JP2017031394A - Novel cyanine compound, optical filter and device using optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyanine compound that can give an optical filter excellent in light fastness, an optical filter using the cyanine compound, and a device using the optical filter.SOLUTION: The cyanine compound is represented, for example, by formula e below, which is a counterion conjunct comprising an anion and a cation.SELECTED DRAWING: None

Description

  The present invention relates to a novel cyanine compound, an optical filter, and an apparatus using the optical filter.

  A solid-state image pickup device such as a video camera, a digital still camera, or a mobile phone with a camera function uses a CCD or CMOS image sensor, which is a solid-state image pickup device for a color image. Silicon photodiodes that are sensitive to near infrared rays that cannot be sensed by the eyes are used. These solid-state image sensors need to be corrected for visibility so that they appear natural to the human eye. Optical filters that selectively transmit or cut light in a specific wavelength region (for example, near-infrared cut) Filter) is often used.

As such a near-infrared cut filter, what was conventionally manufactured by various methods is used. For example, JP-A-6-200113 (Patent Document 1) describes a near-infrared cut filter in which a transparent resin is used as a base material and a near-infrared absorbing dye is contained in the transparent resin. In particular, near-infrared cut filters using cyanine compounds as near-infrared absorbing dyes are widely known (see, for example, Patent Document 2 and Patent Document 3).
However, cyanine compounds generally have low light stability, and there are cases where the light resistance required for solid-state imaging device applications cannot be achieved.

JP-A-6-200113 JP 2007-219114 A JP 2010-072575 A

  An object of the present invention is to improve the drawbacks of conventional optical filters such as near-infrared cut filters and provide a cyanine compound capable of providing an optical filter having excellent light resistance, an optical filter using the cyanine compound, and An object of the present invention is to provide an apparatus using the optical filter.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an optical filter having excellent light resistance can be obtained by applying a specific cyanine compound, and the present invention has been completed. It was. Examples of embodiments of the present invention are shown below.

  [1] A cyanine compound which is a counter ion conjugate comprising an anion and a cation, and the cation is represented by any one of the following general formulas (I-1) to (I-6).

式（Ｉ−１）〜（Ｉ−６）中、
ｍおよびｎは、それぞれ０〜５の整数を表し、複数あるＤは、独立に炭素原子、窒素原子、酸素原子または硫黄原子を表し、
複数あるＲ_a、Ｒ_b、Ｒ_c、Ｒ_d、Ｒ_e、Ｒ_f、Ｒ_g、Ｒ_hおよびＲ_i、ならびに、Ｒ₁、Ｒ₂およびＲ₃は、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、−Ｌ¹、−Ｓ−Ｌ²、−ＳＳ−Ｌ²、−ＳＯ₂−Ｌ³、−Ｎ＝Ｎ−Ｌ⁴、または、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_h、Ｒ_hとＲ_iおよびＲ₁とＲ₂のうち少なくとも１つの組み合わせが結合した、下記式（Ａ）〜（Ｈ）で表される基からなる群より選ばれる少なくとも１種の基を表し、
前記アミノ基、アミド基、イミド基およびシリル基は、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種の置換基Ｌを有してもよく、
Ｌ¹は、下記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ²は、水素原子または下記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ³は、水酸基または下記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ⁴は、下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）前記置換基Ｌを有してもよい炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）前記置換基Ｌを有してもよい炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）前記置換基Ｌを有してもよい炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）前記置換基Ｌを有してもよい炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）前記置換基Ｌを有してもよい炭素数３〜１４の複素環基
Ｑ₁は下記一般式（ｑ１）を表し、Ｑ₂は下記一般式（ｑ２）〜（ｑ４）のいずれかで表される構造を表す。

In formulas (I-1) to (I-6),
m and n each represent an integer of 0 to 5, and a plurality of Ds independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,
A plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i , and R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl ^{group, -L 1, -S-L 2} , -SS-L 2, -SO 2 -L 3, -N = N -L ⁴ or at least of R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , R _h and R _i, and R ₁ and R ₂ Represents at least one group selected from the group consisting of groups represented by the following formulas (A) to (H) to which one combination is bonded;
The amino group, amide group, imide group and silyl group are an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, And may have at least one substituent L selected from the group consisting of an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms,
L ¹ represents any of the following L ^a ~L ^e,
L ² represents either a hydrogen atom or the following L ^a ~L ^e,
L ³ represents either a hydroxyl group or the following L ^a ~L ^e,
L ⁴ are, represents one of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms that may have the substituent L (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms that may have the substituent L ( L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have the substituent L (L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent L (L ^e ) A C 3-14 heterocyclic group that may have the substituent L Q ₁ represents the following general formula (q1), and Q ₂ represents any of the following general formulas (q2) to (q4). Represents the structure represented by

式（Ａ）〜（Ｈ）中、Ｒ_xとＲ_yの組み合わせは、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_h、Ｒ_hとＲ_iおよびＲ₁とＲ₂の組み合わせであり、
複数あるＲ_A〜Ｒ_Lは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、−Ｌ¹、−Ｓ−Ｌ²、−ＳＳ−Ｌ²、−ＳＯ₂−Ｌ³または−Ｎ＝Ｎ−Ｌ⁴（Ｌ¹〜Ｌ⁴は、前記式（Ｉ−１）〜（Ｉ−４）において定義したＬ¹〜Ｌ⁴と同義である。）を表し、前記アミノ基、アミド基、イミド基およびシリル基は、前記置換基Ｌを有してもよい。

In the formulas (A) to (H), the combinations of R _x and R _y are R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , R a combination of _h and R _i and R ₁ and R ₂ ,
Plural R _{A to} R _L are each independently a hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -SL ^{2. _{, -SS-L 2, -SO 2}} -L 3 or ^{-N = N-L 4 (L} 1 ~L 4 , the formula (I-1) ~ (L 1 ~L 4 defined in I-4) The amino group, amide group, imide group and silyl group may have the substituent L.

