JP2017016011A - Coloring composition for solid-state imaging device, color filter, and solid-state imaging device - Google Patents

Abstract

A colored composition for a solid-state imaging device having excellent color characteristics and spectral characteristics, and a solid-state imaging device using the colored composition capable of acquiring a clear narrow-band image using a white light source. An endoscope apparatus that can easily obtain a narrow band image is provided. The colorant contains at least one dye (A) selected from the group consisting of dioxazine-based purple pigments, cyanine dyes, and xanthene dyes, and a blue pigment (B). When the coating film is formed so that the content weight ratio of the pigment and the blue pigment (B) is in the range of 30/70 to 80/20 and the spectral transmittance at the peak wavelength at a film thickness of 1.0 μm is 70% or more. And a coating film having a spectral characteristic in which the peak wavelength of the coating film is in the range of 400 to 430 nm and the transmittance at wavelengths of 380 nm to less than 400 nm and 450 nm to less than 780 nm is 20% or less. Coloring composition. [Selection] Figure 1

Description

  The present invention relates to a color filter used for a solid-state imaging device and a coloring composition for forming the color filter, and more particularly to a solid-state imaging device for medical use used for an endoscope for endoscopic examination of a body cavity or the like And a color filter used in the solid-state imaging device and a coloring composition for forming the color filter.

  In a solid-state imaging device, light captured by the optical system of the imaging device is color-separated by using a color filter to divide the light in the visible light range, converting it into an electrical signal using a CMOS sensor or CCD sensor, and then performing image processing. Obtain digital image data. In general-purpose digital cameras, light in the entire visible light region is a spectroscopic object, but there are cases where visible light in a specific region is imaged. For example, light often scatters and appears blue in water or air, and there are many examples of capturing the blue light. Among them, blood vessels that can be seen through the skin also appear blue, so when photographing such blood vessels, blue is imaged. In order to capture a clearer image, it is necessary to limit the blue wavelength band to an image. (Non-Patent Document 1 and Non-Patent Document 2) As the imaging method, in Patent Document 1, a band-pass filter is used, and a desired narrow-band image is obtained using a light source having a narrow-band wavelength characteristic. In Patent Document 2, a narrow-band image is generated by calculation from image data acquired by a commonly used primary color or complementary color image sensor. In Patent Document 3, normal color pixels and narrowband pixels are formed on an image sensor, and a narrowband image is obtained by a white light source. On the other hand, smaller digital devices are required for photographing equipment. Among the methods described above, a method using a color filter is most suitable for downsizing the apparatus, and a method of forming a color pixel constituting a color filter using a pigment-dispersed negative resist having many color selection options Is the most suitable. However, the blue pigment used for the current blue pixel has a transmission wavelength peak of around 450 nm and a band of 100 nm or more, so it is difficult to obtain a narrow band transmission characteristic as required in Patent Document 3. It is.

Special skill bulletin No. 271 2013 24 pages The Journal of the Institute of Image Information and Television Engineers 62 No. 4 475 pages, 2008

JP 2002-95635 A JP 2003-93336 A JP 2007-20880 A

  In view of the above problems, the present invention provides a colored composition for a solid-state imaging device excellent in color characteristics and spectral characteristics, and a solid capable of obtaining a clear narrow-band image using a white light source using the colored composition. It is an object of the present invention to provide an endoscope apparatus that can easily obtain a narrow-band image with a small image pickup element.

  As a result of intensive studies to solve the above problems in consideration, the present inventors have found that at least one pigment (A) selected from the group consisting of dioxazine-based purple pigments, cyanine-based dyes, and xanthene-based dyes. And the blue pigment (B), and the content ratio of the dye (A) and the blue pigment (B) is in the range of 30/70 to 80/20, the above problem is caused. It has been found to solve.

  That is, the present invention is a colored composition for a solid-state imaging device containing a colorant, a binder resin, and an organic solvent, wherein the colorant is selected from the group consisting of a dioxazine-based purple pigment, a cyanine-based dye, and a xanthene-based dye. A film containing at least one selected dye (A) and blue pigment (B), the weight ratio of the dye (A) and blue pigment (B) being in the range of 30/70 to 80/20; When the coating film is formed so that the spectral transmittance at the peak wavelength at a thickness of 1.0 μm is 70% or more, the peak wavelength of the coating film is in the range of 400 to 430 nm, and the wavelength is 380 nm or more and less than 400 nm and 450 nm. The present invention relates to a coloring composition for a solid-state imaging device, having spectral characteristics such that the transmittance of less than 780 nm is 20% or less.

一般式（１）

［一般式（１）において、Ｙ^-は、無機または有機のアニオンを表す。ただし、Ｙ^-がハロゲン化物イオンである場合は除く。］ The present invention also relates to the above-described coloring composition for a solid-state imaging device, wherein the pigment (A) is a cyanine dye represented by the following general formula (1).

General formula (1)

[In the general formula (1), Y ⁻ represents an inorganic or organic anion. However, this excludes when Y ⁻ is a halide ion. ]

［一般式（２）において、Ｒ²¹およびＲ²²はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］ The present invention also relates to the above colored composition for a solid-state imaging device, wherein the anion represented by Y ⁻ is an imido acid anion represented by the following general formula (2).

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent. It represents an aromatic hydrocarbon group that may have or a heterocyclic group that may have a substituent. ]

  In the present invention, the blue pigment (B) is C.I. I. Pigment blue 15: 3 and C.I. I. It is related with the said coloring composition for solid-state image sensors characterized by being at least any one of pigment blue 15: 6.

  The present invention also relates to the above-described coloring composition for a solid-state imaging device, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

  Moreover, this invention relates to the color filter for solid-state image sensors which comprises the filter segment formed from the said coloring composition on a base material.

  The present invention also relates to a solid-state imaging device provided with the color filter.

  ADVANTAGE OF THE INVENTION According to this invention, the endoscope apparatus which can obtain a narrow-band image simply by a solid-state image sensor which can acquire a clear narrow-band image using a white light source can be obtained.

It is an example of a photomask. It is a schematic diagram of an endoscope apparatus.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” mentioned in the present specification means a color index (CI).

The coloring composition for a solid-state imaging device of the present invention is a coloring composition for a solid-state imaging device for medical use containing a coloring agent, a binder resin, and an organic solvent, and the coloring agent is a dioxazine-based purple pigment or a cyanine-based coloring material. The composition contains at least one dye (A) selected from the group consisting of a dye and a xanthene dye, and a blue pigment (B), and the weight ratio of the dye (A) and the blue pigment (B) is 30/70. It is characterized by being in the range of ~ 80/20.
Hereinafter, various modes for carrying out the present invention will be described.

≪Coloring composition≫
The colored composition for a solid-state imaging device of the present invention is a colored composition containing a colorant, a binder resin, and an organic solvent, and the colorant comprises a dioxazine-based purple pigment, a cyanine-based dye, and a xanthene-based dye. At least one dye (A) selected from the group consisting of the blue pigment (B), and the content ratio of the dye (A) and the blue pigment (B) is in the range of 30/70 to 80/20. .

With such a colored composition, when the coating film is formed such that the spectral transmittance of the peak wavelength at a film thickness of 1.0 μm is 70% or more, the peak wavelength of the coating film is in the range of 400 to 430 nm. In addition, it is possible to have spectral characteristics such that the transmittance of wavelengths less than 400 nm and 450 nm or more is 20% or less. More preferably, when the peak wavelength is in the range of 405 to 425 nm, and particularly preferably when the peak wavelength is in the range of 410 to 425 nm, the spectral characteristics can be very excellent. Moreover, it is preferable that the transmittance | permeability of wavelengths less than 400 nm and 450 nm or more is 15% or less, and when it becomes 10% or less, it can be said that spectral characteristics are very excellent. By having such spectral characteristics, it is possible to obtain a solid-state imaging device capable of acquiring a clearer narrow band image.
Here, the peak wavelength is a wavelength that maximizes the transmittance of the coating film.

<Colorant>
The coloring composition for a solid-state imaging device according to the present invention includes, as a colorant, at least one dye (A) selected from the group consisting of a dioxazine-based purple pigment, a cyanine dye, and a xanthene dye, and a blue pigment (B). including.

