that the pigment dispersion 4 obtained in Formulation Example 4 was used instead of the pigment dispersion 1 obtained in Formulation Example 1. It was. The blue colored resin composition 4 did not increase in viscosity or precipitate even when stored at 23 ° C. for one week, and the stability was good.

Example 5 (Preparation of the blue colored resin composition of the present invention)
A blue colored resin composition 5 of the present invention was obtained in the same manner as in Example 1 except that the pigment dispersion 5 obtained in Formulation Example 5 was used instead of the pigment dispersion 1 obtained in Formulation Example 1. It was. Even when the blue colored resin composition 5 was stored at 23 ° C. for one week, no thickening or precipitation occurred, and the stability was good.

Formulation Example 6 (Preparation of pigment dispersion 6)
Compound No. obtained in Synthesis Example 1 A comparative pigment dispersion 6 containing Pigment Blue and Pigment Violet was obtained in the same manner as Formulation Example 1 except that No. 2 was used.

Comparative Example 1 (Preparation of a blue colored resin composition for comparison)
A blue colored resin composition 6 for comparison was prepared in the same manner as in Example 1 except that the pigment dispersion 6 obtained in Formulation Example 6 was used instead of the pigment dispersion 1 obtained in Formulation Example 1. Obtained.

Formulation Example 7 (Preparation of pigment dispersion 7)
Each component is C.I. I. Pigment Blue 15: 6 / Pigment Violet 23 / Compound I-17 / Disperbyk-2001 / Solsperse 5000 / PGMEA = 11.4 / 2.9 / 0.75 / 6.0 described in JP-A-2015-163955 After mixing at a composition ratio of /1.0/78.0 (mass ratio), the mixture was dispersed with 0.3 mm zirconia beads to obtain Pigment Dispersion Liquid 7 containing Pigment Blue, Pigment Violet and Compound I-17.

Comparative Example 2 (Preparation of a blue colored resin composition for comparison)
A blue colored resin composition 7 for comparison was used in the same manner as in Example 1 except that the pigment dispersion 7 obtained in Formulation Example 7 was used instead of the pigment dispersion 1 obtained in Formulation Example 1. Got.

Formulation Example 8 (Preparation of pigment dispersion 8)
Similar to Formulation Example 7 except that Compound D-10 described in JP-A-2015-163955 was used instead of Compound I-17 described in JP-A-2015-163955 used in Formulation Example 7. By the method, a pigment dispersion 8 was obtained.

Comparative Example 3 (Preparation of a blue colored resin composition for comparison)
A blue colored resin composition 8 for comparison was prepared in the same manner as in Example 1 except that the pigment dispersion 8 obtained in Formulation 8 was used instead of the pigment dispersion 1 obtained in Formulation 1. Got.

Formulation Example 9 (Preparation of pigment dispersion 9)
Each component is C.I. I. Pigment Blue 15: 6 / Pigment Violet 23 / Compound No. obtained in Synthesis Example 1 2 / Disperbyk-2001 / Solsperse 5000 / PGMEA / The following compound A-33 described in JP 2012-77153 A = 11.4 / 1.5 / 0.75 / 6.0 / 1.0 / 78.0 /1.4 (mass ratio), and then mixed with 0.3 mm zirconia beads. 2, pigment dispersion 9 containing Pigment Blue, Pigment Violet and Compound A-33 was obtained. The pigment dispersion 9 gelled when stored at 23 ° C. for 1 week, and the dispersion stability was poor.

Formulation Example 10 (Preparation of Pigment Dispersion Liquid 10)
Similar to Formulation Example 7 except that the following specific example compound R13 described in JP-A-2003-337410 was used instead of Compound I-17 described in JP-A-2015-163955 used in Formulation Example 7. Thus, a pigment dispersion 10 was obtained.

Comparative Example 4 (Preparation of a blue colored resin composition for comparison)
A blue colored resin composition 9 for comparison was prepared in the same manner as in Example 1, except that the pigment dispersion 10 obtained in Formulation 10 was used instead of the pigment dispersion 1 obtained in Formulation 1. Got

<Spectral spectrum, film thickness evaluation>
The blue colored resin compositions 1 to 9 obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were applied onto a glass substrate by a spin coater, pre-baked under conditions of 80 ° C. × 100 seconds, and then high-pressure mercury A lamp was cured by irradiating with 1000 mJ / cm ^{2 of} ultraviolet rays, and then heated at 200 ° C. to obtain a color filter. The spectral transmittance in the range of 400 to 2000 nm of the obtained color filter was measured at a sampling pitch of 1 nm using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-visible spectrophotometer UV-3150). . Based on the measured values obtained, the spectral characteristics of each color filter were evaluated according to the following criteria. Moreover, the film thickness of each color filter was measured with a stylus type step gauge. These results are shown in Table 1.