-C (= O) C _a X _{2a + 1} (q1)
-C _b Y _{2b + 1} (q2)
_{-C c Y 2c -OC d Y 2d} + 1 (q3)

式（ｑ１）中、ａは１〜５の整数を表し、Ｘは水素原子またはハロゲン原子を表し、複数あるＸは同一であっても異なっていてもよい。式（ｑ２）および（ｑ３）中、ｂ〜ｄはそれぞれ１〜５の整数を表し、Ｙは水素原子またはハロゲン原子を表し、複数あるＹは同一であっても異なっていてもよい。式（ｑ４）中、ｐは１〜５の整数を表し、Ｔ₁〜Ｔ₅はそれぞれ独立して水素原子、ハロゲン原子、−ＯＣＺ₃または−ＯＣ_eＺ_2eＣＺ₃（ｅは１〜５の整数を表し、Ｚは水素原子またはハロゲン原子を表し、複数あるＺは同一であっても異なっていてもよい。）を表す。ただし、Ｘ、ＹおよびＺの少なくとも１つはハロゲン原子である。

In formula (q1), a represents an integer of 1 to 5, X represents a hydrogen atom or a halogen atom, and a plurality of Xs may be the same or different. In formulas (q2) and (q3), b to d each represent an integer of 1 to 5, Y represents a hydrogen atom or a halogen atom, and a plurality of Y may be the same or different. In formula (q4), p represents an integer of _{1 to 5} , and T _{1 to} T ₅ are each independently a hydrogen atom, a halogen atom, —OCZ ₃ or —OC _e Z _2e CZ ₃ (e is 1 to 5). Represents an integer, Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be the same or different. However, at least one of X, Y and Z is a halogen atom.

  [2] The cyanine compound according to item [1], wherein the anion is represented by the following general formula (II).

式（ＩＩ）中、Ｙ₁〜Ｙ₂₀は、全てフッ素原子であるか、またはＹ₂、Ｙ₄、Ｙ₇、Ｙ₉、Ｙ₁₂、Ｙ₁₄、Ｙ₁₇、Ｙ₁₉がトリフルオロメチル基であり、残りのＹが水素原子である。

In formula (II), Y _{1 to} Y ₂₀ are all fluorine atoms, or Y ₂ , Y ₄ , Y ₇ , Y ₉ , Y ₁₂ , Y ₁₄ , Y ₁₇ , Y ₁₉ are trifluoromethyl groups. And the remaining Y is a hydrogen atom.

  [3] A substrate comprising a transparent resin layer containing the cyanine compound according to item [1] or [2], and a near-infrared reflective film formed on at least one surface of the substrate, Optical filter.

  [4] The transparent resin constituting the transparent resin layer is a cyclic olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate. Resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, Item 4. The optical filter according to Item [3], which is at least one resin selected from the group consisting of allyl ester curable resins and silsesquioxane ultraviolet curable resins.

[5] The optical filter according to item [3] or [4], wherein the near-infrared reflective film is formed on both surfaces of the substrate.
[6] The optical filter according to any one of items [3] to [5], which is for a solid-state imaging device.
[7] A solid-state imaging device comprising the optical filter according to any one of items [3] to [6].
[8] A camera module comprising the optical filter according to any one of items [3] to [6].
[9] The cyanine compound according to item [1] or [2], a cyclic olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, and a polyamide resin Resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, A resin composition comprising at least one resin selected from the group consisting of an epoxy resin, an allyl ester curable resin, and a silsesquioxane ultraviolet curable resin.

  ADVANTAGE OF THE INVENTION According to this invention, the optical filter excellent in light resistance can be provided.

Hereinafter, the present invention will be specifically described.
The optical filter according to the present invention includes a substrate including a transparent resin layer containing the cyanine compound of the present invention (hereinafter also referred to as “cyanine compound (A)” or “compound (A)”) described later, and at least one of the substrates. A near-infrared reflective film formed on one surface.

[Substrate including transparent resin layer]
The substrate including the transparent resin layer constituting the optical filter of the present invention (hereinafter also simply referred to as “substrate”) may be a single layer or a multilayer (in the case of multiple layers, for example, cured on the transparent resin layer serving as a base). It may be a structure in which an overcoat layer made of a resin is laminated), and contains at least one compound (A) as a near-infrared absorbing dye, and has an absorption maximum at a wavelength of 700 to 1000 nm, more preferably 750. The transmittance at the absorption maximum wavelength is preferably 10% or less, and more preferably 8% or less. If the absorption maximum wavelength of the substrate and the transmittance at the absorption maximum wavelength are in such a range, the substrate can selectively and efficiently cut near infrared rays, and a near infrared reflecting film can be formed on the surface of the substrate. When the film is formed, it is possible to reduce the incident angle dependence of optical characteristics in the visible wavelength to near infrared wavelength region.

  Depending on the use such as a camera module, the average transmittance of the substrate containing the compound (A) in the so-called visible light region having a wavelength of 400 to 700 nm when the thickness of the substrate is 100 μm is 50% or more, preferably 65%. It may be necessary to do this.

  The thickness of the substrate can be appropriately selected according to a desired application and is not particularly limited. However, it is preferable to adjust the substrate so that the incident angle dependency is improved as described above, more preferably 30. It is -250 micrometers, More preferably, it is 40-200 micrometers, Most preferably, it is 50-150 micrometers.