一般式（１）

［一般式（１）において、Ｙ^-は、無機または有機のアニオンを表す。ただし、Ｙ^-がハロゲン化物イオンである場合は除く。］

［一般式（２）において、Ｒ²¹およびＲ²²はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］ [Dye (A)]
By containing a dioxazine-based violet pigment, a cyanine dye, or a xanthene dye, it is possible to achieve excellent spectral characteristics, and a cyanine dye is preferable in order to achieve a narrow band of peak spectrum. Among these, a cyanine dye represented by the following general formula (1) is more preferable, and an anion represented by Y ⁻ in the general formula (1) is more preferably an imido acid anion represented by the following general formula (2). is there.
By including such a specific coloring matter (A) and blue pigment (B), it is possible to exhibit excellent spectral characteristics for obtaining a clear narrow-band image.

General formula (1)

[In the general formula (1), Y ⁻ represents an inorganic or organic anion. However, this excludes when Y ⁻ is a halide ion. ]

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent. It represents an aromatic hydrocarbon group that may have or a heterocyclic group that may have a substituent. ]

  In the colored composition for a solid-state imaging device of the present invention, the concentration of the colorant in the solid content is preferably 20 to 40% by weight from the viewpoint of obtaining sufficient color reproducibility. When the concentration of the colorant component is less than 20% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 40% by weight, the concentration of the colorant carrier such as a binder resin is lowered, and the colored composition May become unstable.

(Dioxazine-based purple pigment)
Examples of the dioxazine-based purple pigment include C.I. I. Pigment Violet 23 and 37 can be mentioned, and among these, C.I. I. Pigment Violet 23 is preferable.

(Cyanine dye)
The cyanine dye can be used without limitation as long as it is a compound having a dye moiety containing a cyanine skeleton in the molecule. Among them, a cyanine dye basic dye is preferable, and a viewpoint that it has excellent spectral characteristics and resistance. Therefore, the cyanine dye having the structure represented by the general formula (1) exhibits excellent spectral characteristics for obtaining a clear narrow-band image, and thus is suitable as a coloring composition for a solid-state imaging device for medical use. .

  Examples of the cyanine basic dye include C.I. I. Basic Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned.

一般式（１−２）

[Cyanine dye represented by the general formula (1)]
The cyanine dye represented by the general formula (1) is a salt-forming compound having a structure in which a cation moiety and an anion moiety are salted. The cationic site is a cationic cyanine dye represented by the following general formula (1-2), and the anion site is an inorganic or organic anion other than halide ions, so that it has excellent not only spectral characteristics but also resistance. This is preferable. In particular, in the cyanine dye of the present invention, it is a more excellent spectroscopic compound to be a salt-forming compound of a cationic cyanine dye represented by the general formula (1-2) and an anion represented by the general formula (2). Desirable to show properties.

General formula (1-2)

<Anion Y ^->
In the general formula (1), Y ⁻ represents an inorganic or organic anion, and any compound having an anion can be used. However, this excludes the case of halide ions (Cl 2 ⁻ etc.).

Typical examples include triflate ion (CF ₃ SO ₃ ⁻ ), benzoate ion (C ₆ H ₅ COO ⁻ ), oxalate ion (C ₂ O ₄ ²⁻ ), perhalogenate ion (ClO ₄ ⁻⁾ , FO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ etc.), thiocyanate ion (SCN ⁻ etc.), sulfate ion (SO ₄ ²⁻ , HSO ₄ ⁻ etc.), heteropolyacid, organic carboxylate ion, organic sulfonate ion (eg C1-C20 alkyl sulfonate, benzene sulfonate, etc.), fatty acid ions (C1-C20 aliphatic carboxylate, etc.), sulfonic acid group-containing nitrogen anion, fluorine group-containing boron anion, methide acid anion, fluorine group-containing Examples include phosphorus anions, cyano group-containing nitrogen anions, anions having a conjugate base of an organic acid having a halogenated hydrocarbon group, or acidic dyes. It is, if these anions, there is no problem in resistance and color properties, can be preferably used.

Among these anions Y ⁻ , from the viewpoint of spectroscopic characteristics, sulfate ion, organic sulfonate ion, sulfonate group-containing nitrogen anion, fluorine group-containing boron anion, or methide acid anion are preferable, and organic sulfonate ion and sulfonate group are contained. A nitrogen anion, a fluorine group-containing boron anion, or a methide acid anion is more preferable, and a sulfonic acid group-containing nitrogen anion is particularly preferable.

  Among the sulfonic acid group-containing nitrogen anions, the imido acid anion represented by the general formula (2) is most preferable.

Specifically as these anions,
Heteropolyacids include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, cytungstomolybdic acid, phosphotungstic acid, Anions such as phosphomolybdic acid, silicotungstic acid, silicomolybdic acid and the like can be mentioned.

  Examples of organic carboxylate ions include tetrachlorophthalic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, elaidic acid, erucic acid, nervonic acid, linoleic acid, gallenic acid, arachidonic acid, α- Examples include anions of anionic compounds such as linolenic acid, stearidonic acid, eicosapentaenoic acid, and docosahexaenoic acid.

  Preferred compounds as organic sulfonate ions are methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, dodecylsulfone. Acid, hexadecanesulfonic acid, icosanesulfonic acid, benzenesulfonic acid 1-naphthalenesulfonic acid, 4-phenylaminobenzenesulfonic acid, 1-naphthylamine-4,8-disulfonic acid, 1-naphthylamine-3,8-disulfonic acid, 1-naphthylamine-5,7-disulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 1-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine-6,8-disulfonic acid, 2-naphthylamine -1,6 Disulfonic acid, 2-naphthylamine-4,8-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid (amino-R acid), 2-naphthylamine-5,7-disulfonic acid (amino J acid), 1-naphthol -4,8-disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,6,8-trisulfonic acid, 2- Naphthol-6,8-disulfonic acid, 2-naphthol-3,6-disulfonic acid (R acid), 2-naphthol-3,6,8-trisulfonic acid, N-phenyl-1-naphthylamine-8-sulfonic acid N-p-tolyl-1-naphthylamine-8-sulfonic acid, N-phenyl-1-naphthylamine-5-sulfonic acid, N-phenyl-2-naphthylamine-6-sulfonic acid, N-acetyl-7-amino-1-naphthol-3-sulfonic acid, N-phenyl-7-amino-1-naphthol-3-sulfonic acid, N-acetyl-6-amino-1-naphthol-3-sulfonic acid N-phenyl-6-amino-1-naphthol-3-sulfonic acid, 1,8-dihydro-3,6-disulfonic acid (chromotropic acid), 8-amino-1-naphthol-3,6-disulfonic acid 8-amino-1-naphthol-5,7-disulfonic acid, 1,6-diamino-2-naphthol-4-sulfonic acid, 1-amino-2-naphthol-6,8-disulfonic acid, 1-amino- 2-naphthol-3,6-disulfonic acid, 2,8-diamino-1-naphthol-5,7-disulfonic acid, 2,7-diamino-1-naphthol-3-sulfonic acid, 2,6-diamino Anions of anionic compounds such as 1-naphthol-3-sulfonic acid, 2,8-diamino-1-naphthol-3,6-disulfonic acid, 2-amino-7-phenylamino-1-naphthol-3-sulfonic acid Can be given.

  Also anthracene sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-1-sulfonic acid, 2-amino-1-naphthalenesulfonic acid (tobias acid), 4-amino-1-naphthalenesulfonic acid (naphthoic acid), 8-amino -1-naphthalenesulfonic acid (peric acid), 2-amino-6-naphthalenesulfonic acid (brenamic acid), 1-amino-5-naphthalenesulfonic acid (Lorentzic acid), 5-amino-2-naphthalenesulfonic acid (molecular weight) 223), anions of anionic compounds such as 1-amino-6-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, and 3-amino-1-naphthalenesulfonic acid can also be used.

  Examples of fatty acid ions include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, serotic acid, decylene acid, dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, petrothelic acid, vacenoic acid, linoleic acid, eleostearic acid Examples include anions of anionic compounds such as acid, licanoic acid, parinaric acid, taliphosphoric acid, gadoleic acid, cetreic acid, and ceracolic acid.

