TWI735603B - Blue colored resin composition containing naphthalocyanine, color filter, solid state imaging device - Google Patents

Abstract

An object of the present invention is to provide a blue colored resin composition excellent in dispersion stability and heat resistance which can produce an optical filter layer having a function of blue color filter for solid state imaging device and a function capable of cutting near-infrared light of 900 nm or more.

The present invention discloses a blue colored resin composition comprising an organic colored pigment classified as Pigment Blue, an organic colored pigment classified as Pigment Violet, a naphthalocyanine compound having a specific structure and a photopolymerizable monomer, wherein the transmittance of a thin film having a thickness of 0.8 μm which is obtained by using the blue colored resin composition is 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.

Description

Blue colored resin composition containing naphthalocyanine, color filter, solid-state imaging element

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 including the color filter. More specifically, the present invention relates to a blue colored resin composition for making a color filter capable of selectively transmitting a blue light region and having a near-infrared absorption function, and having the use of the blue coloring A near infrared cut filter that functions as a color filter with a colored pattern formed by a resin composition.

Generally, if a solid-state image sensor (image sensor) is to be used to capture color images, a color filter is required. The blue color filter used in the past functions as a filter that transmits only the blue light region in the visible light region, but its ability to cut off the light in the near-infrared light region is weak, which will cause near-infrared light. Light transmission. Therefore, when using the spectral sensitivity in the visible light region to near-infrared light region near 1100nm If only the conventional blue color filter is used in the solid-state image sensor on the silicon substrate with high spectral sensitivity, the near-infrared light signal will be mixed into the blue signal due to the influence of near-infrared light. This results in a difference in the visual sensitivity of the human eye.

In order to solve this problem, a method has been proposed to eliminate the influence of near-infrared light by using a near-infrared cut-off filter layer in the color filter layer, and to introduce only visible light into the pixels and convert them into photoelectricity. Patent Document 1 describes a method in which an inorganic multilayer film composed of a low-refractive material and a high-refractive material is provided as a near-infrared cut filter layer under the color filter layer.

On the other hand, for the purpose of miniaturization and high color separation of solid-state imaging elements, thinner near-infrared cut filters and color filters are required. Patent Document 2 and Patent Document 3 describe the improvement of color separation properties by including a pyrrolopyrrole compound and a squarylium compound as a near-infrared absorber in a red colored resin composition or a green colored resin composition The color filter.

In addition, for the purpose of improving the reliability of solid-state imaging devices, color filters and near-infrared cut filters are required to further increase heat resistance. Patent Document 4 describes the combination of a specific dipyrromethene compound, a phthalocyanine compound and a squarionium compound as a near-infrared absorber in a blue colored resin composition. Color filter with improved heat resistance.

In addition, Patent Document 5 describes a photopolymerizable composition capable of suppressing the influence of polymerization inhibition caused by oxygen, which contains (A) ethylenic unsaturation Compound, (B) infrared-absorbing phthalocyanine dye with maximum absorption at 750nm or more and 1200nm or less, (C) photopolymerization initiator, (D) cationic dye, and (E) visible light that is not sensitive to visible light Absorb pigments.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication 2014/041742 pamphlet

[Patent Document 2] JP 2015-163955 A

[Patent Document 3] JP 2015-163956 A

[Patent Document 4] JP 2012-77153 A

[Patent Document 5] JP 2003-337410 A

However, the near-infrared absorbers used in Patent Documents 2 and 3 have an absorption wavelength of 900 nm or less, and there is a problem that the ability to cut off the spectral sensitivity wavelength range of a silicon substrate of 900 nm or more is insufficient. In addition, in Patent Document 4, since the dye is used in the blue colored resin composition, the heat resistance of the color filter or the dispersion stability of the pigment dispersion liquid to which the dye is added are insufficient. Furthermore, since the phthalocyanine compound is used in Patent Document 5, the heat resistance and light resistance of the color filter are insufficient.

The object of the present invention is to provide a blue colored resin composition with excellent dispersion stability, which can be used in a single development step to produce a solid-state imaging device with a near-infrared cut filter function The blue film color filter.

Another object of the present invention is preferably to provide a blue colored resin composition that can form a color filter with improved heat resistance or light resistance.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that by using organic coloring pigments that are classified as pigment blue, organic coloring pigments that are classified as pigment violet, specific naphthalocyanine compounds, and light The blue colored resin composition made of polymerizable monomers can solve the above-mentioned problems, and the present invention has been completed

That is, various aspects of the present invention are as follows.

[1]. A blue colored resin composition comprising: an organic coloring pigment classified as pigment blue, an organic coloring pigment classified as pigment violet, a naphthalocyanine compound represented by the following general formula (1), and Photopolymerizable monomer;

In formula (1), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon atom number 6 To 20 aryl groups, substituted or unsubstituted heterocyclic groups with 4 to 20 carbon atoms, -OR ₂₅ or -SR ₂₆ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, substituted or unsubstituted Substituted alkyl group with 1 to 20 carbon atoms, substituted or unsubstituted aryl group with 6 to 20 carbon atoms; M represents 2 hydrogen atoms, metal atoms, metal oxides or metal halides; wherein, The transmittance of a 0.8 μm thick film obtained by using the blue colored resin composition is 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.

[2]. The blue colored resin composition according to the preceding paragraph [1], wherein a film with a thickness of 0.8 μm obtained by using the blue colored resin composition has a transmittance of 50 in the range of 505 to 515 nm. % Of wavelength.

[3]. The blue colored resin composition according to [1] or [2], wherein the organic colored 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 colored 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 as described in [5] above, wherein the photopolymerizable monomer is an acrylate monomer modified with alkylene oxide. body.

[7]. The blue colored resin composition as described in [5] or [6], which further contains an amino alkyl phenone-based photopolymerization initiator or an oxime-based photopolymerization initiator. Polymerization initiator.

[8]. A color filter consisting of the blue colored resin composition described in any one of [1] to [7].

[9]. The color filter as described in the preceding item [8], which is obtained through the following steps: a step of coating a blue colored resin composition on a substrate; The step of pre-baking the colored resin composition to obtain a film; the step of irradiating the film with radiation through a mask pattern; and the step of developing the film after the radiation has been irradiated.

[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 a color filter that has excellent dispersion stability and can form a thin film. The blue colored resin composition is used to obtain a blue color that has the function of a near-infrared cut filter. The color filter system has excellent heat resistance, and its near-infrared absorption ability above 900nm is also excellent. Moreover, most of the blue color filter systems also have excellent light resistance.

The blue colored resin composition of the present invention contains an organic coloring pigment classified as pigment blue (hereinafter abbreviated as "blue pigment") and an organic color pigment classified as pigment violet (hereinafter, abbreviated as "purple pigment") . The organic pigments preferably have spectral characteristics suitable for color filters.

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. Pigment blue 15:3, pigment blue 15:4 or pigment blue 15:6 are preferred.

Specific examples of purple pigments 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, etc. Pigment Violet 23 etc. are preferred.

The content of the organic coloring pigment in the blue coloring resin composition of the present invention is relative to the total solid content in the blue coloring resin composition (blue pigments, purple pigments which are essential components, and naphthalene of the aforementioned formula (1) Phthalocyanine compound and photopolymerizable monomer, and dispersing agent, dispersing aid and binder resin belonging to optional components (all solid content except solvent) 100 parts by mass, usually 1 to 60 parts by mass, preferably 20 To 50 parts by mass. By setting the content of the organic coloring pigment in the blue coloring resin composition within the aforementioned range, the problem of dispersion stability such as aggregation and the like is not caused, and sufficient color purity can be obtained. In addition, the blending ratio of the blue pigment and the purple pigment in the blue colored resin composition of the present invention is such that The transmittance of the 0.8 μm-thick film obtained by using the blue colored resin composition of the present invention is within the specific range described later, and is not particularly limited.