  When the thickness of the substrate is in the above range, an optical filter using the substrate can be reduced in size and weight, and can be suitably used for various applications such as a solid-state imaging device. In particular, when the substrate is used in a lens unit such as a camera module, it is preferable because the lens unit can be reduced in height.

  In addition to the compound (A), the substrate further contains at least one near-infrared absorbing dye (X) selected from the group consisting of a squarylium compound, a cyanine compound other than the compound (A), and a phthalocyanine compound. be able to. By using such a substrate, the incident angle dependence in the visible wavelength region to the near infrared wavelength region can be further reduced, the absorption band waveform can be further sharpened, and an optical filter having a wide viewing angle can be obtained. Can be obtained.

  The compound (A) and the near-infrared absorbing dye (X) may be contained in the same layer or in different layers. When included in the same layer, for example, a form in which both the compound (A) and the near-infrared absorbing dye (X) are included in the same transparent resin layer can be cited, and when included in separate layers, For example, the form by which the layer containing the said near-infrared absorption pigment | dye (X) is laminated | stacked on the transparent resin layer containing a compound (A) can be mentioned.

  The compound (A) and the near-infrared absorbing dye (X) are more preferably contained in the same layer. In such a case, the compound (A) and the near-infrared absorbing dye are contained in a case where they are contained in separate layers. It becomes easier to control the content ratio of (X).

[Cyanine compound (A)]
The cyanine compound (A) of the present invention includes a cation represented by any one of the following general formulas (I-1) to (I-6) (hereinafter, collectively referred to as “cation (I)”) and an anion. (Hereinafter also referred to as “anion (II)”).

  ≪Cation (I) ≫

式（Ｉ−１）〜（Ｉ−６）中、
ｍおよびｎは、それぞれ０〜５の整数を表し、複数あるＤは、独立に炭素原子、窒素原子、酸素原子または硫黄原子を表し、
複数あるＲ_a、Ｒ_b、Ｒ_c、Ｒ_d、Ｒ_e、Ｒ_f、Ｒ_g、Ｒ_hおよびＲ_i、ならびに、Ｒ₁、Ｒ₂およびＲ₃は、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、−Ｌ¹、−Ｓ−Ｌ²、−ＳＳ−Ｌ²、−ＳＯ₂−Ｌ³、−Ｎ＝Ｎ−Ｌ⁴、または、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_h、Ｒ_hとＲ_iおよびＲ₁とＲ₂のうち少なくとも１つの組み合わせが結合した、下記式（Ａ）〜（Ｈ）で表される基からなる群より選ばれる少なくとも１種の基を表し、
前記アミノ基、アミド基、イミド基およびシリル基は、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のハロゲン置換アルキル基、炭素数３〜１４の脂環式炭化水素基、炭素数６〜１４の芳香族炭化水素基および炭素数３〜１４の複素環基からなる群より選ばれる少なくとも１種の置換基Ｌを有してもよく、
Ｌ¹は、下記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ²は、水素原子または下記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ³は、水酸基または下記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ⁴は、下記Ｌ^a〜Ｌ^eのいずれかを表し、
（Ｌ^a）前記置換基Ｌを有してもよい炭素数１〜１２の脂肪族炭化水素基
（Ｌ^b）前記置換基Ｌを有してもよい炭素数１〜１２のハロゲン置換アルキル基
（Ｌ^c）前記置換基Ｌを有してもよい炭素数３〜１４の脂環式炭化水素基
（Ｌ^d）前記置換基Ｌを有してもよい炭素数６〜１４の芳香族炭化水素基
（Ｌ^e）前記置換基Ｌを有してもよい炭素数３〜１４の複素環基
Ｑ₁は下記一般式（ｑ１）を表し、Ｑ₂は下記一般式（ｑ２）〜（ｑ４）のいずれかで表される構造を表す。

In formulas (I-1) to (I-6),
m and n each represent an integer of 0 to 5, and a plurality of Ds independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,
A plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i , and R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl ^{group, -L 1, -S-L 2} , -SS-L 2, -SO 2 -L 3, -N = N -L ⁴ or at least of R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , R _h and R _i, and R ₁ and R ₂ Represents at least one group selected from the group consisting of groups represented by the following formulas (A) to (H) to which one combination is bonded;
The amino group, amide group, imide group and silyl group are an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, And may have at least one substituent L selected from the group consisting of an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms,
L ¹ represents any of the following L ^a ~L ^e,
L ² represents either a hydrogen atom or the following L ^a ~L ^e,
L ³ represents either a hydroxyl group or the following L ^a ~L ^e,
L ⁴ are, represents one of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms that may have the substituent L (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms that may have the substituent L ( L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have the substituent L (L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent L (L ^e ) A C 3-14 heterocyclic group that may have the substituent L Q ₁ represents the following general formula (q1), and Q ₂ represents any of the following general formulas (q2) to (q4). Represents the structure represented by

式（Ａ）〜（Ｈ）中、Ｒ_xとＲ_yの組み合わせは、Ｒ_bとＲ_c、Ｒ_dとＲ_e、Ｒ_eとＲ_f、Ｒ_fとＲ_g、Ｒ_gとＲ_h、Ｒ_hとＲ_iおよびＲ₁とＲ₂の組み合わせであり、
複数あるＲ_A〜Ｒ_Lは、それぞれ独立に水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、−Ｌ¹、−Ｓ−Ｌ²、−ＳＳ−Ｌ²、−ＳＯ₂−Ｌ³または−Ｎ＝Ｎ−Ｌ⁴（Ｌ¹〜Ｌ⁴は、前記式（Ｉ−１）〜（Ｉ−４）において定義したＬ¹〜Ｌ⁴と同義である。）を表し、前記アミノ基、アミド基、イミド基およびシリル基は、前記置換基Ｌを有してもよい。

In the formulas (A) to (H), the combinations of R _x and R _y are R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , R a combination of _h and R _i and R ₁ and R ₂ ,
Plural R _{A to} R _L are each independently a hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -SL ^{2. _{, -SS-L 2, -SO 2}} -L 3 or ^{-N = N-L 4 (L} 1 ~L 4 , the formula (I-1) ~ (L 1 ~L 4 defined in I-4) The amino group, amide group, imide group and silyl group may have the substituent L.