Examples of the sulfonic acid group-containing nitrogen anion include trifluoromethanesulfonamide anion, N- (trimethylsilyl) trifluoromethanesulfonamide anion, N- (2-methoxyethyl) trifluoromethanesulfonamide anion, and p-trifluoromethylbenzenesulfonamide anion. In addition, a sulfonyl imido acid anion is mentioned.
Among these, a sulfonyl imido acid anion is preferable in terms of heat resistance, and an imido acid anion represented by the general formula (2) described later is particularly preferable.

Examples of the fluorine group-containing boron anion include BF _4- or fluorine group-containing boron anion.

Fluorine group-containing phosphorus anions include PF ₆ ⁻ , (CF ₃ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF ^{_{] 2 PF 4 -, [(}} CF 3) 2 CF] 3 PF 3 -, (n-C 3 F 7) 2 PF 4 -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (N-C ₄ F ₉ ) ₂ PF ₄ ⁻ , (n-C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^{— and the} like.
Among ^{_{these, PF 6 -, (C 2}} F 5) 2 PF 4 -, (C 2 F 5) 3 PF 3 -, ((n-C 3 F 7) 3 PF 3 -, (n-C 4 F ₉ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , [( CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- is preferred.

Cyano group-containing nitrogen anions include [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF ^{_{3 CF 2 SO 2)] -}} , [(FSO 2) N {(CF 3) 2 CFSO 2}] -, [(FSO 2) N (CF 3 CF 2 CF 2 SO 2)] -, [(FSO 2 ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like.

The conjugate base of the organic acid having a halogenated hydrocarbon group is not particularly limited, but examples of the organic acid having a halogenated hydrocarbon group include sulfonic acid having a halogenated hydrocarbon group (-SO ₃ H), sulfonimide acid (—SO ₂ NHSO ₂ —) and the like.

Examples of the acid dye include anthraquinone acid dyes, monoazo acid dyes, disazo acid dyes, oxazine acid dyes, amino ketone acid dyes, quinoline acid dyes, and triarylmethane acid dyes.
The hue can also be controlled by using an acid dye.

  Among these, in the present invention, it is desirable in terms of spectral characteristics to use an imido acid anion represented by the general formula (2).

［一般式（２）において、Ｒ²¹およびＲ²²はそれぞれ独立に、置換基を有してもよい脂肪族炭化水素基、置換基を有してもよい脂環式炭化水素基、置換基を有してもよい芳香族炭化水素基、または置換基を有してもよい複素環基を表す。］ "Imidate anion represented by general formula (2)"

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent. It represents an aromatic hydrocarbon group that may have or a heterocyclic group that may have a substituent. ]

In the general formula (2), examples of the “aliphatic hydrocarbon group” include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Linear alkyl groups such as tridecyl group, pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group, pentadecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group And the like.
In the general formula (2), examples of the “alicyclic hydrocarbon group” include cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cycloalkyl groups such as cyclononyl groups, cyclodecyl groups, and the like. It is done.
In the general formula (2), examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.

  In the general formula (2), examples of the “heterocyclic group” include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, quinoline And a ring.

R ²¹ and R ²² may form an aliphatic saturated hydrocarbon ring structure.

  In the general formula (2), examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, Aliphatic hydrocarbon groups such as neopentyl group and tert-pentyl group; polymerizable functional groups such as (meth) acryloyl group, vinylaryl group, vinyloxy group, allyl group and epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy Group, isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; phenoxy Aryloxy groups such as benzyloxy groups; aralkyloxy groups such as benzyloxy groups; groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfa Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyls Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; can be nitro group, a cyano group and the like; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.

In the general formula (2), R ²¹ and R ²² may have an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent. It is preferably a good aromatic hydrocarbon group, and R ²² is preferably an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.

Among the above, R ²¹ and R ^{22 in} the general formula (2) are preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group substituted with a fluorine atom, and 1 carbon atom substituted with a fluorine atom. An alkyl group of ˜20 is more preferred, and a trifluoromethyl group is particularly preferred.

Among the above, R ²¹ and R ^{22 in} the general formula (2) are preferably an aromatic hydrocarbon group substituted with a fluorine atom, and more preferably a p-fluorophenyl group or a pentafluorophenyl group.

Specific examples of the imido acid anion include the following imido acid anions, but the present invention is not limited thereto. Moreover, l and n show the integer of 1-5. In addition, when performing salt formation, the counter of the anionic compound which has the imido acid anion (IC-1 to IC-59) shown below is Na ⁺ or K ^+, tetrabutylammonium or trimethylammonium.

<Salt formation between a cationic cyanine dye and an anionic compound>
The salt-forming compound of the cationic cyanine dye and the anionic compound is prepared by stirring or vibrating an aqueous solution in which the anionic compound having the anion Y ⁻ and the cationic cyanine dye are dissolved, or an aqueous solution of the anionic compound It can be easily obtained by mixing with an aqueous solution of a cationic cyanine dye under stirring or vibration. In the aqueous solution, the anionic group of the anionic compound and the cationic group of the cationic cyanine dye are ionized, and these are ionically bonded, the ion-bonded portion becomes water-insoluble, and the salt-forming compound is precipitated. On the contrary, a salt composed of a counter anion of an anionic compound and a counter anion of a cationic cyanine dye is water-soluble, and therefore can be removed by washing with water. As the anionic compound and the cationic cyanine dye to be used, only a single type or a plurality of types having different structures may be used.

  If the cationic cyanine dye or anionic compound is insoluble in water, each is appropriately dissolved in a soluble organic solvent, heated and stirred, and then the organic solvent is distilled off under reduced pressure or normal pressure. Then, a solid product may be obtained, and by adding water to the slurry and reslurry, the salt as a by-product may be removed, and then the solid product may be filtered to obtain a salt-forming compound. At this time, the water-soluble organic solvent mentioned later can be used for the organic solvent to be used.

  The salt-forming compound of the cationic cyanine dye and the anionic compound is preferably a salt-forming compound obtained by removing a salt composed of a counter cation of the anionic compound and a counter anion of the cationic cyanine dye. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the salt-forming compound may precipitate over time in the colored composition.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the anionic compound and the cationic cyanine dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N -Dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, tetrahydrofurfuryl Examples include alcohol and 4-methoxy-4-methylpentanone. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the anionic compound to the cationic cyanine dye is that the molar ratio of the anionic unit of the anionic compound to the total cationic groups of the cationic cyanine dye is in the range of 10/1 to 1/4. The salt-forming compound can be suitably adjusted, and it is more preferable if it is in the range of 2/1 to 1/2.

(Xanthene dyes)
Xanthene dyes are dyes containing a xanthene ring, and are roughly classified into acidic forms containing hydroxyl groups (fluorescein), basic forms containing amino groups (rhodamines), and mixed systems (rhodols). The Most of them belong to basic dyes or acid dyes and have a remarkably clear color tone. Of these, rhodamine dyes are preferred in terms of color tone.

[Xanthene oil-soluble dye]
Examples of xanthene oil-soluble dyes include C.I. I. Solvent Red 35, 36, 42, 43, 44, 45, 46, 47, 48, 49, 72, 73, 109, 140, 141, 237, 246, C.I. I. Solvent violet 2, 10 etc. are mentioned.

  Among them, C.I., which is a rhodamine-based oil-soluble dye having high color developability. I. Solvent Red 35, 36, 49, 109, 237, 246, C.I. I. Solvent violet 2 is more preferable.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (food red 3)), 52 (acid rhodamine), 87 (eosin G (food red 103)), 92 (acid phloxin PB (food red 104)), 289, 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, 92, 388, or C.I. I. Acid Red 52 (Acid Rhodamine), 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

These acidic dyes are preferably salt-forming compounds of acidic dyes and nitrogen-containing compounds, such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and their functionalities. It is preferable to form a salt using a resin component having a group to form a salt forming compound of a xanthene-based acidic dye because high heat resistance, light resistance, and solvent resistance can be imparted.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, thereby reducing the brightness and resistance. It can be set as the outstanding coloring composition.