In addition, the finer the blue pigment and the purple pigment system contained in the blue colored resin composition of the present invention, the better. In consideration of handling properties, the average primary particle size is preferably 100 nm or less, preferably 5 to 80 nm, and more preferably 5 to 50 nm. The average primary particle size of the pigment can be measured using, for example, a known method such as an electron microscope.

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

In formula (1), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group having 4 to 20 carbon atoms. The cyclic 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 may have a substituent. 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.

_{The halogen atoms represented by R 1} to R _{24 in} formula (1) include fluorine atom, chlorine atom, bromine atom and iodine atom.

_{The alkyl group having 1 to 20 carbon atoms represented by R 1} to R _{24 of} formula (1) is not particularly limited as long as it is a saturated aliphatic hydrocarbon group composed of 1 to 20 carbon atoms, and the alkyl group may have Branches can also form rings.

_{Specific examples of the alkyl group having 1 to 20 carbon atoms represented by R 1} to R _{24 in} formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Second butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, 1,2-dimethyl-propyl, n-hexyl, isohexyl, second hexyl, n-heptyl, isoheptyl , Second heptyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropylbutyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3,5 , 5-Trimethylhexyl, n-decyl, n-dodecyl, cyclohexyl, cyclopentyl, cyclohexylmethyl, cyclohexylethyl, cyclopentylmethyl and cyclopentylethyl, etc.

_{The alkyl group having 1 to 20 carbon atoms represented by R 1} to R _{24 in the} formula (1) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. A straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms is preferred.

_{The substituents that the alkyl group having 1 to 20 carbon atoms represented by R 1} to R _{24 in the} formula (1) may have, are, for example, an alkoxy group (the above-mentioned alkyl group having 1 to 20 carbon atoms is combined with an oxygen atom The bonded alkoxy group, etc.), halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom), amino group, cyano group, nitro group, etc., but are not limited to these.

In addition, in the present specification, the phrase "substituent" in a substituted alkyl group having 1 to 20 carbon atoms means one of the saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms. One or more hydrogen atoms are replaced by substituents such as the aforementioned alkoxy, halo, amino, cyano, nitro, etc. The phrase "unsubstituted" means that it is composed of 1 to 20 carbon atoms The hydrogen atom of the saturated aliphatic hydrocarbon group is not substituted by substituents such as alkoxy, halo, amine, cyano, and nitro. In this specification, "substituent" and "unsubstituted" are used in the same meaning as explained here.

_{The aryl group having 6 to 20 carbon atoms represented by R 1} to R _{24 in} formula (1) is a residue obtained by removing one hydrogen atom from an aromatic ring composed of 6 to 20 carbon atoms, There are no special restrictions. Specific examples include phenyl, phenethyl, ortho, meta or p-tolyl, 2,3- or 2,4-xylyl (2,3- or 2,4-xylyl), 2,4 ,6-Mesityl, naphthyl, anthracenyl, phenanthryl, biphenyl, benzhydryl, trityl and pyrenyl, etc. Phenyl is particularly preferred.

The aryl group having 6 to 20 carbon atoms represented _{by R 1} to R _{24 in the} formula (1) may have a substituent. The substituents which may be possessed include the same substituents which may be possessed by the alkyl group having 1 to 20 carbon atoms represented by _{R 1} to R _{24 in the formula (1).}

唑基、異

唑基、噻唑基、異噻唑基、咪唑基、

二唑基、噻二唑基、三唑基、四唑基、吡唑基、嘧啶基、嗒嗪基(pyridazinyl)、吡嗪基、三嗪基、吲哚基、異吲哚基、苯并咪唑基、苯并

唑基、苯并噻唑基、喹啉基、異喹啉基、嘌呤基、咔唑基、吖啶基、啡

嗪基(phenoxazinyl)及啡噻嗪基等。以吡啶基為特佳。 _{The heterocyclic group having 4 to 20 carbon atoms represented by R 1} to R _{24 of} formula (1) is a residue obtained by removing one hydrogen atom from a heterocyclic ring composed of 4 to 20 carbon atoms, There are no special restrictions. Specific examples include pyridyl, pyrrolyl,

Azolyl, iso

Azolyl, thiazolyl, isothiazolyl, imidazolyl,

Diazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, benzo Imidazolyl, benzo

Azolyl, benzothiazolyl, quinolinyl, isoquinolinyl, purinyl, carbazolyl, acridinyl, phenanthrene

Phenoxazinyl (phenoxazinyl) and phenothiazinyl and so on. Pyridyl is particularly preferred.

The heterocyclic group having 4 to 20 carbon atoms represented _{by R 1} to R _{24 in the} formula (1) may have a substituent. The substituents which may be possessed include the same substituents which may be possessed by the alkyl group having 1 to 20 carbon atoms represented by _{R 1} to R _{24 in the formula (1).}

The alkyl group having 1 to 20 carbon atoms represented by R ₂₅ and R ₂₆ of formula (1) is the same as the alkyl group having 1 to 20 carbon atoms represented by _{R 1} to R _{24 of formula (1)} .

The alkyl group having 1 to 20 carbon atoms represented _{by R 25} and R _{26 in the} formula (1) may have a substituent. The substituents which may be possessed include the same substituents which may be possessed by the alkyl group having 1 to 20 carbon atoms represented by _{R 1} to R _{24 in the formula (1).}

The aryl groups having 6 to 20 carbon atoms represented by R ₂₅ and R ₂₆ of the formula (1) may be the same as the aryl groups having 6 to 20 carbon atoms represented by _{R 1} to R _{24 of the formula (1).}

The aryl group having 6 to 20 carbon atoms represented _{by R 25} and R _{26 in the} formula (1) may have a substituent. The substituents which may be possessed include the same substituents which may be possessed by the alkyl group having 1 to 20 carbon atoms represented by _{R 1} to R _{24 in the formula (1).}

_{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. More preferably: all of R ₁ to R ₂₄ are 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 carbons; 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 groups having 6 to 20 carbon atoms. More preferably: all of R ₁ to R ₂₄ are 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 are hydrogen atoms, 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 hydrogen atoms, and R ₁ , R ₇ , R ₁₃ and R ₁₉ are phenyl groups.

In formula (1), M represents two hydrogen atoms, metal atoms, Metal oxide or metal halide. When M represents two hydrogen atoms, the N-M-N part in formula (1) forms a structure represented by two N-Hs.

The metal atom represented by M in the formula (1) includes iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, tin, and the like.

The metal oxide represented by M in the formula (1) includes titanyl and vanadyl.

The metal halide represented by M in the formula (1) includes aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, silicon chloride, and the like.

M in formula (1) is preferably copper, zinc, cobalt, nickel, iron, vanadium, titanium, indium chloride or tin(II) chloride. Copper, zinc, vanadium or titanium is preferred, and vanadium is particularly preferred.

The naphthalocyanine compound represented by the formula (1) can be used alone or in combination of plural kinds. 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 relative to 100 parts by mass of the total solid content. By setting the content of the naphthalocyanine compound in the blue colored resin composition within the aforementioned range, it does not cause problems with dispersion stability such as a decrease in transmittance in the visible wavelength region or aggregation, and it is possible to obtain a dispersion stability in the infrared wavelength region. Full shading.

The naphthalocyanine compound represented by formula (1) preferably has a maximum absorption wavelength in the wavelength region of 750 to 1500 nm, and 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 aforementioned wavelength region, light in the target wavelength region can be efficiently absorbed.

In addition, the "maximum absorption wavelength" in the present invention refers to the wavelength at which the absorbance becomes the maximum in the wavelength region measured by the ultraviolet-visible-near-infrared spectrophotometer.

Moreover, when the naphthalocyanine compound represented by formula (1) is dissolved in an oil-soluble organic solvent or an aqueous medium and is present in the pigment dispersion, the cured product of the coloring resin composition containing the pigment dispersion is heat resistant There is a decrease in sex. Therefore, the naphthalocyanine compound is preferably present in the pigment dispersion in a state dispersed in an oil-soluble organic solvent or an aqueous medium.