-C (= O) C _a X _{2a + 1} (q1)
-C _b Y _{2b + 1} (q2)
_{-C c Y 2c -OC d Y 2d} + 1 (q3)

式（ｑ１）中、ａは１〜５の整数を表し、Ｘは水素原子またはハロゲン原子を表し、複数あるＸは同一であっても異なっていてもよい。式（ｑ２）および（ｑ３）中、ｂ〜ｄはそれぞれ１〜５の整数を表し、Ｙは水素原子またはハロゲン原子を表し、複数あるＹは同一であっても異なっていてもよい。式（ｑ４）中、ｐは１〜５の整数を表し、Ｔ₁〜Ｔ₅はそれぞれ独立して水素原子、ハロゲン原子、−ＯＣＺ₃または−ＯＣ_eＺ_2eＣＺ₃（ｅは１〜５の整数を表し、Ｚは水素原子またはハロゲン原子を表し、複数あるＺは同一であっても異なっていてもよい。）を表す。ただし、Ｘ、ＹおよびＺの少なくとも１つはハロゲン原子である。

In formula (q1), a represents an integer of 1 to 5, X represents a hydrogen atom or a halogen atom, and a plurality of Xs may be the same or different. In formulas (q2) and (q3), b to d each represent an integer of 1 to 5, Y represents a hydrogen atom or a halogen atom, and a plurality of Y may be the same or different. In formula (q4), p represents an integer of _{1 to 5} , and T _{1 to} T ₅ are each independently a hydrogen atom, a halogen atom, —OCZ ₃ or —OC _e Z _2e CZ ₃ (e is 1 to 5). Represents an integer, Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be the same or different. However, at least one of X, Y and Z is a halogen atom.

Wherein L ^a ~L ^e is the total number of carbon atoms including the substituent is preferably respectively 50 or less, still more preferably a few 40 or less carbon atoms, and particularly preferably 30 or less carbon atoms. When the number of carbon atoms is larger than this range, it may be difficult to synthesize the dye, and the absorption intensity per unit weight tends to decrease.

The aliphatic hydrocarbon group having 1 to 12 carbon atoms in the L ^a and L, for example, a methyl group (Me), ethyl (Et), n-propyl group (n-Pr), isopropyl (i-Pr ), N-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Alkyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group And alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L ^b and L include, for example, trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloro Mention may be made of propyl and heptafluoropropyl groups.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L ^c and L include cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a norbornane group and an adamantane group And polycyclic alicyclic groups such as

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include, for example, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, Mention may be made of phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenylyl groups.

Wherein L Examples of the heterocyclic group having 3 to 14 carbon atoms in the ^e and L, for example, furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indolenine, benzofuran Benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridine, morpholine and phenazine.

As the L ^a, the aforementioned "aliphatic hydrocarbon group having 1 to 12 carbon atoms", and include those in which the aliphatic hydrocarbon group further has the substituent L, preferably a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 4-phenylbutyl group, 2-cyclohexylethyl, more preferably methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and hexyl group.

Examples of L ^b include the above-mentioned “halogen-substituted alkyl group having 1 to 12 carbon atoms” and those in which the halogen-substituted alkyl group further has the substituent L, preferably a trichloromethyl group or a pentachloroethyl group. , Trifluoromethyl group, pentafluoroethyl group, 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, more preferably trichloromethyl group, pentachloroethyl group, trifluoromethyl group, pentafluoroethyl It is a group.

Examples of L ^c include the above-mentioned “C3-C14 alicyclic hydrocarbon group” and those in which the alicyclic hydrocarbon group further has the substituent L, preferably a cyclobutyl group, cyclopentyl. Group, cyclohexyl group, 4-ethylcyclohexyl group, cyclooctyl group and 4-phenylcycloheptyl group, more preferably cyclopentyl group, cyclohexyl group and 4-ethylcyclohexyl group.

Examples of L ^d include the above-mentioned “aromatic hydrocarbon group having 6 to 14 carbon atoms” and those in which the aromatic hydrocarbon group further has the substituent L, preferably a phenyl group, 1-naphthyl. Group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group, 2,3,6-triphenylphenyl group, 2, A 3,4,5,6-pentaphenylphenyl group, more preferably a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, and a 2,3,4,5,6-pentaphenylphenyl group.

As the L ^e, described above, "heterocyclic group having 3 to 14 carbon atoms", and include those in which the heterocyclic group further has the substituent L, preferably furan, thiophene, pyrrole, indole, indoline, A group consisting of indolenine, benzofuran, benzothiophene and morpholine, more preferably a group consisting of furan, thiophene, pyrrole and morpholine.

Wherein L ^a ~L ^e further halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, have at least one atom or group selected from the group consisting of a phosphate group and an amino group May be. Examples include 4-sulfobutyl, 4-cyanobutyl, 5-carboxypentyl, 5-aminopentyl, 3-hydroxypropyl, 2-phosphorylethyl, 6-amino-2,2-dichloro. Hexyl group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group, 4-hydroxyphenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-nitrophenyl group, group consisting of 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyano Propoxy group, 4-fluorobenzoyl group, 2-hydroxyethoxycarbonyl , It may be mentioned 4-cyano-butoxycarbonyl group.