<Salt-forming compound of xanthene acid dye>
Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

  The quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride Id, benzyl dimethyl stearyl ammonium chloride, and benzyl dimethyl octyl ammonium chloride, dialkyl (alkyl C14 -C18) dimethyl ammonium chloride (hydrogenated tallow), and the like.

  Specific examples of the quaternary ammonium salt compound products include, for example, Cotamin 24P, Cotamin 86P Conk, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 manufactured by Kao Corporation, and Lion Corporation's Arcade 210- 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, and the like. Among them, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

"Resin having a cationic group in the side chain"
The resin having a cationic group in the side chain will be described. The resin having a cationic group in the side chain for obtaining a salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure is available. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and in consideration of storage stability (thermal stability), they are ammonium salts, iodonium salts, and sulfonium salts. It is more preferable. More preferred is an ammonium salt.

  The resin having a cationic group in the side chain is an alkali resin containing a structural unit represented by the following general formula (3), and the cationic group in the general formula (3) is an anionic group of the xanthene acid dye. A salt-forming compound can be obtained by forming a salt.

一般式（３）

［一般式（３）中、Ｒ⁵¹は水素原子、または置換もしくは無置換のアルキル基を表す。Ｒ⁵²〜Ｒ⁵⁴は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、または置換されていてもよいアリール基を表し、Ｒ⁵²〜Ｒ⁵⁴のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ⁵⁵−、−ＣＯＯ−Ｒ⁵⁵−を表し、Ｒ⁵⁵はアルキレン基を表す。Ｙ^-は無機または有機のアニオンを表す。］

General formula (3)

[In the general formula (3), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁵² to R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group which may be substituted or an optionally substituted aryl group, the R ⁵² to R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

"Salt formation"
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination while stirring. Here, the sulfonic acid group (—SO ₃ H), sodium sulfonate group (—SO ₃ Na) part in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

Further, the salt-forming compound used in the present invention is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (3) and an acidic dye are dissolved, or the general formula (3 ), An aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an acidic dye can be easily obtained by mixing under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acidic dye are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, only a single type or a plurality of types having different structures may be used.
In addition, with other acidic dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained in the same manner as the xanthene dye.

[Blue pigment (B)]
The colored composition for a solid-state imaging device of the present invention further uses a blue pigment (B). This makes it possible to adjust the hue and improve resistance. In addition, the color separation characteristics for the solid-state imaging device can be excellent.
The use ratio of at least one dye (A) and blue pigment (B) selected from the group consisting of dioxazine-based purple pigment, cyanine dye, and xanthene dye is the ratio between the dye (A) and the blue pigment (B). The content weight ratio is in the range of 30/70 to 80/20, more preferably in the range of 40/60 to 70/30. When it exists in this range, it can be set as the composition which was excellent also in the spectral characteristics and the reproducible chromaticity area | region.

As the blue pigment (B) constituting the colorant used in the present invention, phthalocyanine pigments and / or triarylmethane lake pigments are used. As the phthalocyanine pigment, it is preferable to use a copper phthalocyanine blue pigment.
Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and β-type structures are preferable. Since such a preferable pigment is excellent in spectral characteristics, specifically, C.I. I. Pigment Blue 15: 6 or C.I. I. Pigment Blue 15: 3.

  Examples of triarylmethane lake pigments include C.I. I. Pigment blue 1, 1: 2, 1: 3, C.I. I. Pigment Blue 2, 2: 1, 2: 2, C.I. I. Pigment blue 3, C.I. I. Pigment Blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment Blue 10, 10: 1, C.I. I. Pigment blue 11, C.I. I. Pigment blue 12, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, 56: 1, C.I. I. Pigment blue 57, C.I. I. Pigment blue 58, C.I. I. Pigment blue 59, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62 and the like.

[Other colorants]
The coloring composition for a solid-state imaging device of the present invention may further be used in combination with other colorants. As other colorants, organic pigments other than dioxazine-based purple pigments and blue pigments (B), and dyes other than cyanine dyes or xanthene dyes can be used without limitation.
Colorants that can be used in combination include pigments such as diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, aminoanthraquinones, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrones, indantrons. Anthraquinone pigments such as pyranthrone, violanthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments or metal complex pigments Etc.

Examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing companies), oil-soluble dyes, Examples include acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, and mordant dyes. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
According to chemical structure, azo dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, etc. Is mentioned.
In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

[Miniaturization of pigment]
The pigment used in the present invention of the present invention can be used after being refined. The dioxazine-based purple pigment and the blue pigment (B) are also preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation methods are used. In addition, as exemplified in the present invention, it can be refined by performing a salt milling process or the like by a kneader method which is a kind of wet grinding. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the total weight of the pigment from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the total weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total weight of the pigment.

  It is also preferable to add the cyanine dye of the present invention at the same time when the pigment is subjected to a salt milling process (miniaturization). When the pigment is refined, a good colorant can be obtained by adding it together.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin and a thermosetting resin. The resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

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

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

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

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, a fat that functions as an affinity group for the colorant carrier and the organic solvent. Resin having an acid value of 20 to 300 mgKOH / g is important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured portion, and the durability. Is preferably used. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics. Is preferably used in an amount of 500 parts by weight or less. More preferably, it is 100-400 weight part. More preferably, it is 160-320 weight part. The chromaticity region can be widened by such a composition ratio of the colorant.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These organic solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, pentaerythri Oltri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane Acrylic esters and methacrylic esters such as acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene Examples include, but are not necessarily limited to, lenglycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

  Moreover, the photopolymerizable monomer may contain an acid group. For example, esterified product of poly (meth) acrylates containing free hydroxyl group of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; esterified product of polycarboxylic acid and monohydroxyalkyl (meth) acrylates, etc. Can be mentioned. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

  These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The colored composition for a solid-state imaging device of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the coloring composition for solid-state imaging devices from being oxidized and yellowed by the thermal process during thermal curing and ITO annealing. The rate can be increased. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the colored composition for a solid-state imaging device (100% by weight), because the brightness and sensitivity are good. preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

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

<Method for producing colored composition>
The coloring composition of the present invention comprises a coloring agent in a coloring agent carrier such as a binder resin and / or an organic solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill. Further, it can be produced by finely dispersing using various dispersing means such as a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, the dye (A), the blue pigment (B), and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. If the colorant has high solubility, specifically, it is highly soluble in the organic solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, an organic solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

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

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

≪Color filter≫
Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter comprising at least one filter segment formed on the support by the colored composition for a solid-state imaging device of the present invention. The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and further includes a magenta filter segment, a cyan filter segment, a yellow filter segment, or other A filter segment may be provided, and the at least one filter segment is formed from the colored composition of the present invention.

In addition, the color filter of the present invention includes two or more filter segments, and at least one filter segment is formed from the colored composition of the present invention. This is preferable because it is possible to obtain an image.
Preferred filter segment combinations include, for example, at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and further other filter segments. When the segment is a red-purple to blue-violet filter segment, it is preferable because a clearer narrow band image can be obtained using a white light source.
Alternatively, it may have at least one red filter segment, at least one green filter segment, and at least two blue filter segments.

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

<Pigment forming red filter segment>
As a red pigment for a red coloring composition forming a red filter segment,
C. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 224, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP 2011-523433, or JP2013 Although the naphthol azo pigment etc. which are described in -161025 gazette are mentioned, it is not limited in particular.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Red 177, 242, 254, or 269 is preferably used. More preferably, C.I. I. Pigment Red 177 or 254.

  In order to form a red filter segment, a yellow or orange pigment may be used in combination. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026, but not limited thereto. .
Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Yellow 138, 139, 150, or 185 is preferably used. More preferably, C.I. I. Pigment Yellow 139.

  These organic pigments can be used alone or in admixture of two or more at any ratio as required.

<Pigment forming green filter segment>
As a green pigment for a green coloring composition forming a green filter segment,
C. I. Pigment Green 7, 10, 36, 37, 58, zinc phthalocyanine pigment described in JP 2008-193833 A, JP 2007-320986 A, JP 2004-70342 A, or the like, or Japanese Patent No. 4893859 The aluminum phthalocyanine pigment described in 1) is mentioned, but it is not particularly limited thereto.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Green 7, 36, or 58 is preferably used.