Next, the method for producing the compound represented by formula (1) will be explained. The method for producing the compound represented by formula (1) is not particularly limited, and conventionally known methods can be suitably used. For example, it is known that naphthalene dicarboxylic acid or its derivatives (anhydrides, dibasic (Imidine, dinitrile, etc.) are synthesized by direct cyclization reaction to synthesize naphthalocyanine having a metal in the center (for example, refer to Chemistry-A. European Journal, Vol. 9, pages 5123 to 5134 (issued in 2003)). At this time, it is preferable to coexist a catalyst (for example, ammonium molybdate) and urea. Alternatively, a lithium compound may be used to temporarily synthesize a metal-free body of naphthalocyanine, and then a metal compound such as a vanadium compound may be used for synthesis as described later.

The above-mentioned cyclization reaction can also be carried out without a solvent, but it is preferably carried out in an organic solvent. The organic solvent that can be used in the cyclization reaction is not particularly limited as long as the reactivity with naphthalene dicarboxylic acid or its derivatives as the starting material is low, but it is preferably inert, which does not show reactivity. Solvent. Examples of organic solvents include benzene, toluene, xylene, Inert solvents such as nitrobenzene, monochlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; methanol, ethanol, 1-propanol , 2-propanol, 1-butanol, 1-hexanol, 1-pentanol and 1-octanol and other alcohols; pyridine, N,N-dimethylformamide, N,N-dimethylethyl Aprotic polar solvents such as amide, N-methyl-2-pyrrolidone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfide and cyclobutyl sulfide, etc. . Among them, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene, benzonitrile and cyclobutene are preferred. 1-octanol, dichlorobenzene, benzonitrile and cyclobutane are preferred. These solvents may be used individually by 1 type, and may use 2 or more types together.

The amount of naphthalenedicarboxylic acid or its derivative and metal compound used in the cyclization reaction is not particularly limited as long as the reaction can proceed. For example, the naphthalene dicarboxylic acid or its derivative is usually used in the range of 1 to 500 parts by mass, preferably 10 to 350 parts by mass relative to 100 parts by mass of the organic solvent, and relative to the naphthalene dicarboxylic acid The acid or its derivative is 1 mol, and the metal compound is usually used in the range of 0.25 to 0.5 mol, preferably 0.25 to 0.4 mol. In addition, the conditions of the cyclization reaction are not particularly limited, and the reaction temperature is preferably in the range of 30 to 250°C, and more preferably in the range of 80 to 200°C. The reaction time is preferably 1 to 30 hours. In addition, the cyclization reaction can be carried out in an atmospheric environment, but it is preferably carried out in an inert gas environment (for example, under the circulation of nitrogen, helium, argon, etc.).

The ratio of the raw materials used when synthesizing the compound represented by formula (1) using the metal-free body of naphthalocyanine and the metal compound is 1 mol relative to the metal-free body of naphthalocyanine to use 0.1 to 10 mol of metal The compound is better, preferably 0.5 to 5 mol is used, and 1 to 3 mol is used as Better. For the metal compound system, inorganic and organic metal compounds can be used. Specific examples thereof include halides (for example, chlorides and bromides), oxyhalides, sulfates, acetates, and metal acetone acetonates. Halides and oxyhalides are preferred, and oxyhalides are preferred.

The compound obtained by the above reaction may be subjected to crystallization, filtration, washing, drying, etc. according to a conventionally known method.

By this operation, the naphthalocyanine compound represented by 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 by these.

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 irradiation with light. The polymerizable group is not particularly limited as long as it is a group that contributes to polymerization. From the viewpoint of the design of the photolithography method, an acrylate monomer is preferred. The acrylate single system is not particularly limited, and from the viewpoint of good solubility in a developer and fine pattern formation, an acrylate monomer having a molecular weight of 2000 or less is preferred. The acrylate monomer modified by alkylene oxide is particularly preferred.

In addition, the so-called "alkylene oxide modified acrylate monomer" in the present invention means that it has an alkylene oxide structure (a structure formed by bonding an alkylene group and an oxygen atom) and acrylic acid in its structure. A compound whose weight average molecular weight (in terms of polystyrene; measured by GPC) of the ester group or methacrylate group is 3000 or less.

Specific examples of acrylate monomers 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 (manufactured by Shinnakamura 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 (manufactured by Nippon Kayaku Co., Ltd.), etc.

Specific examples of acrylate monomers modified by alkylene oxide include ARONIX M-310, M-321, M-350, M-360, M-313, M-315, and M-460 (Toa Synthetic Co., Ltd. Company-made), NK ester, A-9300, ATM-35E, A-GLY-3E, A-GLY-9E, A-GLY-20E (manufactured by Shinnakamura Chemical Industry Co., Ltd.), KAYARAD TPA-330, GPO- 303, THE-330, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), etc.

The content of the photopolymerizable monomer in the blue colored resin composition of the present invention is for a colored resin composition obtained by applying the colored resin composition of the present invention to a substrate and removing the solvent as required There is no particular limitation on what can form a cured film by exposure to the film, and it can be set to any ratio. Specifically, it is usually 1 to 80 parts by mass, preferably 10 to 50 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition.

A film with a thickness of 0.8 μm obtained by using the blue colored resin composition of the present invention shows a transmittance of 60% or more at a wavelength of 450 nm, 15% or less at a wavelength of 700 nm, and a transmittance of 80% or less at a wavelength of 910 nm. By having the aforementioned transmittance characteristics, the film (blue color filter) composed of the blue colored resin composition of the present invention has excellent color separation from the red color filter and the green color filter sex. In addition, the transmittance in the present invention means a value measured using an ultraviolet-visible-near-infrared spectrophotometer.

The thickness obtained by using the blue colored resin composition of the present invention is 0.8 A μm film preferably exhibits 70% or more at a wavelength of 450nm, 12% or less at a wavelength of 700nm, and a transmittance of 70% or less at a wavelength of 910nm, more preferably 75% or more at a wavelength of 450nm, and a transmittance at a wavelength of 700nm 10% or less, and shows a transmittance of 60% or less at a wavelength of 910nm.

In addition, a film with a thickness of 0.8 μm obtained by using the blue colored resin composition of the present invention preferably has a wavelength in the range of 505 to 515 nm at which the transmittance becomes 50%, and is preferably in the range of 508 to 512 nm. It is better to have, more preferably at 510nm.

In addition, when the thickness of the film is not 0.8μm, the coefficient obtained by the following calculation formula can be converted into the transmittance of the 0.8μm film by multiplying the measured value of the transmittance: actual film thickness (μm)/ 0.8(μm)

Specifically, for example, when the transmittance of a film with a thickness of 1.6 μm is 25%, the transmittance when converted to a film with a thickness of 0.8 μm is 1.6 μm/0.8 μm×25%=50%.

An oil-soluble organic solvent or an aqueous medium may be used in combination with the blue colored resin composition of the present invention. The oil-soluble organic solvent or aqueous medium system that can be used in combination is not particularly limited, and it is preferably one that can maintain dispersion stability when producing the colored resin composition.

烷等醚類；丙酮、甲基乙基酮、甲基丁基酮、環己酮等酮類；甲醇、乙醇、丁醇、異丙醇、苄醇類等醇類。因為在此所舉出的有機溶劑之一部分係為油溶性且同時亦為水性，故亦可列舉為以下的水性介質之具體例。 Specific examples of oil-soluble organic solvents include: benzenes such as toluene and xylene; methyl cellosolve, ethyl cellosolve, butyl cellosolve and other cellosolves; methyl cellosolve Xyloxo acetate, ethyl Xyloxo acetate, butyl Xyloxo acetate, etc.; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether Acetate and other propylene glycol monoalkyl ether acetates; methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate and other propionic esters; Lactates such as methyl lactate, ethyl lactate, and butyl lactate; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetic acid such as methyl acetate, ethyl acetate, and butyl acetate Esters; dimethyl ether, diethyl ether, tetrahydrofuran, two

Ethers such as alkanes; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, butanol, isopropanol, and benzyl alcohol. Since some of the organic solvents listed here are oil-soluble and also water-based, the following specific examples of aqueous media can also be cited.