In R _{a to} R _i and R _{1 to} R ₃ , the amino group which may have a substituent L is an amino group, ethylamino group, dimethylamino group, methylethylamino group, dibutylamino group, diisopropylamino. Group and the like.

In R _{a to} R _i and R _{1 to} R ₃ , as an amide group which may have a substituent L, an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, Examples thereof include a dibutylamide group, an α-lactam group, a β-lactam group, a γ-lactam group, and a δ-lactam group.

In R _{a to} R _i and R _{1 to} R ₃ , the imide group that may have a substituent L is an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group, A dibutylimide group etc. are mentioned.

In R _{a to} R _i and R _{1 to} R ₃ , examples of the silyl group which may have a substituent L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a triethylsilyl group. .

In the above R _{a to} R _i and R _{1 to} R ₃ , —SL ² includes thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, isobutyl sulfide group, sec-butyl sulfide group Tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl fluoride group, and the like.

In R _{a to} R _i and R _{1 to} R ₃ , —SS-L ² is a disulfide group, a methyl disulfide group, an ethyl disulfide group, a propyl disulfide group, a butyl disulfide group, an isobutyl disulfide group, or a sec-butyl disulfide group. Tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group, 4-cumylphenyl disulfide group and the like.

In R _{a to} R _i and R _{1 to} R ₃ , examples of —SO ₂ —L ³ include a sulfoxyl group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, and a p-toluenesulfonyl group.

In R _{a to} R _i and R _{1 to} R ₃ , examples of —N═N—L ⁴ include a methylazo group, a phenylazo group, a p-methylphenylazo group, and a p-dimethylaminophenylazo group.

≪Anion (II) ≫
The anion (II) is not particularly limited as long as it is an anion body of a cyanine compound, and examples thereof include an anion represented by the following general formula (II) from the viewpoint of improving the light resistance of the cyanine compound.

式（ＩＩ）中、Ｙ₁〜Ｙ₂₀は、全てフッ素原子であるか、またはＹ₂、Ｙ₄、Ｙ₇、Ｙ₉、Ｙ₁₂、Ｙ₁₄、Ｙ₁₇、Ｙ₁₉がトリフルオロメチル基であり、残りのＹが水素原子である。

In formula (II), Y _{1 to} Y ₂₀ are all fluorine atoms, or Y ₂ , Y ₄ , Y ₇ , Y ₉ , Y ₁₂ , Y ₁₄ , Y ₁₇ , Y ₁₉ are trifluoromethyl groups. And the remaining Y is a hydrogen atom.

<Near-infrared absorbing dye (X)>
The near-infrared absorbing dye (X) is at least one selected from the group consisting of a squarylium compound, a phthalocyanine compound, and a cyanine compound other than the compound (A), and particularly preferably contains a squarylium compound. The absorption maximum wavelength of the near-infrared absorbing dye (X) is preferably 620 nm or more, more preferably 650 nm or more, particularly preferably 670 nm or more, and preferably less than 800 nm, more preferably 750 nm or less, particularly preferably 730 nm or less. In addition, it is desirable that the compound (A) contained at the same time has an absorption maximum on a shorter wavelength side than the absorption maximum wavelength. When the absorption maximum wavelength is in such a wavelength range, the waveform of the absorption band can be further sharpened, the absorption band due to the near-infrared absorbing dye can be sufficiently widened, and the incident angle dependent improvement performance and ghosting can be improved. A reduction effect can be achieved.

  In the substrate, the content of the near-infrared absorbing dye (X) is preferably 0.01 to 5.0 parts by weight, more preferably 0.02 to 100 parts by weight of the transparent resin constituting the transparent resin layer. 3.5 parts by weight, particularly preferably 0.03 to 2.5 parts by weight. When the content of the near-infrared absorbing dye (X) is within the above range, it is possible to achieve both good near-infrared absorption characteristics and high visible light transmittance.

《Squaryllium compound》
The squarylium-based compound preferably includes at least one selected from the group consisting of a squarylium-based compound represented by the formula (III-1) and a squarylium-based compound represented by the formula (III-2).

式（ＩＩＩ−１）中、Ｒ^a、Ｒ^bおよびＹは、下記（ｉ）または（ii）の条件を満たす。

In formula (III-1), R ^a , R ^b and Y satisfy the following condition (i) or (ii).

Condition (i)
A plurality of R ^a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L ¹ or —NR ^e R ^f group. R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d, or -L ^e .

Plural R ^{b s} each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L ¹ or —NR ^g R ^h group. R ^g and R ^h are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C (O) R ⁱ group (R ⁱ is -L ^a , -L ^b, -L ^c, represents a -L ^d or -L ^e.) represents the.

Plural Ys each independently represent a —NR ^j R ^k group. R ^j and R ^k each independently represents a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d, or -L ^e .
L ¹ , L ^a , L ^b , L ^c , L ^d , and ^Le are L ¹ , L ^a , L ^b , and L defined in the formulas (I-1) to (I-4), respectively. ^c, L ^d, it is synonymous with L ^e.

Condition (ii)
At least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 member atoms containing at least one nitrogen atom; The heterocyclic ring may have a substituent, and R ^b and R ^a that does not participate in the formation of the heterocyclic ring are each independently synonymous with R ^b and R ^a in the above (i).