  In addition, a yellow pigment can be used in combination with the green coloring composition in order to adjust the hue.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026, etc. Not.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Yellow 138, 139, 150, or 185 is preferably used.

<Pigment forming blue filter segment>
As a blue pigment for a blue coloring composition forming a blue filter segment,
C. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not particularly limited thereto.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 or the like, but not limited thereto.
Among these, the spectral characteristics excellent in color reproducibility and sensitivity can be obtained. I. Pigment Blue 1 or 15: 6 is preferably used.

≪Solid-state imaging device≫
The colored pixels according to the present invention can be formed using a known method without any particular limitation, but it is preferable to use photolithography because the pixels of the imaging device are as fine as submicron to several tens of microns. It is.
The colored pixels according to the present invention can be formed using a known method without any particular limitation, but it is preferable to use photolithography because the pixels of the imaging device are as fine as submicron to several tens of microns. It is.
An embodiment of the present invention is a method for producing a color filter characterized by having colored pixels formed by curing the above-described colored composition. The color pixel obtained by hardening | curing the coloring composition which concerns on embodiment of this invention mentioned above is included.
The color filter according to the present embodiment includes a pixel that transmits the narrow band containing the above-described pigment and, if necessary, at least one visible light transmitting pixel. Visible light transmitting pixels include, but are not limited to, red pixels, green pixels, and blue pixels, and pixels of other colors such as yellow pixels, cyan pixels, magenta pixels, and transparent pixels as necessary. May be included. Other than the colored pixels according to the present invention, a known coloring composition containing a color pigment, a color dye, or both a color pigment and a color dye may be used. The method for forming the colored pixel is not particularly limited, but a photosensitive coloring composition that is a negative resist is generally used.
In the case where the colored pixels are formed on a predetermined corresponding photoelectric conversion element, a negative color resist layer is constituted by a negative green film formed of a negative photosensitive green composition, and in this case, the negative color The thickness of the resist layer is set in the range of 0.1 μm to 3.0 μm.
A plurality of portions corresponding to a plurality of photoelectric conversion elements to be formed are subjected to pattern exposure on a surface of the negative color resist layer formed of the negative coloring film using a photomask.
FIG. 6 shows a schematic plan view of the photomask 20 to be used. Normally, the photomask has a size 4 to 5 times the size of the pattern to be actually formed, and pattern exposure is performed by reducing the size to 1/4 to 1/5 during pattern exposure.
The photomask 20 is a 4 to 5 times reticle, and has a pattern with a size 4 to 5 times larger than the size of the pattern exposed on the surface of the negative color resist layer. Then, using a stepper exposure apparatus (not shown), the pattern of the photomask is reduced to ¼ to し て to expose the surface of the negative color resist layer.
Subsequent to the exposure step, an alkali development treatment (development step) is performed to elute the uncured portion after the exposure into the developer and leave the photocured portion. By this development step, a patterned film composed of colored pixels can be formed.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined with these.
Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkaline agent contained in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, Organic alkali compounds such as 0] -7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
As the developer, an alkaline aqueous solution diluted with pure water so that the concentration of these alkali agents is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used. . In the case of using a developer comprising such an alkaline aqueous solution, generally, after development, the excess developer is washed and removed by rinsing with pure water, followed by drying.
Finally, the filter segment thus formed is hardened.
In the production method of the present invention, after performing the above-described colored layer forming step, exposure step, and development step, if necessary, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure. May be included. Post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 to 270 ° C. is performed. In the case of using light, it can be performed by g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray, etc., but with an existing high-pressure mercury lamp at a low temperature of about 20-50 ° C. Preferably, the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. In the case of combined use of post-exposure and post-heating, post-exposure is preferably performed first.
By repeating the colored layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.
<Image sensor>
The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. Can be mentioned.
A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state image pickup device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) is provided on the substrate, and the photodiode and the transfer electrode are disposed on the substrate. A light-shielding film made of tungsten or the like that is open only in the light-receiving part of the photodiode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part, It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having a light collecting means (for example, a microlens, etc., the same shall apply hereinafter) on the device protection layer and under the color filter (on the side close to the substrate), a structure having the light collecting means on the color filter, etc. It may be.
The organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film and a CMOS signal readout substrate as a photoelectric conversion layer, and an organic material plays a role of capturing light and converting it into an electric signal. This is a two-layer hybrid structure in which an inorganic material plays a role of taking out an electric signal to the outside. In principle, the aperture ratio can be 100% with respect to incident light. The organic photoelectric conversion film is a structure-free continuous film that can be laid on a CMOS signal reading substrate, and therefore does not require an expensive fine processing process and is suitable for pixel miniaturization.
The arrangement of the colored pixels is not particularly limited, and a known method can be used. For example, as described in Japanese Laid-Open Patent Publication No. 2007-20880, four sets of red, blue, and green wide-band colored pixels and narrow-band transmissive pixels that are used in a general imaging device are formed as one set. A method is mentioned.
<Endoscope device>
The endoscope apparatus includes an endoscope, a control device that controls the endoscope, a display unit that displays captured image / moving image information, and an input unit. The endoscope includes an illumination optical system that emits illumination light from a distal end of an endoscope insertion portion that is inserted into a subject, and an imaging optical system that includes an imaging element that images an observation region. It is a endoscope.

The endoscope includes an endoscope insertion portion, an operation portion that operates the distal end of the endoscope insertion portion, and a connector portion that connects the endoscope to a control device. The endoscope insertion portion is provided with various paths for inserting a tissue collection treatment tool and the like.

At the distal end of the endoscope, an irradiation port for irradiating light and an image sensor for acquiring image information of the observation region are arranged. A CCD (Charge Coupled Device) type image sensor, a CMOS (Complementary Metal-Oxide Semiconductor) type image sensor, or the like is used as the imaging device. An objective lens may be arranged on the light receiving surface of the image sensor.

A white light source is used for the illumination light. Examples of white light sources include halogen lamps, fluorescent tubes, and LEDs. The NBI using the narrow band filter according to the present invention desirably includes a light source having a short wavelength, and for example, an ultraviolet LED or a laser light source can be used. As the ultraviolet LED, NVSU233AU405, NVSU233AU395, NCSU276AU405, NCSU276AU385, NC4U134B, NC4U133B, etc. manufactured by Nichia Corporation can be used. In addition, a laser can be used as a light source.

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

  Prior to the examples, a method for measuring the weight average molecular weight of the resin will be described.

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

  Subsequently, the binder resin used in Examples and Comparative Examples, the imido acid anion compound represented by the general formula (2), the salt-forming compound, the dye solution, the method for producing the fine pigment, and the preparation of the resin-type dispersant solution The method, the pigment dispersion, and the method for producing the photosensitive coloring composition will be described.

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Ethyl ether acetate was added to prepare an acrylic resin solution 1.

温度計、撹拌機、冷却管を具備した４つ口セパラブルフラスコに、トリフルオロメタンスルホンアミド ３．５８ ｇ（１．１当量）と炭酸カリウム ５．５３ ｇ（２当量）、アセトニトリル ６０ ｍｌを加えた後、ペンタフルオロベンゼンスルホニルクロリド ３．５３ ｇを分割添加し、５時間加熱還流した。室温まで冷却後、アセトニトリル ４００ ｍｌを加えてよく撹拌した後、吸引ろ過により得られたろ液を濃縮して、７．３０ ｇの生成物を得た。¹ Ｈ、¹³ Ｃ − Ｎ Ｍ Ｒ スペクトル（ 溶剤： 重水素化クロロホルム） 測定により、得られた化合物が目的化合物（ Ｇ−1 ） で表される化合物であることを確認した。 <The manufacturing method of the imido acid anion compound represented by General formula (2)>
(Imidic acid anion compound (G-1))

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube was added 3.58 g (1.1 equivalents) of trifluoromethanesulfonamide, 5.53 g (2 equivalents) of potassium carbonate, and 60 ml of acetonitrile. Then, 3.53 g of pentafluorobenzenesulfonyl chloride was added in portions, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, 400 ml of acetonitrile was added and stirred well, and then the filtrate obtained by suction filtration was concentrated to obtain 7.30 g of product. ¹ H, ¹³ C—N MR spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the target compound (G-1).