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

These can be used individually or in combination of 2 or more types. The use amount of the oil-soluble organic solvent or the aqueous medium is relative to 100 parts by mass of the total solid content of the blue colored resin composition, and is usually 10,000 parts by mass or less, preferably 50 to 1,000 parts by mass.

The blue colored resin composition of the present invention may also use a photopolymerization initiator in combination. From the application of the colored resin composition of the present invention to the base From the viewpoint that the colored resin composition film obtained by removing the solvent after the material can be easily formed into a cured film by exposure, it is preferable to use a photopolymerization initiator in combination. The photopolymerization initiator system that can be used in combination is not particularly limited, but an aminoalkylphenone-based photopolymerization initiator or an oxime-based photopolymerization initiator is preferred. Specific examples of aminoalkyl phenone-based photopolymerization initiators include methyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamine benzoate Ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4,4'-bis(dimethylaminodiphenyl ketone), 4,4'-bis(ethylmethylamino) ) Benzophenone, IRGACURE 369, 379, 379EG, 907, KAYACURE EPA (manufactured by Nippon Kayaku Co., Ltd.), EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc. Specific examples of the oxime-based photopolymerization initiator include IRGACURE OXE-01, OXE-02, PAG103, PAG121, PAG203 (manufactured by BASF) and the like.

The content of the photopolymerization initiators in the blue colored resin composition of the present invention is not particularly limited. It is usually 50 parts by mass or less and 0.5 to 25 parts by mass relative to 100 parts by mass of the total solid content of the colored resin composition. The mass part is better.

The blue colored resin composition of the present invention may also use a dispersant in combination. By using a dispersant in combination, the dispersibility of the pigment is improved. Examples of the dispersant include: pigment-based dispersants, resin-based dispersants, and surfactants that have good pigment absorption properties.

The methods of using pigment-based dispersants, for example, are known in the prior art: methods of mixing organic pigments, carbon oxides or their metal salts with pigments; methods of mixing substituted aminomethyl derivatives with pigments, etc. .

Examples of the resin-based dispersant system include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, and No. 95 (Manufactured by Kyoeisha Chemical Industry Co., Ltd.) and other cationic surfactants; or polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Non-ionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester ; Anionic surfactants such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymerization Polymeric dispersants such as material 450 (any of them are manufactured by CIBA SPECIALTY CHEMICALS), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (any of them are manufactured by SANNOPCO); in addition, there are also Adeka pulronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and ISONET S- 20 (manufactured by Sanyo Chemical 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 BYK-Chemie Co., Ltd.), AJISPER PB711, PB411, PB111, PB814, PB821, 822, 824, 881 (manufactured by Ajinomoto Fine-Techno), SOLSPERSE 5000, 13240, 20000, 24000, 26000, 28000, 71000 (manufactured by Avecia). In addition, there can be mentioned acrylic copolymers in the molecule An oligomer or polymer having a polar group at the end or side chain.

The content of the dispersants in the blue colored resin composition of the present invention is not particularly limited, and is usually 70 parts by mass or less, preferably 3 to 40 parts by mass, relative to 100 parts by mass of the total solid content.

The blue colored resin composition of the present invention may also use a binder resin in combination. From the design aspect of the lithography method used for manufacturing the color filter of the present invention, it is preferable that the binder resin is soluble in the alkaline developer used in the development process. Moreover, as for the binder resin, it is preferable that it has sufficient curing characteristics with a photopolymerization initiator, a photopolymerizable monomer, etc. in order to form a good fine pattern.

As the binder resin system, conventional resins can be used. The binder resin is preferably one listed below: an ethylenically unsaturated monomer having one or more carboxyl groups or hydroxyl groups, or an ethylenically unsaturated monomer having other copolymerizable aromatic hydrocarbon groups and aliphatic hydrocarbon groups And other copolymers. Moreover, the epoxy acrylate resin which has an epoxy group in these side chains, a terminal, etc., and further added an acrylate, can also be used. These monomers etc. may be used individually or in combination of 2 or more types.

Specific examples of the aforementioned carboxyl-containing ethylenically unsaturated monomers that can be used in the present invention include: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid and other unsaturated monocarboxylic acids Acids; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids (anhydrides); Unsaturated polycarboxylic acids (anhydrides) with three or more valences; 2-(meth)acryloyloxy ethylhexahydrophthalic acid, phthalic acid 2-(meth)acryloyloxy Ethyl-2-hydroxypropyl ester, 2-propenyloxyethyl-2-hydroxyethyl phthalic acid and the like. These systems can be used alone or in combination of two or more types.

Specific examples of the aforementioned hydroxyl-containing ethylenically unsaturated monomers that can be used in the present invention include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl) ) 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate Ester, 3-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, (meth) 5-hydroxy-3-methyl-pentyl acrylate, cyclohexane-1,4-dimethanol-mono(meth)acrylate, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, Glycerol monomethacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) monomethacrylate and other hydroxyl-terminated polyalkylene glycol one (Meth)acrylate and the like. These can be used individually or in combination of 2 or more types.

In addition, the aforementioned other copolymerizable ethylenically unsaturated monomers include, for example, styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, and o-chlorostyrene. , M-chlorostyrene, p-chlorostyrene, p-methoxystyrene and other aromatic vinyl compounds; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, ( Isopropyl meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, benzyl (meth)acrylate, p-cumylphenoxyglycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, Unsaturated carboxylic acid esters such as o-phenylphenol glycidyl ether (meth)acrylate, o-phenylphenol (meth)acrylate hydroxyethylate, and phenoxyethyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, norbornylmethyl (meth)acrylate, ( Phenylnorbornyl meth)acrylate, cyannorbornyl (meth)acrylate, isobornyl (meth)acrylate, camphenyl (meth)acrylate, menthol (meth)acrylate, (meth) ) Fenchyl acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl (meth)acrylate, (meth)acrylate Base) tricyclo[5.2.1.0 ^2,6 ]dec-4-methyl acrylate, cyclodecyl (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, ( Alicyclic skeletons such as tertiary butyl cyclohexyl methacrylate; polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol)-methyl Acrylates and other hydroxyl-terminated polyalkylene glycol mono(meth)acrylates; methoxy polyethylene glycol monomethacrylate, lauryloxy polyethylene glycol mono(meth)acrylate, octoxy poly Ethylene glycol polypropylene glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polypropylene glycol monoacrylate, allyloxy polyethylene glycol-polypropylene glycol mono( Alkyl-terminated polyalkylene glycol mono(meth)acrylates such as meth)acrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, methyl Unsaturated carboxylic acid aminoalkyl esters such as 2-aminopropyl acrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, etc.; glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl) methyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Carboxylic acid glycidyl esters; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other vinyl carboxylates; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, Unsaturated ethers such as methyl allyl glycidyl ether; C Acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide and other vinyl cyanide compounds; acrylamide, methacrylamide, α-chloroacrylamide, N-phenyl Maleimide, N-cyclohexylmaleimide, N-(meth)acrylonitrile phthalimide, N-(2-hydroxyethyl)acrylamide, Unsaturated amides such as N-(2-hydroxyethyl) methacrylamide and maleimines or unsaturated and imines; 1,3-butadiene, isoprene, chlorine Aliphatic conjugated dienes such as butadiene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysilicone, etc. Macromonomers such as monoacrylic acid group or monomethacrylic acid group at the end of the polymer molecular chain. These can be used individually or in combination of 2 or more types.