式（ＩＩＩ−２）中、Ｘは、Ｏ、Ｓ、Ｓｅ、Ｎ−Ｒ^cまたはＣ−Ｒ^dＲ^dを表し；複数あるＲ^cは、それぞれ独立に水素原子、−Ｌ^a、−Ｌ^b、−Ｌ^c、−Ｌ^dまたは−Ｌ^eを表し；複数あるＲ^dは、それぞれ独立に水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、−Ｌ¹または−ＮＲ^eＲ^f基を表し、隣り合うＲ^d同士は連結して置換基を有していてもよい環を形成してもよく；Ｌ^a〜Ｌ^e、Ｌ¹は前記式（Ｉ−１）〜（Ｉ−４）にて定義したＬ^a〜Ｌ^eと同義であり、Ｒ^eおよびＲ^fは、前記（ｉ）のＲ^eおよびＲ^fと同義である。

In formula (III-2), X represents O, S, Se, N—R ^c or C—R ^d R ^d ; a plurality of R ^{c s} independently represent ^a hydrogen atom, —L ^a , —L ^b , -L ^c , -L ^d or -L ^e ; a plurality of R ^{d s} independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ or -NR ^e R ^f group, and adjacent R ^d groups may be linked to form a ring which may have a substituent; L ^{a to} L ^e and L ¹ are ^each represented by the above formula (I -1) ~ (I-4) has the same meaning as defined L ^a ~L ^e at, R ^e and R ^f have the same meanings as R ^e and R ^f of the (i).

The left and right substituents bonded to the central four-membered ring of the squarylium-based compound may be the same or different, but it is preferable that they are the same because synthesis is easier.
The squarylium compound may be synthesized by a generally known method, for example, a method described in JP-A-1-228960, JP-A-2001-40234, JP-A-3196383, or the like. Etc. and can be synthesized.

《Phthalocyanine compound》
As the phthalocyanine-based compound, a compound having a generally known arbitrary structure can be used. For example, it is described in Japanese Patent No. 4081149 or “phthalocyanine-chemistry and function” (IPC, 1997). Can be synthesized by any method.

<Cyanine compounds>
As the cyanine compound, those having any structure generally known other than the compound (A) can be used, and can be synthesized, for example, by the method described in JP-A-2009-108267. .

<Transparent resin>
The substrate can be formed using a transparent resin.
The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it ensures thermal stability and moldability to a film, and dielectrics are formed by high-temperature deposition performed at a deposition temperature of 100 ° C. or higher. In order to obtain a film that can form a body multilayer film, a resin having a glass transition temperature (Tg) of preferably 110 to 380 ° C, more preferably 110 to 370 ° C, and still more preferably 120 to 360 ° C. Further, it is particularly preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film capable of depositing a dielectric multilayer film at a higher temperature can be obtained.

  As a transparent resin, when a resin plate having a thickness of 0.1 mm made of the resin is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, Particularly preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.

  The weight average molecular weight (Mw) in terms of polystyrene measured by a gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000. The average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

  Examples of the transparent resin include cyclic olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfones. Resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl Examples include ester-based curable resins and silsesquioxane-based ultraviolet curable resins.

≪Cyclic olefin resin≫
The cyclic olefin-based resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). A resin and a resin obtained by hydrogenating the resin are preferable.

式（Ｘ₀）中、Ｒ^x1〜Ｒ^x4は、それぞれ独立に下記（ｉ’）〜（ix’）より選ばれる原子または基を表し、ｋ^x、ｍ^xおよびｐ^xは、それぞれ独立に０または正の整数を表す。
（ｉ’）水素原子
（ii’）ハロゲン原子
（iii’）トリアルキルシリル基
（iv’）酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、
置換または非置換の炭素数１〜３０の炭化水素基
（ｖ’）置換または非置換の炭素数１〜３０の炭化水素基
（vi’）極性基（但し、（iv’）を除く。）
（vii’）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成されたアルキリデン基（但し、前記結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ’）〜（vi’）より選ばれる原子または基を表す。）
（viii’）Ｒ^x1とＲ^x2またはＲ^x3とＲ^x4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1〜Ｒ^x4は、それぞれ独立に前記（ｉ’）〜（vi’）より選ばれる原子または基を表す。）
（ix’）Ｒ^x2とＲ^x3とが、相互に結合して形成された単環の炭化水素環または複素環（但し、前記結合に関与しないＲ^x1とＲ^x4は、それぞれ独立に前記（ｉ’）〜（vi’）より選ばれる原子または基を表す。）

In the formula (X ₀ ), R ^{x1 to} R ^x4 each independently represents an atom or group selected from the following (i ′) to (ix ′), and k ^x , ^mx and p ^x are each independently 0 Or represents a positive integer.
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (v ′) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi ′) polar group (excluding (iv ′))
(Vii ′) an alkylidene group formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (provided that R ^{x1 to} R ^x4 not involved in the bonding are independently the above (i ′ )-(Vi ′) represents an atom or group selected from.
(Viii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R ^{x1 to} R not involved in the bonding) ^x4 each independently represents an atom or group selected from the above (i ′) to (vi ′).
(Ix ′) A monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other (provided that R ^x1 and R ^x4 not involved in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').

式（Ｙ₀）中、Ｒ^y1およびＲ^y2は、それぞれ独立に前記（ｉ’）〜（vi’）より選ばれる原子または基を表すか、Ｒ^y1とＲ^y2とが、相互に結合して形成された単環もしくは多環の脂環式炭化水素、芳香族炭化水素または複素環を表し、ｋ^yおよびｐ^yは、それぞれ独立に０または正の整数を表す。

In the formula (Y ₀ ), R ^y1 and R ^y2 each independently represents an atom or group selected from the above (i ′) to (vi ′), or R ^y1 and R ^y2 are bonded to each other. formed monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or heterocyclic, k ^y and p ^y are each independently 0 or a positive integer.

≪Aromatic polyether resin≫
The aromatic polyether-based resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄは、それぞれ独立に０〜４の整数を示す。

In formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.

式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄは、それぞれ独立に前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは、単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈは、それぞれ独立に０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０のとき、Ｒ⁷はシアノ基ではない。

Wherein (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

  The aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Is preferred.