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えて３，４−ジフルオロベンゼンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−２を得た。 (Synthesis of imido acid anion compound (G-2))

Compound G-2 was obtained in the same manner as in the synthesis of G-1, except that 3,4-difluorobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−フルオロベンゼンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−３を得た。 (Synthesis of imido acid anion compound (G-3))

Compound G-3 was obtained in the same manner as in the synthesis of G-1, except that p-fluorobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えて３，５−ビス（トリフルオロメチル）ベンゼンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−４を得た。 (Synthesis of imido acid anion compound (G-4))

Compound G-4 was obtained in the same manner as in the synthesis of G-1, except that 3,5-bis (trifluoromethyl) benzenesulfonyl chloride was used in place of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−トリフルオロメチルベンゼンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−５を得た。 (Synthesis of imido acid anion compound (G-5))

Compound G-5 was obtained in the same manner as in G-1, except that p-trifluoromethylbenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−トリフルオロメトキシベンゼンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−６を得た。 (Synthesis of imido acid anion compound (G-6))

Compound G-6 was obtained in the same manner as in G-1, except that p-trifluoromethoxybenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えてｐ−トリフルオロメチルベンゼンスルホンアミドを使用した以外は同様にして、上記化合物Ｇ−７を得た。 (Synthesis of imido acid anion compound (G-7))

Compound G-7 was obtained in the same manner as in the synthesis of G-1, except that p-trifluoromethylbenzenesulfonamide was used instead of trifluoromethanesulfonamide.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えて２，５−ジフルオロベンゼンスルホンアミドを使用した以外は同様にして、上記化合物Ｇ−８を得た。 (Synthesis of imido acid anion compound (G-8))

Compound G-8 was obtained in the same manner as in the synthesis of G-1, except that 2,5-difluorobenzenesulfonamide was used instead of trifluoromethanesulfonamide.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えてｐ−トリフルオロメトキシベンゼンスルホンアミドを使用した以外は同様にして、上記化合物Ｇ−９を得た。 (Synthesis of imido acid anion compound (G-9))

Compound G-9 was obtained in the same manner as in G-1, except that p-trifluoromethoxybenzenesulfonamide was used instead of trifluoromethanesulfonamide.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えて２−ナフタレンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−１０を得た。 (Synthesis of imido acid anion compound (G-10))

Compound G-10 was obtained in the same manner as in the synthesis of G-1, except that 2-naphthalenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−トルエンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−１１を得た。 (Synthesis of imido acid anion compound (G-11))

Compound G-11 was obtained in the same manner as in the synthesis of G-1, except that p-toluenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−ニトロベンゼンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−１１を得た。 (Synthesis of imido acid anion compound (G-12))

Compound G-11 was obtained in the same manner as in the synthesis of G-1, except that p-nitrobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えて４−ビフェニルスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−１３を得た。 (Synthesis of imido acid anion compound (G-13))

Compound G-13 was obtained in the same manner as in the synthesis of G-1, except that 4-biphenylsulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えてメタンスルホンアミドを、ペンタフルオロベンゼンスルホニルクロリドに代えて2-チオフェンスルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−１４を得た。 (Synthesis of imido acid anion compound (G-14))

Compound G-14 was obtained in the same manner as in the synthesis of G-1, except that methanesulfonamide was used instead of trifluoromethanesulfonamide, and 2-thiophenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えてメタンスルホンアミドを、ペンタフルオロベンゼンスルホニルクロリドに代えてベンゼンスルホニルクロリド使用した以外は同様にして、上記化合物Ｇ−１５を得た。 (Synthesis of imido acid anion compound (G-15))

The above compound G-15 was obtained in the same manner as in the synthesis of G-1, except that methanesulfonamide was used instead of trifluoromethanesulfonamide and benzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えてベンゼンスルホンアミドを、ペンタフルオロベンゼンスルホニルクロリドに代えてベンゼンスルホニルクロリド使用した以外は同様にして、上記化合物Ｇ−１６を得た。 (Synthesis of imido acid anion compound (G-16))

Compound G-16 was obtained in the same manner as in the synthesis of G-1, except that benzenesulfonamide was used instead of trifluoromethanesulfonamide and benzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、トリフルオロメタンスルホンアミドに代えてベンゼンスルホンアミドを、ペンタフルオロベンゼンスルホニルクロリドに代えて１−オクタンスルホニルクロリド使用した以外は同様にして、上記化合物Ｇ−１７を得た。 (Synthesis of imido acid anion compound (G-17))

The above compound G-17 was obtained in the same manner as in the synthesis of G-1, except that benzenesulfonamide was used instead of trifluoromethanesulfonamide and 1-octanesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えてｐ−アセトアミドベンゼンスルホニルクロリド使用した以外は同様にして、上記中間体Ｇ−１８aを得た。 (Synthesis of imido acid anion compound (G-18))

The intermediate G-18a was obtained in the same manner as in the synthesis of G-1, except that p-acetamidobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

温度計、撹拌機、冷却管を具備した４つ口セパラブルフラスコに、化合物Ｇ−１８ａ ３．８６ ｇと５％塩酸 １５ ｍｌを加えた後、９０℃で２時間加熱撹拌した。室温まで冷却後、炭酸水素ナトリウム飽和水溶液で中和し、エバポレーターにて濃縮し、白色固体を得た。これを吸引ろ過中、テトラヒドロフランで洗浄し、得られたろ液を濃縮して、３．０３ ｇの生成物を得た。¹ Ｈ、¹³ Ｃ − Ｎ Ｍ Ｒ スペクトル（ 溶剤： 重水素化クロロホルム） 測定により、得られた化合物が目的化合物（ Ｇ−１８ ） で表される化合物であることを確認した。

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, 3.86 g of compound G-18a and 15 ml of 5% hydrochloric acid were added, followed by heating and stirring at 90 ° C. for 2 hours. After cooling to room temperature, the mixture was neutralized with a saturated aqueous solution of sodium bicarbonate and concentrated with an evaporator to obtain a white solid. This was washed with tetrahydrofuran during suction filtration, and the obtained filtrate was concentrated to obtain 3.03 g of a product. ¹ H, ¹³ C—N MR spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the objective compound (G-18).

温度計、撹拌機、冷却管を具備した４つ口セパラブルフラスコに、化合物Ｇ−１８ａ ３．０３ ｇと塩化シアヌル １８．４ ｇ、水 ４０ ｍｌを加えた後、室温で１時間撹拌した。次いで、アニリン塩酸塩 ０．９３ ｇを添加し、２時間撹拌した。また、ブチルアミン塩酸塩 ０．７３ ｇを加え、８０℃で３時間加熱撹拌した。室温まで冷却後、塩化ナトリウムにて塩析することで、５．３０ ｇの生成物を得た。¹ Ｈ、¹³ Ｃ − Ｎ Ｍ Ｒ スペクトル（ 溶剤： 重水素化クロロホルム） 測定により、得られた化合物が目的化合物（ Ｇ−１９ ） で表される化合物であることを確認した。 (Synthesis of imido acid anion compound (G-19))

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, 3.03 g of compound G-18a, 18.4 g of cyanuric chloride, and 40 ml of water were added, followed by stirring at room temperature for 1 hour. Next, 0.93 g of aniline hydrochloride was added and stirred for 2 hours. Moreover, 0.73 g of butylamine hydrochloride was added, and the mixture was heated and stirred at 80 ° C. for 3 hours. After cooling to room temperature, salting out with sodium chloride gave 5.30 g of product. ¹ H, ¹³ C—N M R spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the target compound (G-19).

Ｇ−１の合成において、ペンタフルオロベンゼンスルホニルクロリドに代えて２，３−ジヒドロベンゾフラン−５−スルホニルクロリドを使用した以外は同様にして、上記化合物Ｇ−２０を得た。 (Synthesis of imido acid anion compound (G-20))

Compound G-20 was obtained in the same manner as in the synthesis of G-1, except that 2,3-dihydrobenzofuran-5-sulfonyl chloride was used in place of pentafluorobenzenesulfonyl chloride.