In addition, a polymer obtained by further introducing an unsaturated double bond into the side chain of the copolymer is also useful. For example, for the maleic anhydride part in the copolymer of maleic anhydride and copolymerizable styrene, vinyl phenol, acrylic acid, acrylate, acrylamide, etc., the acrylic acid hydroxyl group Acrylates with alcoholic hydroxyl groups such as ethyl esters or acrylates with epoxy groups such as glycidyl methacrylate are reacted and semi-esterified compounds; and for compounds composed of acrylic acid, acrylate and hydroxyethyl acrylate, etc. The hydroxyl group in the copolymer of acrylic ester with alcoholic hydroxyl group, the compound formed by the reaction of acrylic acid, etc. Moreover, urethane can also be used 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 Co., Ltd.) ), UXE-3024 (Nippon Kayaku), UXE-3000 (Nippon Kayaku), ZGA-287H (Nippon Kayaku), TCR-1338H (Nippon Kayaku), ZXR-1722H (Nippon Kayaku) ), ZFR-1401H (manufactured by Nippon Kayaku), ZCR-1642 (manufactured by Nippon Kayaku).

When manufacturing the binder resin (copolymer) used in the present invention, a polymerization initiator is used. Here, specific examples of the polymerization initiator used when synthesizing the copolymer include: α,α'-azobis(isobutyronitrile), 2,2'-azobis(2-methyl Butyronitrile), t-butyl peroxy octanoate, di-tert-butyl peroxide, benzyl peroxide, methyl ethyl ketone peroxide and the like. The usage ratio of the polymerization initiator is usually 0.01 to 25 parts by mass relative to the total of all monomers used in synthesizing the copolymer. Moreover, when synthesizing a copolymer, it is preferable to use the organic solvent demonstrated below, and it can use the thing which has sufficient solubility with respect to the monofunctional monomer, a polymerization initiator, etc. used. The reaction temperature during the synthesis of the copolymer is preferably 50 to 120°C, particularly preferably 80 to 100°C. In addition, the reaction time is preferably 1 to 60 hours, preferably 3 to 20 hours. The preferred acid value of the copolymer is 10 to 300 (mgKOH/g), and the more preferred hydroxyl value is 10 to 200 (mgKOH/g). By setting the acid value or the hydroxyl value to 10 or more, the developability can be appropriately maintained. The weight average molecular weight (Mw) of the copolymer is preferably 2,000 to 400,000, more preferably 3,000 to 100,000. By setting the weight average molecular weight to be 2,000 or more and 400,000 or less, it is possible to appropriately maintain sensitivity, developability, and the like.

In the present invention, the aforementioned binder resin system can be used alone Use or combine two or more types to use. The content of the binder resin of the present invention is relative to 100 parts by mass of the total solid content of the colored resin composition, and is usually 0.5 to 99 parts by mass, preferably 5 to 50 parts by mass. At this time, by making the content of the binder resin 0.5 parts by mass or more, the alkali developability can be appropriately maintained, and the possibility of problems such as contamination or film residues in regions other than the pixel formation portion can be suppressed.

In the blue colored resin composition of the present invention, various additives such as surfactants, thermal polymerization initiators, polymerization inhibitors, and ultraviolet absorbers can also be used in combination as required. The additives that can be used in combination are not particularly limited as long as they do not impair the effect of the blue colored resin composition of the present invention. As for the additives, for example, if a dipyrromethene compound represented by the following general formula (a) is coordinated to a boron atom, a boron compound, a metal atom, or a metal compound, a dipyrromethene complex is used in combination. The chemical compound or its tautomer is not good because the storage stability of the blue colored resin composition is reduced.

In formula (a), R ₃₁ to R ₃₆ each independently represent 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 preparation method of the blue colored resin composition of the present invention Method, as long as the organic coloring pigment classified as pigment blue, the organic coloring pigment classified as pigment violet, the naphthalocyanine compound represented by the above formula (1) and the photopolymerizable monomer, which are essential components, can be The optional components of the oil-soluble organic solvent or aqueous medium, photopolymerization initiator, dispersant, and binder resin are uniformly mixed and are not particularly limited. The preparation method includes, for example, a method of mixing and dispersing using a dissolver or a homomixer.

In addition, one of the preferred aspects is as follows: an organic coloring pigment classified as pigment blue, an organic coloring pigment classified as pigment violet, the naphthalocyanine compound represented by the above formula (1), and a dispersant and Oil-soluble organic solvent or aqueous medium, by using vertical or horizontal sand grinder, pin mill, slit mill or ultrasonic dispersion machine After preparing a pigment dispersion liquid by using beads made of glass, zirconia, etc. with a particle size of 0.01 to 1 mm, a photopolymerizable monomer and various optional components are added to the pigment dispersion. Pigment dispersion liquid to obtain a blue colored resin composition.

In addition, the preferred aspect for obtaining the pigment dispersion is as follows: Before performing the aforementioned bead dispersion, a two-roll mill, a three-roll mill, a ball mill, a trommel, and a dispersion are used. Kneader, kneader, co-kneader, homogenizer, blender, uniaxial or biaxial extruder, etc., while applying a strong shear force, while mixing and dispersing deal with.

The time for the kneading and dispersion treatment is not particularly limited, but it is usually preferably 1 hour or more. Also, for details of mixing and dispersion, please refer to T.C. Patton's "Paint Flow and Pigment Dispersion" (the publication of John Wiley and Sons in 1964), etc.

The blue colored resin composition obtained by the aforementioned method or the like may also be subjected to a precision filtration treatment with a filter or the like for removing foreign matter and the like as required.

Next, a typical method of preparing a color filter composed of the blue colored resin composition of the present invention will be described. First, the blue colored resin composition of the present invention can be applied using spin coating, roll coating, slit & spin, die coating, bar coating, etc., so that the film thickness becomes about 0.1 to 20μm (preferably 0.5 to 5μm) coated on glass substrates, silicon substrates and other substrates, according to needs, in a reduced pressure processing chamber at a temperature of 23 to 150 ℃ for 1 to 60 minutes (preferably at a temperature of 60 to Under the drying conditions of 120°C and 1 to 10 minutes), the film is dried under reduced pressure, and a hot plate or a clean oven is used for pre-baking treatment to form a film. Secondly, the usual lithography method can be used to irradiate radiation (for example, electron beams and ultraviolet rays, but ultraviolet rays are preferred) through a predetermined mask pattern, and then use a surfactant aqueous solution, an alkaline aqueous solution, or a surfactant A mixed aqueous solution with an alkali agent is used for development. The development method includes a dipping method, a spray method, a shower method, a puddle method, an ultrasonic development method, etc., and any combination of these methods may be used. The unirradiated part can be removed by development, and after rinsing with water, post-baking treatment is performed. The post-baking treatment can be carried out, for example, at a temperature of 130 to 300°C and a time of 1 to 120 minutes (preferably a temperature of 150 to 250°C and a time of 1 to 30 minutes). In this way, we can get A color filter composed of a bright blue colored resin composition.

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

The color filter composed of the blue colored resin composition of the present invention has both a thin-filmed blue color filter function and a near-infrared cutoff function suitable for solid-state imaging elements used in digital cameras, etc. By. The solid-state imaging device of the present invention including the color filter is formed by installing filters, which is lightweight and has excellent image quality with reduced noise. During the development step, the film is formed to have the functions of both the blue color filter and the near-infrared cut-off filter.

In addition, the color filter composed of the blue colored resin composition of the present invention has both functions of a blue color filter function and a near-infrared cutoff function, so it is preferable that it is not necessary to be a conventional solid-state imaging device. A known two-layer structure can be a single layer formed into a thin film. However, in one embodiment, the color filter of the present invention can also be used instead of one of the above-mentioned conventional two-layer structures.

[Example]

Hereinafter, the present invention will be explained in more detail through the examples bright. In addition, the present invention is not limited by these embodiments. In addition, in the examples, "parts" means "parts by mass" unless otherwise specified.

In the examples, the mass spectrum was measured using LC-MS (Agilent 6100; manufactured by Agilent Technologies Co., Ltd.), and the maximum absorption wavelength was measured using an ultraviolet-visible near-infrared spectrophotometer (UV-3150; manufactured by Shimadzu Corporation). ) And measured.