式（３）中、Ｒ⁵およびＲ⁶は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示す。

In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —,> C = O, -CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.

式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈは、それぞれ独立に前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆは、それぞれ独立に前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2), and R ⁵ , R ⁶ , Z, n, e and f are independently the same as R ⁵ , R ⁶ , Z, n, e and f in the formula (3).

≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in a repeating unit. For example, it is synthesized by a method described in JP-A-2006-199945 or JP-A-2008-163107. can do.

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized by, for example, a method described in JP-A-2008-163194.

≪Fluorene polyester resin≫
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, the fluorene polyester resin can be synthesized by a method described in JP 2010-285505 A or JP 2011-197450 A. it can.

≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer-based resin is not particularly limited, but at least one selected from the group consisting of an aromatic ring having at least one fluorine, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Any polymer containing a repeating unit containing one bond may be used, and for example, the polymer can be synthesized by the method described in JP-A-2008-181121.

≪Commercial product≫
The following commercial products etc. can be mentioned as a commercial item of transparent resin. Examples of commercially available cyclic olefin-based resins include Arton manufactured by JSR Corporation, ZEONOR manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available polyethersulfone resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. As a commercial item of acrylic resin, there can be cited NIPPON CATALYST ACRYVIEWER Co., Ltd. Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other ingredients>
The substrate may further contain additives such as an antioxidant, a near-ultraviolet absorber, a dye that absorbs near-infrared light, a fluorescence quencher, and a metal complex compound, as long as the effects of the present invention are not impaired. Good. Moreover, when manufacturing a board | substrate by cast molding mentioned later, manufacture of a board | substrate can be made easy by adding a leveling agent and an antifoamer. These other components may be used alone or in combination of two or more.

Examples of the near ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, and triazine compounds.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, and And tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane.

  Examples of the dye that absorbs near infrared rays include dithiol dyes, diimonium dyes, porphyrin dyes, and croconium dyes. The structures of these dyes are not particularly limited, and generally known ones can be used as long as the effects of the present invention are not impaired.

  These additives may be mixed together with a resin or the like when manufacturing a substrate, or may be added when manufacturing a resin. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin. Part.

<Substrate manufacturing method>
The substrate can be formed by, for example, melt molding or cast molding, and if necessary, can be manufactured by a method of coating a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. it can.

≪Melt molding≫
The substrate is formed by melt-molding a pellet obtained by melt-kneading a resin and a near-infrared absorbing dye; by melt-molding a resin composition containing the resin and the near-infrared absorbing dye; It can be produced by a method of melt-molding pellets obtained by removing the solvent from the resin composition containing the absorbing dye, the resin and the solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
The substrate is formed by casting a resin composition containing a near-infrared absorbing dye, a resin and a solvent on an appropriate base material to remove the solvent; coating with an antireflection agent, a hard coat agent and / or an antistatic agent, etc. A method of casting a resin composition comprising an agent, a near-infrared absorbing dye, and a resin on a suitable substrate; or a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent; It can also be produced by a method in which a curable composition containing an infrared-absorbing dye and a resin is cast on a suitable substrate and cured and dried.

Examples of the substrate include a glass plate, a steel belt, a steel drum, and a transparent resin (for example, a polyester film and a cyclic olefin resin film).
The substrate can be obtained by peeling from the base material, and unless the effect of the present invention is impaired, the laminate of the base material and the coating film (transparent resin layer) without being peeled from the base material. It may be a substrate.

  Further, the optical component such as glass plate, quartz or transparent plastic is coated with the resin composition and the solvent is dried, or the curable composition is coated and cured and dried. A transparent resin layer can also be formed directly on the part.

  The amount of residual solvent in the substrate obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less with respect to the weight of the substrate. When the amount of the residual solvent is within the above range, a substrate that can easily perform a desired function is obtained, in which deformation and characteristics are hardly changed.

[Near-infrared reflective film]
The near-infrared reflective film constituting the optical filter of the present invention is a film having the ability to reflect near-infrared light. In the present invention, the near-infrared reflective film may be provided on one side of the substrate or on both sides. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, an optical filter having high strength and less warpage can be obtained. When the optical filter is applied to a solid-state imaging device, it is preferable to provide a near infrared reflecting film on both sides of the substrate because it is preferable that the optical filter has a smaller warp.

  Examples of the near-infrared reflective film include an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles mainly containing indium oxide and containing a small amount of tin oxide are dispersed, a high refractive index material layer, and a low refractive index material. A dielectric multilayer film in which layers are alternately stacked can be mentioned. Among the near-infrared reflective films, a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated is more preferable.

  As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide, and the like, and titanium oxide, tin oxide. And / or a material containing a small amount of cerium oxide or the like (for example, 0 to 10% by weight based on the main component).

  As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of usually 1.2 to 1.6 is selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium.

  The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a dielectric multilayer in which high-refractive index material layers and low-refractive index material layers are alternately stacked on a substrate directly by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A film can be formed.

  The thicknesses of the high-refractive index material layer and the low-refractive index material layer are usually preferably 0.1λ to 0.5λ, where λ (nm) is the near infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the optical film thickness, the high refractive index material layer, and the low refractive index, where the product (n × d) of the refractive index (n) and the film thickness (d) is calculated by λ / 4. The thickness of each layer of the material layer becomes almost the same value, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection / refraction.

  The total number of laminated high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 5 to 60 layers, more preferably 10 to 50 layers, as a whole.

  Furthermore, when the substrate is warped when the dielectric multilayer film is formed, the dielectric multilayer film is formed on both surfaces of the substrate or the substrate dielectric multilayer film is formed in order to solve this problem. A method of irradiating the surface with electromagnetic waves such as ultraviolet rays can be used. In addition, when irradiating electromagnetic waves, you may irradiate during formation of a dielectric multilayer, and you may irradiate separately after formation.