撹拌子を入れた３００ ｍｌナスフラスコに、化合物Ｇ−１８３．０３ ｇを溶解させたテトラヒドロフランと、無水マレイン酸 １．０７ ｇを溶解させた１，４−ジオキサンを、体積比１：１で混ぜあわせ、室温で１２時間撹拌した。反応によって生じた白色固体を吸引ろ過でろ別することで、３．８１ ｇの生成物（Ｇ−２１ａ）を得た。¹ Ｈ、¹³ Ｃ − Ｎ Ｍ Ｒ スペクトル（ 溶剤： 重水素化クロロホルム） 測定により、得られた化合物が目的化合物（ Ｇ−２１ａ） で表される化合物であることを確認した。 (Synthesis of imido acid anion compound (G-21))

In a 300 ml eggplant flask containing a stir bar, tetrahydrofuran in which compound G-183.03 g was dissolved and 1,4-dioxane in which 1.07 g of maleic anhydride was dissolved were mixed at a volume ratio of 1: 1. Combined and stirred at room temperature for 12 hours. The white solid produced by the reaction was separated by suction filtration to obtain 3.81 g of the product (G-21a). ¹ H, ¹³ C—N MR spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the target compound (G-21a).

撹拌子を入れた３００ ｍｌナスフラスコに、酢酸ナトリウムを含む無水酢酸溶液（酢酸ナトリウム：無水酢酸＝１：１０）、化合物Ｇ−２１ａ ４．０１ ｇを加え、７０℃で３時間撹拌した。室温まで放冷した後、ジエチルエーテルを加え生じた沈殿物を吸引ろ過で得た。その後、アセトニトリルで洗い、そのろ液にジエチルエーテルを加え再沈殿させて、３．４５ ｇ の生成物を得た。¹ Ｈ、¹³ Ｃ − Ｎ Ｍ Ｒ スペクトル（ 溶剤： 重水素化クロロホルム） 測定により、得られた化合物が目的化合物（ Ｇ−２１） で表される化合物であることを確認した。

An acetic anhydride solution containing sodium acetate (sodium acetate: acetic anhydride = 1: 10) and 4.01 g of compound G-21a were added to a 300 ml eggplant flask containing a stir bar, and the mixture was stirred at 70 ° C. for 3 hours. After allowing to cool to room temperature, diethyl ether was added and the resulting precipitate was obtained by suction filtration. Thereafter, it was washed with acetonitrile, and diethyl ether was added to the filtrate for reprecipitation to obtain 3.45 g of a product. ¹ H, ¹³ C—N MR spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the target compound (G-21).

<Method for producing salt-forming compound>
(Salt-forming compound (ZC-1))
A salt-forming compound (ZC-1) comprising a cationic cyanine dye and an imido acid anion compound (G-1) was produced by the following procedure. In addition, C.I. used in (ZC-1 to 21). I. For Basic Red 12, Aizen Astra Phloxine manufactured by Hodogaya Chemical Co., Ltd. was used.
In a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone, and 100 parts of acetone, 8.23 parts of imidic acid anion compound (G-1) and 10 parts of cationic cyanine dye (CI basic) Red 12) was dissolved and stirred at 60 ° C. for 240 minutes to sufficiently react. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The taken out salt-forming compound was dried with a dryer, and 14.3 parts of a salt-forming compound (ZC) of a cationic cyanine dye (CI Basic Red 12) and an imido acid anion compound (G-1). -1) was obtained.

(Salt-forming compound (ZC-2 to ZC-26))
The salt-forming compound (ZC) except that the type and blending amount (parts by weight) of the cationic cyanine dye and imido acid anion compound were changed to the type and blending amount (parts by weight) of the cationic dye and anion compound shown in Table 1. In the same manner as in -1), salt-forming compounds (ZC-22 to ZC-26) composed of various cationic dyes and various anion compounds were obtained. In addition, C.I. I. Basic Violet 10 and C.I. For I. Basic Violet 11, a commercially available dye was used.

<Method for producing dye solution>
(Dye solution (SY-1))
The following mixture was subjected to ultrasonic irradiation for 1 hour to obtain a cyanine dye solution (SY-1).

Salt-forming compound (ZC-1): 10.0 parts Propylene glycol monomethyl ether acetate: 90.0 parts

(Dye solution (SY-2 to 26))
Except for changing the salt-forming compound (ZC-1) in the production of the dye solution (SY-1) to the composition described in Table 2, the dye solution (SY-1) was prepared in the same manner as in the dye solution (SY-1). -2 to 26 were obtained.

<Production method of fine pigment>
(Miniaturized blue pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 3 (PB15: 3, 200 parts “LIONOL BLUE FG-7351” manufactured by Toyocolor Co., Ltd., 600 parts of sodium chloride, and 600 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Next, the kneaded product was put into 8000 parts of warm water, stirred for 8 hours while heating to 120 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, Drying at 85 ° C. for a whole day and night gave a phthalocyanine-based fine blue pigment 1.

(Miniaturized blue pigment 2)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) at 80 ° C. For 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine blue pigment 2 was obtained.

(Miniaturized blue pigment 3)
Triphenylmethane blue pigment C.I. I. Pigment Blue 1 (“Fana Blue D 6340” manufactured by BASF, specific surface area 65 m 2 / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 6 ° C. Kneaded for hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based blue fine pigment 3 was obtained.

(Miniaturized purple pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A dioxazine-based purple refined purple pigment 1 was obtained.

(Miniaturized green pigment 1)
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine green pigment 1 was obtained.

(Miniaturized yellow pigment 1)
Yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A refined yellow pigment 1 was obtained.

(Miniaturized yellow pigment 2)
Yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Pariotor Yellow D1819” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A refined yellow pigment 2 was obtained.

(Miniaturized red pigment 1)
Red pigment C.I. I. Pigment Red 254 (BASF “B-CF”) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Thus, a refined red pigment 1 was obtained.

<Preparation of resin-type dispersant solution>
(Resin Dispersant Solution 1)
A resin type dispersant solution 1 was prepared by using a commercially available resin type dispersant, EFKA4300 manufactured by BASF, and ethylene glycol monomethyl ether acetate to prepare a 40 wt% nonvolatile content solution.

<Method for producing pigment dispersion>
(Pigment dispersion (P-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (P-1) whose non-volatile component is 20 weight% was produced.

Refined blue pigment 1: 13.0 parts Acrylic resin solution 1: 30.0 parts Propylene glycol monomethyl ether acetate: 52.0 parts Resin-type dispersant solution 1: 5.0 parts

(Pigment dispersion (P-2 to 8))
The pigment was prepared in the same manner as for the pigment dispersion (P-1) except that the type of the fine organic pigment (miniaturized blue pigment 1) in the production of the pigment dispersion (P-1) was changed as shown in Table 3. Dispersions (P-2 to 8) were produced.

<Method for producing colored composition for solid-state imaging device>
[Example 1]
(Resist material (R-1))
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a resist material (R-1).

Dye solution (SY-1): 35.0 parts Pigment dispersion (P-1): 22.0 parts Acrylic resin solution 1: 16.0 parts Trimethylolpropane triacrylate: 3.0 parts (manufactured by Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT")
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 23.0 parts

[Examples 2 to 30, Comparative Examples 1 to 4]
(Resist material (R-2 to 35))
The dye solution (SY-1) and the pigment dispersion (P-1) were changed to the types and blending amounts (parts by weight) of the dye solution and the pigment dispersion shown in Table 4, respectively, and the solid content of the resist material was changed. Resist material (R-1) except that it was adjusted with acrylic resin solution 1 and propylene glycol monomethyl ether acetate so that the colorant concentration with respect to the solid content of the resist material was 17.0% by weight and 40.0% by weight. Similarly, resist materials (R-2 to 35) were obtained.

<Evaluation method of resist material>
The spectral characteristics of the obtained resist materials (R-1 to 35) were evaluated by the following methods. The results are shown in Table 5.