Synthesis Example 1 (Synthesis of vanadyl 2,3-naphthalocyanine (the compound represented by No. 2 of the above specific example))

Add 70 parts of 2,3-naphthalenedicarboxylic acid anhydride, 125 parts of urea, 1.8 parts of ammonium molybdate, 15.3 parts of vanadium(V) trichloride and 450 mL of cyclobutene to a 2000mL four-necked flask, and stir at room temperature for 10 Minutes later, it was heated and stirred at an internal temperature of 195 to 205°C for 6 hours. The reaction liquid 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, and 500 mL of N,N-dimethylformamide (abbreviated as DMF) was further added to suspend it, and heated and stirred at 100°C for 1 hour. Subsequently, the internal temperature was cooled to 50°C, and the solid was collected by filtration. The obtained solid was dried to obtain 68.8 parts of the compound represented by No. 2 of the above specific example. The mass spectrum and maximum absorption wavelength measurement results of the obtained compound are as follows.

Mass spectrum M+=779

Maximum absorption wavelength 792nm (N-methyl-2-pyrrolidone)

Synthesis Example 2 (Synthesis of titanyl 2,3-naphthalocyanine (the compound represented by No. 3 of the above specific example))

Add 25 parts of 2,3-naphthalenedicarboxylic anhydride and urine to a 500mL four-necked flask. After stirring for 10 minutes at room temperature for 10 minutes, heating and stirring for 6 hours at an internal temperature of 195 to 205° C. The reaction liquid 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 150 mL of N,N-dimethylformamide (abbreviated as DMF) was further added to suspend it, and heated and stirred at 100°C for 1 hour. Subsequently, the internal temperature was cooled to 50°C, and the solid was collected by filtration. The obtained solid was dried to obtain 19.1 parts of the compound represented by No. 3 of the above specific example. The mass spectrum and maximum absorption wavelength measurement results of the obtained compound are as follows.

Mass spectrum M+=776

Maximum absorption wavelength 791nm (N-methyl-2-pyrrolidone)

Synthesis Example 3 (Synthesis of vanadyl-1-phenyl-2,3-naphthalocyanine (the compound represented by No. 10 of the above specific example))

Add 10 parts of 1-phenyl-2,3-naphthalenedicarboxylic acid anhydride, 13 parts of urea, 0.2 parts of ammonium molybdate, 1.6 parts of vanadium (V) trichloride and 100 mL of cyclobutene to a 500 mL four-necked flask, After stirring at room temperature for 10 minutes, it was heated and stirred at an internal temperature of 195 to 205°C for 6 hours. The reaction liquid 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 150 mL of N,N-dimethylformamide (abbreviated as DMF) was further added to suspend it, and heated and stirred at 100°C for 1 hour. Subsequently, the internal temperature was cooled to 50°C, and the solid was collected by filtration. The obtained solid was dried to obtain 9.9 parts of the compound represented by No. 10 of the above specific example. The mass spectrum and maximum absorption wavelength measurement results of the obtained compound are as follows.

Mass spectrum M+=1084

Maximum absorption wavelength 808nm (N-methyl-2-pyrrolidone)

Synthesis Example 4 (Synthesis of zinc 2,3-naphthalocyanine (the compound represented by No. 5 of the above specific example))

Add 18 parts of 2,3-dicyanonaphthalene, 9.4 parts of zinc (II) chloride, and 150 mL of quinoline to a 500 mL four-necked flask. After stirring at room temperature for 10 minutes, heat and stir at an internal temperature of 195 to 205°C 6 Hour. The reaction liquid 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, and 100 mL of N,N-dimethylformamide (abbreviated as DMF) was further added to suspend it, and heated and stirred at 100°C for 1 hour. Subsequently, the internal temperature was cooled to 50°C, and the solid was collected by filtration. The obtained solid was dried to obtain 5.2 parts of the compound represented by No. 5 of the above specific example. The mass spectrum and maximum absorption wavelength measurement results of the obtained compound are as follows.

Mass spectrum M+=778

Maximum absorption wavelength 759nm (N-methyl-2-pyrrolidone)

Synthesis Example 5 (Synthesis of magnesium 2,3-naphthalocyanine (the compound represented by No. 41 in the above specific example))

Add 18 parts of 2,3-dicyanonaphthalene, 9.4 parts of magnesium (II) acetate tetrahydrate, and 500 mL of isoamyl alcohol to a 2000 mL four-necked flask. After stirring at room temperature for 10 minutes, it was heated and stirred under reflux for 10 hours. . The reaction liquid 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, and 100 mL of N,N-dimethylformamide (abbreviated as DMF) was further added to suspend it, and heated and stirred at 100°C for 1 Hour. Subsequently, the internal temperature was cooled to 50°C, and the solid was collected by filtration. The obtained solid was dried to obtain 5.5 parts of the compound represented by No. 41 of the above specific example. The mass spectrum and maximum absorption wavelength measurement results of the obtained compound are as follows.

Mass spectrum M+=737

Maximum absorption wavelength 750nm (N-methyl-2-pyrrolidone)

Blending example 1 (preparation of pigment dispersion liquid 1)

The components are represented by CI Pigment Blue 15:6/Pigment Violet 23/No. 2 of the specific example obtained in Synthesis Example 1/Disperbyk-2001/SOLSPERSE 5000/PGMEA=11.4/2.9/0.75/6.0/1.0 After mixing at a composition ratio of /78.0 (mass ratio), dispersion was performed using 0.3 mm zirconia beads to obtain a pigment dispersion liquid 1. Pigment Dispersion Liquid No. 1 does not produce precipitates even if stored at 23°C for 1 week, and has good dispersion stability.

Formulation example 2 (preparation of pigment dispersion liquid 2)

Except that Compound No. 3 obtained in Synthesis Example 2 was used instead of Compound No. 2 obtained in Synthesis Example 1, the same method as in Formulation Example 1 was used to obtain a pigment dispersion containing Compound No. 3, Pigment Blue, and Pigment Violet液2. Pigment Dispersion Liquid 2 does not produce precipitates even if stored at 23°C for 1 week, and has good dispersion stability.

Blending example 3 (preparation of pigment dispersion liquid 3)

Except that Compound No. 10 obtained in Synthesis Example 3 was used instead of Compound No. 2 obtained in Synthesis Example 1, the same method as in Formulation Example 1 was used to obtain a pigment dispersion containing compound No. 10, pigment blue, and pigment violet.液3. Pigment dispersion 3 series will not produce even if stored at 23°C for 1 week Precipitate, and good dispersion stability.

Blending example 4 (preparation of pigment dispersion 4)

Except that Compound No. 5 obtained in Synthesis Example 4 was used instead of Compound No. 2 obtained in Synthesis Example 1, the same method as in Formulation Example 1 was used to obtain a pigment dispersion containing compound No. 5, pigment blue, and pigment violet.液4. Pigment Dispersion Solution 4 does not produce precipitates even if stored at 23°C for one week, and has good dispersion stability.

Blending example 5 (preparation of pigment dispersion 5)

Except that Compound No. 41 obtained in Synthesis Example 5 was used instead of Compound No. 2 obtained in Synthesis Example 1, the same method as in Formulation Example 1 was used to obtain a pigment dispersion containing Compound No. 41, Pigment Blue, and Pigment Violet液5. Pigment Dispersion Liquid No. 5 does not produce deposits even if stored at 23°C for 1 week, and has good dispersion stability.

Synthesis Example 6 (Synthesis of binder resin (copolymer (A)))

Add 160 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 33 parts of benzyl methacrylate and 1 part of α,α'-azobis(isobutyronitrile) to a 500mL four-necked flask. Nitrogen gas flows into the flask for 30 minutes. Then, it heated up to 80 degreeC, and stirred in this state at 80-85 degreeC for 4 hours. After the reaction was completed, it was cooled to room temperature to obtain a colorless, transparent and uniform copolymer solution. It was precipitated in a 1:1 mixed solution of isopropanol and water and filtered, and the solid content was taken out and dried to obtain a copolymer (A). The polystyrene conversion weight average molecular weight of the obtained copolymer (A) was 18,000, and the acid value was 152.