<Evaluation criteria 1>
○: The maximum value of spectral transmittance at 420 to 500 nm converted to the value of a thin film having a thickness of 0.8 μm is 60% or more, the minimum value of spectral transmittance at 600 to 750 nm is 20% or less, and at 750 to 2000 nm. The minimum value of the spectral transmittance is 80% or less.
X: The above condition is not satisfied.

<Evaluation criteria 2>
In order to evaluate the coexistence of the spectral characteristic of blue in the visible part (high spectral transmittance of blue) and the spectral characteristic of the infrared part (high absorption ability in a long wavelength region of 900 nm or more), evaluation was performed under the following more preferable conditions. These results are shown in Table 2.
[450 nm spectral transmittance evaluation]
A: The spectral transmittance at 450 nm converted to a value of a thin film having a thickness of 0.8 μm is 60% or more.
Δ: The above condition of ○ is not satisfied.
[700 nm spectral transmittance evaluation]
A: The spectral transmittance at 700 nm converted to a value of a thin film having a thickness of 0.8 μm is 15% or less.
Δ: The above condition of ○ is not satisfied.
[910 nm spectral transmittance evaluation]
A: The spectral transmittance at 910 nm converted to a value of a thin film having a thickness of 0.8 μm is 80% or less.
Δ: The above condition of ○ is not satisfied.
[50% transmittance wavelength]
A: The wavelength at which the spectral transmittance converted to the value of a thin film having a thickness of 0.8 μm is 50% is in the range of 505 to 515 nm.
Δ: The above condition of ○ is not satisfied.
[Comprehensive judgment]
○: The spectral transmittance at 450 nm converted to the value of a thin film having a thickness of 0.8 μm is 60% or more, the spectral transmittance at 700 nm is 15% or less, the spectral transmittance at 910 nm is 80% or less, and the thickness is 0.8 μm. The wavelength at which the spectral transmittance converted to the value of the thin film becomes 50% is in the range of 505 to 515 nm.
Δ: The above condition of ○ is not satisfied.

<Heat resistance evaluation>
Using the blue colored resin compositions 1 to 3 and 6 to 9 obtained in Examples 1 to 3 and Comparative Examples 1 to 4, each color filter obtained in the above <spectral spectrum, film thickness evaluation> is 230 ° C. For 60 minutes, and the spectral transmittance in the range of 400 to 2000 nm of the color filter before and after heating is 1 nm using an ultraviolet visible near infrared spectrophotometer (manufactured by Shimadzu Corporation, ultraviolet visible spectrophotometer UV-3150). The sampling pitch was measured. Based on the spectral transmittance of each wavelength region obtained before and after heating at 230 ° C. for 60 minutes, the heat resistance characteristics of each optical filter were judged according to the following evaluation criteria. Table 3 shows the spectral characteristic results of the color filter before heating (before heat resistance evaluation), and Table 4 shows the spectral characteristic (heat resistance evaluation) results of the color filter after heating.
As shown in Table 3, the spectral characteristics of the color filters of Comparative Examples 1, 2, and 4 before the heat resistance evaluation are determined to be evaluation x because they do not absorb at 910 nm.

<Evaluation criteria for blue color filter>
[450 nm spectral transmittance evaluation]
(Circle): The spectral transmittance in 450 nm converted into the value of the 0.8 micrometer-thick thin film after a heating is 60% or more.
×: The above condition of ○ is not satisfied.
[700 nm spectral transmittance evaluation]
A: The spectral transmittance at 700 nm converted to a value of a thin film having a thickness of 0.8 μm after heating is 15% or less.
×: The above condition of ○ is not satisfied.
[910 nm spectral transmittance evaluation]
(Circle): The spectral transmittance in 910 nm converted into the value of the 0.8-micrometer-thick thin film after a heating is 80% or less.
×: The above condition of ○ is not satisfied.
[50% transmittance wavelength]
A: The wavelength at which the spectral transmittance converted to a value of a thin film having a thickness of 0.8 μm after heating is 50% is in the range of 505 to 515 nm.
×: The above condition of ○ is not satisfied.
[Comprehensive judgment]
○: Spectral transmittance at 450 nm converted to a value of a thin film having a thickness of 0.8 μm after heat resistance test after heating is 60% or more, spectral transmittance at 700 nm is 15% or less, and spectral transmittance at 910 nm is 80% or less. The wavelength at which the spectral transmittance converted to the value of a thin film having a thickness of 0.8 μm is 50% is in the range of 505 to 515 nm.
X: The above condition is not satisfied.

<Light resistance evaluation>
Using each of the blue colored resin compositions 1 to 3 and 6 to 9 obtained in Examples 1 to 3 and Comparative Examples 1 to 4, the color filters obtained in the above <spectral spectrum and film thickness evaluation> were subjected to a light resistance test. A spectral filter in the range of 400 to 2000 nm of the color filter after irradiation in an ultraviolet (Xenon arc lamp, 100 W / m ² ), and an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV Measurement was performed at a sampling pitch of 1 nm using a visible spectrophotometer UV-3150). Based on the spectral transmittance of each wavelength region obtained before and after irradiation, the light resistance of each optical filter was evaluated according to the following evaluation criteria. Table 5 shows the results of spectral characteristics of the color filters before irradiation (before light resistance evaluation), and Table 6 shows the results of spectral characteristics (light resistance evaluation) of the color filters after irradiation.
As shown in Table 5, the spectral characteristics of the color filters of Comparative Examples 1, 2, and 4 before the light resistance test are evaluated as x because they do not absorb at 910 nm.