(Spectral characteristic evaluation)
The obtained resist material was applied on a 1.1 mm thick glass substrate using a spin coater so that the transmittance at a peak wavelength at a film thickness of 1.0 μm was 70% or more, and dried at 70 ° C. for 20 minutes. Thereafter, it was further heated at 230 ° C. for 60 minutes to obtain a coated substrate. The spectrum of the obtained substrate was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics). The evaluation criteria are as follows.

“Spectral transmittance peak wavelength range”
◎ ... 410 nm or more, 425 nm or less ○ ・ ・ ・ 400 nm or more, less than 410 nm, or 425 nm or more, 430 nm or less × ・ ・ ・ Less than 400 nm, more than 430 nm

"Transmittance with wavelength less than 400nm and 450nm or more"
◎ ... 10.0% or less ○ ... Greater than 10.0%, 15.0% or less △ ... More than 15.0%, 20.0% or less × ... From 20.0% large

  In addition, the colored composition (R-34, 35) of Comparative Examples 3 and 4 could not produce a coating film having a peak wavelength transmittance of 70% or more at a film thickness of 1.0 μm.

  From the result of Table 5, it contains at least one kind of dye (A) selected from the group consisting of the dioxazine-based purple pigment, cyanine dye, and xanthene dye of the present application, and a blue pigment (B), and the dye (A ) And the blue pigment (B) in the range of 30/70 to 80/20, the colored composition was excellent in color characteristics and spectral characteristics.

Especially, the coloring composition (R-1-21, R-27-29) whose pigment | dye (A) is a cyanine dye represented by General formula (1) has a transmittance | permeability of wavelength 400nm or less, and wavelength 450nm. The above transmittance was low and the spectral characteristics were more excellent.
Among the cyanine dyes represented by the general formula (1), a colored composition (R) in which the anion represented by Y ⁻ in the general formula (1) is an imido acid anion represented by the general formula (2) -1 to 21 and R-27 to 29) have a peak transmittance wavelength range of 410 to 425 nm, and not only a transmittance of a wavelength of 400 nm or less, but also a transmittance of a wavelength of 450 nm or more is 15.0%. As a result, the following spectral characteristics were obtained, and the results were particularly excellent.

Among the cyanine dyes represented by the general formula (1), an aromatic imido group represented by the general formula (2) in which R ²¹ and R ²² are substituted with fluorine atoms is: The wavelength range of the peak transmittance is a better range, particularly in the case of a pentafluorophenyl group, the wavelength range of the peak transmittance is 410 to 425 nm, and the transmittance of wavelengths less than 400 nm and 450 nm or more is also 10.0%. The following was particularly good.

On the other hand, in the colored composition (R-32 to 35) in which the content ratio of the dye (A) and the blue pigment (B) is outside the range of 30/70 to 80/20, the colored composition (R-32, 33) has a transmittance at a wavelength of 450 nm or more greater than 20.0%, and the colored composition (R-34, 35) has a coating film having a spectral transmittance at a peak wavelength of 70.0% or more. It could not be formed, and the results were inferior to those of the examples.
Further, the colored composition (R-35) using PB1 as the blue pigment (B) had a peak transmittance wavelength range of less than 400 nm, which was inferior to the examples from the viewpoint of spectral characteristics.

<Method for producing colored composition>

(Green coloring composition (RG-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a green coloring composition (RG-1).

Pigment dispersion (P-5): 38.5 parts Pigment dispersion (P-6): 16.5 parts Acrylic resin solution 1: 3.5 parts Trimethylolpropane triacrylate: 3.7 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 36.8 parts

(Red coloring composition (RR-1))

Pigment dispersion (P-7): 15.0 parts Pigment dispersion (P-8): 40.0 parts Acrylic resin solution 1: 3.5 parts Trimethylolpropane triacrylate: 3.7 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 36.8 parts

(Blue coloring composition (RB-1))

Pigment dispersion (P-2): 40.0 parts Pigment dispersion (P-4): 15.0 parts Acrylic resin solution 1: 3.5 parts Trimethylolpropane triacrylate: 3.7 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator (“OXE-02” manufactured by BASF): 1.0 part Propylene glycol monomethyl ether acetate: 36.8 parts

<Method for producing color filter for solid-state imaging device>
(Color filter for solid-state image sensor)
[Example 32]
A UV absorption layer (thickness: 0.06 μm) was formed on a silicon wafer on which a CMOS sensor was formed. The green coloring composition RG-1 was applied with a spin coater. After drying on a hot plate at 70 ° C. for 1 minute, exposure was performed through a photomask with an i-line stepper (FPA-5510iZ manufactured by Canon Inc.). The photomask has a 5.0 μm pitch pattern as shown in FIG. The exposure illuminance at this time was 27000 W / m ² , and the exposure amount was 3000 J / m ² . Subsequently, it developed with the organic type alkali developing solution (PK-DEX4310 by Parker Corporation), and post-baked for 5 minutes with a 230 degreeC hotplate, and obtained the green colored pixel. The film thickness of the green colored pixel was 0.9 μm. Subsequently, a red filter and a blue filter were formed using the red coloring composition RR-1 and the blue coloring composition RB-1 in the same manner. In either case, the film thickness was 0.9 μm. Next, a narrow band pixel was formed using the colored resist R-1. The film thickness was formed to be 1.5 μm. By the above method, a CMOS sensor wafer on which color filters were laminated was obtained.
[Examples 33 to 62]
A CMOS sensor wafer was obtained in which the color filters of Examples 33 to 62 were stacked in the same manner except that R-2 to R-31 were used to form the narrowband pixels.
<Endoscope device>
The imaging device cut out from the CMOS sensor wafer created in Example 32 and packaged was mounted on the endoscope apparatus. An outline of the endoscope apparatus is shown in FIG. When image processing was performed using pixel data of three colors of red, blue, and green, a blood vessel image having a relatively deep mucosa was obtained. On the other hand, in narrow-band light observation images including narrow-band pixels, fine capillaries on the mucosal surface layer can be seen clearly. The same evaluation was performed on the CMOS sensor wafers of Examples 33 to 62, but the same results as in Example 32 were obtained.
On the other hand, the same evaluation was performed on the CMOS sensor wafers produced in Comparative Examples 1 and 2, but a fine capillary image of the mucosal surface layer as obtained in the Examples could not be obtained.

Claims (7)

A color composition for a solid-state imaging device comprising a colorant, a binder resin, and an organic solvent, wherein the colorant is at least one selected from the group consisting of dioxazine-based purple pigments, cyanine dyes, and xanthene dyes It contains the dye (A) and the blue pigment (B), the content weight ratio of the dye (A) and the blue pigment (B) is in the range of 30/70 to 80/20, and the film thickness is 1.0 μm. When the coating film is formed so that the spectral transmittance at the peak wavelength is 70% or more, the peak wavelength of the coating film is in the range of 400 to 430 nm, and the transmission wavelength is 380 nm or more and less than 400 nm and 450 nm or more and less than 780 nm. A coloring composition for a solid-state imaging device, which has spectral characteristics such that the rate is 20% or less.
The coloring composition for a solid-state imaging device according to claim 1, wherein the coloring matter (A) is a cyanine dye represented by the following general formula (1).
General formula (1)

[In the general formula (1), Y ⁻ represents an inorganic or organic anion. However, this excludes when Y ⁻ is a halide ion. ] Y ^- anion represented by the following general formula (2) imide anion represented by claim 2 for a solid image pickup device colored composition wherein.
General formula (2)

[In General Formula (2), each of R ²¹ and R ²² independently represents an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent. It represents an aromatic hydrocarbon group that may have or a heterocyclic group that may have a substituent. ]   The blue pigment (B) is C.I. I. Pigment blue 15: 3 and C.I. I. The coloring composition for a solid-state imaging device according to any one of claims 1 to 3, wherein the coloring composition is at least one of CI Pigment Blue 15: 6.   Furthermore, the coloring composition for solid-state image sensors of any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator.   The color filter for solid-state image sensors which comprises the filter segment formed from the coloring composition of any one of Claims 1-5 on a base material.   A solid-state imaging device comprising the color filter according to claim 6.

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