Example 1 (One of the blue colored resin composition of the present invention modulation)

Using 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 Co., Ltd.) as a photopolymerizable monomer, and 1.0 part of IRGACURE907 (BASF) as a photopolymerization initiator Preparation), 1.0 part of IRGACURE OXE-02 (manufactured by BASF), 50 parts of the pigment dispersion 1 obtained in the preparation example 1 of the pigment dispersion liquid, and 39 parts of propylene glycol monomethyl ether acetate as the solvent were mixed to obtain this Invented blue colored resin composition 1. This blue colored resin composition 1 system did not generate stickiness and sedimentation even when stored at 23°C for one week, 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 by the same method as in Example 1, except that the pigment dispersion liquid 2 obtained in the formulation example 2 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1. This blue colored resin composition 2 does not generate adhesion and sedimentation even if it is stored at 23°C for one week, and has 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 by the same method as in Example 1, except that the pigment dispersion liquid 3 obtained in the formulation example 3 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1. This blue colored resin composition 3 does not generate adhesion and sedimentation even if it is stored at 23°C for one week, and has good stability.

Example 4 (One of the blue colored resin composition of the present invention modulation)

The blue colored resin composition 4 of the present invention was obtained by using the same method as in Example 1 except that the pigment dispersion liquid 4 obtained in the formulation example 4 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1. The blue colored resin composition 4 does not generate adhesion and sedimentation even if stored at 23°C for one week, and has good stability.

Example 5 (Preparation of the blue colored resin composition of the present invention)

The blue colored resin composition 5 of the present invention was obtained by using the same method as in Example 1 except that the pigment dispersion liquid 5 obtained in the formulation example 5 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1. This blue colored resin composition 5 system does not generate stickiness and sedimentation even if it is stored at 23°C for one week, and has good stability.

Formulation example 6 (preparation of pigment dispersion liquid 6)

Except that the compound No. 2 obtained in Synthesis Example 1 was not used, the same method as in Formulation Example 1 was used to obtain a pigment dispersion liquid 6 for comparison containing pigment blue and pigment violet.

Comparative Example 1 (Preparation of blue colored resin composition for comparison)

Except having used the pigment dispersion liquid 6 obtained by the preparation example 6 instead of the pigment dispersion liquid 1 obtained by the preparation example 1, the method similar to Example 1 was used, and the comparative blue colored resin composition 6 was obtained.

Formulation example 7 (preparation of pigment dispersion liquid 7)

The components are C.I. Pigment Blue 15:6/Pigment Violet 23/Japan Special Publication 2 The following compound I-17/Disperbyk-2001/SOLSPERSE 5000/PGMEA=11.4/2.9/0.75/6.0/1.0/78.0 (mass ratio) described in 015-163955 was mixed and 0.3mm zirconia was used. The beads are dispersed to obtain a pigment dispersion liquid 7 containing pigment blue, pigment violet, and compound I-17.

Comparative Example 2 (Preparation of blue colored resin composition for comparison)

Except that the pigment dispersion liquid 7 obtained in the formulation example 7 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1, the same method as in Example 1 was used to obtain a blue colored resin composition 7 for comparison.

Formulation example 8 (preparation of pigment dispersion liquid 8)

Except that the following compound D-10 described in Japanese Patent Application Publication No. 2015-163955 was used instead of the compound I-17 described in Japanese Patent Application Publication No. 2015-163955 used in Formulation Example 7, the same method as in Formulation Example 7 was used. Thus, pigment dispersion liquid 8 was obtained.

Comparative Example 3 (Preparation of blue colored resin composition for comparison)

Except that the pigment dispersion liquid 8 obtained in the formulation example 8 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1, the same method as in Example 1 was used to obtain a blue colored resin composition 8 for comparison.

Formulation example 9 (preparation of pigment dispersion 9)

The components are the following compound A described in CI Pigment Blue 15:6/Pigment Violet 23/Compound No. 2/Disperbyk-2001/SOLSPERSE 5000/PGMEA/JP 2012-77153 obtained in Synthesis Example 1 -33=11.4/1.5/0.75/6.0/1.0/78.0/1.4 (mass ratio) after mixing, using 0.3mm zirconia beads for dispersion to obtain compound No. 2, pigment blue, pigment violet and Compound A-33 Pigment Dispersion Liquid 9. The pigment dispersion 9 system gelled when stored at 23°C for one week, and the dispersion stability was poor.

Blending example 10 (preparation of pigment dispersion 10)

Except that the following specific example compound R13 described in JP 2003-337410 A was used instead of the compound I-17 described in JP 2015-163955 used in Formulation Example 7, the same method as that of Formulation Example 7 was used. Thus, a pigment dispersion liquid 10 was obtained.

Comparative Example 4 (One of the blue colored resin composition for comparison modulation)

Except that the pigment dispersion liquid 10 obtained in the formulation example 10 was used instead of the pigment dispersion liquid 1 obtained in the formulation example 1, the same method as in Example 1 was used to obtain a blue colored resin composition 9 for comparison.

<Spectroscopic spectroscopy, film thickness evaluation>

The blue colored resin compositions 1 to 9 obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were coated on a glass substrate using a spin coater, and prebaked under the conditions of 80°C×100 seconds After baking, a high-pressure mercury lamp was used to irradiate ^{ultraviolet rays of 1000 mJ/cm 2} to harden, and then heated at 200° C. to obtain a color filter. Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, ultraviolet-visible spectrophotometer UV-3150), the spectral transmittance of the obtained color filter in the range of 400 to 2000 nm was measured at a sampling interval of 1 nm. Based on the obtained measurement values, the spectral characteristics of each color filter were evaluated in accordance with the following criteria. In addition, the film thickness of each color filter was measured using a stylus-type level difference meter. The results are shown in Table 1.

<Evaluation Criteria 1>

○: The maximum value of the spectral transmittance between 420 and 500nm is 60% or more, and the minimum value of the spectral transmittance between 600 and 750nm is 20% or less, and it is 750. The minimum value of the spectral transmittance to 2000nm is 80% or less.

×: The above condition of ○ is not satisfied.

<Evaluation Criteria 2>

In order to evaluate the balance between the blue spectral characteristics of the visible part (high spectral transmittance of blue) and the spectral characteristics of the infrared part (high absorption capacity in the long wavelength region above 900 nm), it is better to perform the following conditions Evaluation. These results are shown in Table 2.

[Evaluation of 450nm spectral transmittance]

○: The spectral transmittance at 450nm converted to "the value of a 0.8μm thick film" is 60% or more.

△: The condition of ○ above is not satisfied.

[Evaluation of 700nm Spectral Transmittance]

○: 700nm converted to "the value of a film with a thickness of 0.8μm" The spectral transmittance is 15% or less.

△; does not satisfy the above-mentioned condition of ○.

[Evaluation of 910nm Spectral Transmittance]

○: The spectral transmittance at 910nm converted to "the value of a 0.8μm thick film" is 80% or less.

△: The condition of ○ above is not satisfied.

[50% transmittance wavelength]

◯: The wavelength at which the spectral transmittance becomes 50% converted into "the value of a film with a thickness of 0.8 μm" is in the range of 505 to 515 nm.

△: The condition of ○ above is not satisfied.

[Comprehensive judgment]

○: Converted to "the value of a film with a thickness of 0.8μm", the spectral transmittance at 450nm is 60% or more, the spectral transmittance at 700nm is 15% or less, and the spectral transmittance at 910nm is 80% or less, and converted into "The value of a film with a thickness of 0.8μm" is within the range of 505 to 515nm at a wavelength that makes the spectral transmittance 50%.

△: The condition of ○ above is not satisfied.