<Evaluation criteria for blue color filter>
[450 nm spectral transmittance evaluation]
(Circle): The spectral transmittance in 450 nm converted into the value of the 0.8 micrometer-thick thin film after irradiation is 60% or more.
×: The above condition of ○ is not satisfied.
[700 nm spectral transmittance evaluation]
(Circle): The spectral transmittance in 700 nm converted into the value of the 0.8-micrometer-thick thin film after irradiation is 15% or less.
×: The above condition of ○ is not satisfied.
[910 nm spectral transmittance evaluation]
(Circle): The spectral transmittance in 910 nm converted into the value of the thin film of thickness 0.8 micrometer after irradiation is 80% or less.
×: The above condition of ○ is not satisfied.
[50% transmittance wavelength]
A: The wavelength at which the spectral transmittance converted to a value of a thin film having a thickness of 0.8 μm after irradiation is 50% is in the range of 505 to 515 nm.
Δ: The above condition of ○ is not satisfied.
[Comprehensive judgment]
○: Spectral transmittance at 450 nm converted to a value of a thin film having a thickness of 0.8 μm after irradiation is 60% or more, spectral transmittance at 700 nm is 15% or less, spectral transmittance at 910 nm is 80% or less, and thickness The wavelength at which the spectral transmittance converted to a 0.8 μm thin film value is 50% is in the range of 505 to 515 nm.
X: The above condition is not satisfied.

<Pattern evaluation>
The colored resin composition obtained in Examples 1 to 5 was applied onto a silicon substrate with an organic base film (UC-2L, manufactured by Nippon Kayaku Co., Ltd.) using a spin coater, prebaked at 80 ° C. for 100 seconds, and then a reticle. Was cured by irradiating with 1000 mJ / cm ^{2 of} ultraviolet rays with an i-line stepper. Then, it developed with the aqueous alkali solution containing surfactant, rinsed with water, and heated at 200 degreeC, and the colored pattern was obtained. The obtained colored pattern had a resolution of 4 μm square in line and space, and no residue or peeling of pixels was confirmed.

The blue colored resin composition of the present invention is excellent in dispersion stability and can form a thin film color filter. A blue color filter having the function of a near-infrared cut filter obtained using the blue colored resin composition is excellent in heat resistance and in the near-infrared absorbing ability of 900 nm or more.

Claims (10)

Organic color pigments classified as pigment blue, organic color pigments classified as pigment violet, the following general formula (1)
(In Formula (1), R _{1 to} R ₂₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom. Represents an aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, —OR ₂₅ or —SR ₂₆ , wherein R ₂₅ and R ₂₆ are each independently a hydrogen atom, Represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, M represents two hydrogen atoms, a metal atom, a metal Represents oxide or metal halide.)
A blue colored resin composition containing a naphthalocyanine compound represented by: and a photopolymerizable monomer,
The transmittance of a thin film having a thickness of 0.8 μm obtained using the blue colored resin composition is
60% or more at a wavelength of 450 nm,
A blue colored resin composition that is 15% or less at a wavelength of 700 nm and 80% or less at a wavelength of 910 nm.   2. The blue colored resin composition according to claim 1, wherein a 0.8 μm-thick thin film obtained using the blue colored resin composition has a wavelength at which the transmittance is 50% within a range of 505 to 515 nm. A blue colored resin composition.   The blue colored resin composition according to claim 1 or 2, wherein the organic coloring pigment classified as pigment blue is any one of pigment blue 15: 4 and pigment blue 15: 6.   The blue colored resin composition according to any one of claims 1 to 3, wherein the organic coloring pigment classified as pigment violet is pigment violet 23.   The blue colored resin composition according to claim 1, wherein the photopolymerizable monomer is an acrylate monomer.   The blue colored resin composition according to claim 5, wherein the photopolymerizable monomer is an alkylene oxide-modified acrylate monomer.   The blue colored resin composition according to claim 5 or 6, further comprising an aminoalkylphenone photopolymerization initiator or an oxime photopolymerization initiator.   A color filter comprising the blue colored resin composition according to any one of claims 1 to 7.   The color filter according to claim 8, wherein a step of applying a blue colored resin composition to a substrate, a step of pre-baking the blue colored resin composition applied to the substrate to obtain a thin film, and a mask pattern on the thin film A color filter obtained through a step of irradiating radiation through and a step of developing a thin film irradiated with the radiation. A solid-state imaging device comprising the color filter according to claim 8.