<Evaluation of heat resistance>

The color filters obtained by 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 in the above-mentioned <spectroscopic spectrum and film thickness evaluation> were measured at 230 Heat for 60 minutes at °C. Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, ultraviolet-visible spectrophotometer UV-3150), with a sampling interval of 1 nm, the spectral transmittance of the color filter before and after heating in the range of 400 to 2000 nm 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 determined in accordance with the following evaluation criteria. The results of the spectral characteristics of the color filter before heating (before heat resistance evaluation) are shown in Table 3, and the results of the spectral characteristics of the color filter after heating (heat resistance evaluation) are shown in Table 4.

In addition, as shown in Table 3, the spectral characteristics of the color filters of Comparative Examples 1, 2 and 4 before the heat resistance evaluation had no absorption at 910 nm, so it was judged to be evaluated as x.

<Evaluation Criteria for Blue Color Filter>

[Evaluation of 450nm spectral transmittance]

○: After heating, the spectral transmittance at 450nm is 60% or more converted into "the value of a film with a thickness of 0.8μm".

×: The condition of ○ is not satisfied.

[Evaluation of 700nm Spectral Transmittance]

○: After heating, the spectral transmittance at 700nm is 15% or less converted to "the value of a film with a thickness of 0.8μm".

×: The condition of ○ is not satisfied.

[Evaluation of 910nm Spectral Transmittance]

○: After heating, the spectral transmittance at 910nm is 80% or less converted into "the value of a film with a thickness of 0.8μm".

×: The condition of ○ is not satisfied.

[50% transmittance wavelength]

○: After heating, the wavelength at which the spectral transmittance becomes 50% is in the range of 505 to 515 nm, which is converted into "the value of a film with a thickness of 0.8 μm".

×: The condition of ○ is not satisfied.

[Comprehensive judgment]

○: After heating, the spectral transmittance at 450nm is 60% or more, the spectral transmittance at 700nm is 15% or less, and the spectral transmittance at 910nm is 80% or less, converted into "the value of a film with a thickness of 0.8μm", After heating, the wavelength at which the spectral transmittance becomes 50% is within the range of 505 to 515 nm, which is converted into "the value of a film with a thickness of 0.8 μm".

×: The condition of ○ is not satisfied.

<Light resistance evaluation>

The blue colored resin compositions 1 to 3 and 6 to 9 obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were used for each color filter obtained in the above <spectroscopic spectrum, film thickness evaluation>, and placed in Light resistance tester (xenon arc lamp, 100W/m ² ) for 300 hours. Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, ultraviolet-visible spectrophotometer UV-3150), the spectral transmittance of the irradiated color filter in the range of 400 to 2000 nm was measured at a sampling interval of 1 nm. Based on the spectral transmittance of each wavelength region obtained before and after irradiation, the light resistance characteristics of each optical filter were evaluated in accordance with the following evaluation criteria. The results of the spectral characteristics of the color filters before irradiation (before light resistance evaluation) are shown in Table 5, and the results of the spectral characteristics (light resistance evaluation) of the color filters after irradiation are shown in Table 6.

In addition, as shown in Table 5, the spectral characteristics of the color filters of Comparative Examples 1, 2 and 4 before the light resistance test were judged to be evaluation × because they had no absorption at 910 nm.

<Evaluation Criteria for Blue Color Filter>

[Evaluation of 450nm spectral transmittance]

○: After heating, the spectral transmittance at 450nm is 60% or more converted into "the value of a film with a thickness of 0.8μm".

×: The condition of ○ is not satisfied.

[700nm spectral transmittance evaluation 1

○: After heating, the spectral transmittance at 700nm is 15% or less converted to "the value of a film with a thickness of 0.8μm".

×: The condition of ○ is not satisfied.

[Evaluation of 910nm Spectral Transmittance]

○: The value after heating is converted into "the value of a film with a thickness of 0.8μm" The spectral transmittance at 910nm is 80% or less.

×: The condition of ○ is not satisfied.

[50% transmittance wavelength]

○: After heating, the wavelength at which the spectral transmittance becomes 50% is in the range of 505 to 515 nm, which is converted into "the value of a film with a thickness of 0.8 μm".

△: The condition of ○ above is not satisfied.

[Comprehensive judgment]

○: After heating, converted into "the value of a film with a thickness of 0.8μm", the spectral transmittance at 450nm is 60% or more, the spectral transmittance at 700nm is 15% or less, and the spectral transmittance at 910nm is 80% or less, After heating, the wavelength at which the spectral transmittance becomes 50% is within the range of 505 to 515 nm, which is converted into "the value of a film with a thickness of 0.8 μm".

×: The condition of ○ is not satisfied.

<Pattern Evaluation>

The colored resin compositions obtained in Examples 1 to 5 were coated on a silicon substrate with an organic base film (UC-2L manufactured by Nippon Kayaku Co., Ltd.) using a spin coater at 80°C for 100 seconds After the pre-baking, through the reticle, the i-line stepper is used to irradiate the ultraviolet rays at ^{1000 mJ/cm 2 and harden.} Subsequently, it was developed using an alkaline aqueous solution containing a surfactant, washed with water, and heated at 200° C. to obtain a colored pattern. The resulting coloring pattern had a resolution of 4 μm square in line and space, and no residue, pixel peeling, etc. were confirmed.

[Industrial availability]

The blue colored resin composition of the present invention has excellent dispersion stability and can form a color filter of a thin film. Use the blue colored resin composition to obtain a near-infrared cut filter function The blue color filter has excellent heat resistance, and its near-infrared absorption ability above 900nm is also excellent.

Claims (10)

A blue colored resin composition containing: an organic colored pigment classified as pigment blue, an organic colored pigment classified as pigment violet, a naphthalocyanine compound represented by the following general formula (1), and a photopolymerizable monomer body;

In formula (1), R ₁ to R ₂₄ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon atom number 6 To 20 aryl groups, substituted or unsubstituted heterocyclic groups with 4 to 20 carbon atoms, -OR ₂₅ or -SR ₂₆ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, substituted or unsubstituted Substituted alkyl group with 1 to 20 carbon atoms, substituted or unsubstituted aryl group with 6 to 20 carbon atoms; M represents 2 hydrogen atoms, metal atoms, metal oxides or metal halides; wherein, The transmittance of a film with a thickness of 0.8 μm obtained by using the blue colored resin composition is 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; but the aforementioned blue coloring The resin composition does not contain a dipyrromethene complex compound formed by coordinating a dipyrromethene compound represented by the following general formula (a) to a boron atom, a boron compound, a metal atom or a metal compound, or Its tautomers,

In formula (a), R ₃₁ to R ₃₆ each independently represent 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 blue colored resin composition described in item 1 of the scope of patent application, wherein a film with a thickness of 0.8 μm obtained by using the blue colored resin composition has a transmittance of 50% in the range of 505 to 515 nm wavelength. The blue colored resin composition described in the first item of the scope of patent application, wherein the organic colored pigment classified as pigment blue is any one of pigment blue 15:4 and pigment blue 15:6. The blue colored resin composition described in the first item of the scope of patent application, wherein the organic colored pigment classified as pigment violet is pigment violet 23. The blue colored resin composition described in the first item of the scope of patent application, wherein the photopolymerizable monomer is an acrylate monomer. The blue colored resin composition described in item 5 of the scope of patent application, wherein the photopolymerizable monomer is an acrylate monomer modified with alkylene oxide. The blue colored resin composition described in item 5 of the scope of the patent application further contains an aminoalkylphenone-based photopolymerization initiator or an oxime-based photopolymerization initiator. A color filter is composed of the blue colored resin composition described in any one of items 1 to 7 of the scope of patent application. The color filter described in item 8 of the scope of patent application is obtained through the following steps: the step of coating the blue colored resin composition on the substrate; and the blue colored resin coated on the substrate The step of pre-baking the composition to obtain a film; the step of irradiating the film with radiation through the mask pattern; and the step of developing the film after the radiation has been irradiated. A solid-state imaging element is formed by including the color filter described in item 8 of the scope of patent application.