[Other functional membranes]
As long as the optical filter of the present invention does not impair the effects of the present invention, between the substrate and the near-infrared reflective film such as a dielectric multilayer film, the surface of the substrate opposite to the surface provided with the near-infrared reflective film, Alternatively, on the surface opposite to the surface on which the substrate of the near-infrared reflective film is provided, the anti-reflective film is used for the purpose of improving the surface hardness of the substrate or the near-infrared reflective film, improving the chemical resistance, antistatic and scratching. Functional films such as a hard coat film and an antistatic film can be provided as appropriate.

  The optical filter of the present invention may include one layer composed of the functional film, or may include two or more layers. When the optical filter of the present invention includes two or more layers made of the functional film, it may include two or more similar layers or two or more different layers.

  The method of laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded on the resin substrate or near-infrared reflective film in the same manner as described above. Or the method of cast molding etc. can be mentioned.

  Moreover, it can also manufacture by applying the curable composition containing the said coating agent etc. on a board | substrate or an infrared reflective film with a bar coater etc., and hardening | curing by ultraviolet irradiation etc. after that.

  Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxy And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.

  Moreover, the said curable composition may contain the polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, when the total amount of the curable composition is 100% by weight. More preferably, it is 1 to 5% by weight. When the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflective film, a hard coat film or an antistatic film having excellent curing characteristics and handleability of the curable composition and having a desired hardness. it can.

  Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The thickness of the functional film is preferably 0.1 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 0.7 μm to 5 μm.
In addition, for the purpose of improving the adhesion between the substrate and the functional film and / or the near-infrared reflective film, and the adhesion between the functional film and the near-infrared reflective film, the surface of the substrate or the functional film is subjected to a surface such as corona treatment or plasma treatment. Processing may be performed.

[Characteristics etc. of optical filter]
The optical filter of the present invention has the substrate. For this reason, the optical filter of the present invention has excellent transmittance characteristics and is not restricted when used. In addition, the compound (A) contained in the substrate has an absorption maximum at a wavelength of 700 to 1000 nm, so that it can efficiently absorb near-infrared light. Can be obtained.

  When the optical filter is used for a solid-state imaging device, it is preferable that the visible light transmittance is higher. In particular, in recent years, there has been a strong demand for higher image quality in camera modules, and in order to improve imaging sensitivity and color reproducibility, it is necessary to increase the transmittance on the short wavelength side of wavelengths 430 to 460 nm. Specifically, the average transmittance at a wavelength of 430 to 460 nm is preferably 81% or more, more preferably 83% or more, and particularly preferably 85% or more. Similarly, the average transmittance at wavelengths of 461 to 580 nm is preferably higher, preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more. When the average transmittance is within this range in each wavelength region, excellent imaging sensitivity and color reproducibility can be achieved when used as a solid-state imaging device.

  When the optical filter is used for a solid-state imaging device, it is preferable that the transmittance in the near infrared wavelength region is low. In particular, it is known that the light receiving sensitivity of the solid-state imaging device is relatively high in the wavelength region of 800 to 1000 nm. By reducing the transmittance in this wavelength region, it is effective to correct the visibility of the camera image and the human eye. And excellent color reproducibility can be achieved. The average transmittance at a wavelength of 800 to 1000 nm is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less. When the average transmittance at a wavelength of 800 to 1000 nm is in this range, it is preferable because near infrared rays can be sufficiently cut and excellent color reproducibility can be achieved.

[Application of optical filter]
The optical filter of the present invention has a wide viewing angle and has excellent near-infrared cutting ability and the like. Therefore, it is useful for correcting the visibility of a solid-state image sensor such as a CCD or CMOS image sensor of a camera module. In particular, digital still cameras, mobile phone cameras, digital video cameras, personal computer cameras, surveillance cameras, automotive cameras, TVs, in-vehicle devices for car navigation systems, personal digital assistants, video game machines, portable game machines, fingerprint authentication Useful for system devices, digital music players, etc. Furthermore, it is also useful as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

[Solid-state imaging device]
The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device is an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor, and specifically used for applications such as a digital still camera, a mobile phone camera, and a digital video camera. it can. For example, the camera module of the present invention includes the optical filter of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. “Parts” means “parts by weight” unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of the physical property are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.
(B) Standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Corporation.

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.

<Spectral transmittance>
The absorption maximum and the transmittance in each wavelength region were measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

<Light resistance evaluation of cyanine compounds>
The substrate was exposed to an indoor fluorescent lamp for 500 hours, and the light resistance (environmental light resistance) of the near-infrared absorbing dye contained in the resin was evaluated. The light fastness is the wavelength before and after the fluorescent lamp exposure at the wavelength with the highest absorption intensity of the substrate (hereinafter referred to as “λa”. When the substrate has a plurality of absorption maxima, λa is the wavelength with the highest absorption intensity among them). The dye residual ratio (%) was calculated from the change in absorbance and evaluated. The residual ratio of the dye after exposure with a fluorescent lamp for 500 hours is preferably 90% or more, more preferably 95% or more.

[Synthesis example]
<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodec-3-ene (hereinafter also referred to as “DNM”) 100 parts, 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were substituted with nitrogen. The vessel was charged and the solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”). The obtained resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Cyanine compound synthesis example 1>
(1) The reaction scheme of the first stage in this synthesis example is shown below.

  Compound a (2.9 mmol) and compound b (5.8 mmol) shown in the above reaction scheme were added to nitrogen-substituted dimethylformamide (DMF), and the mixture was reacted at 120 ° C. for 3 hours. The product was extracted with diethyl ether and purified with a silica gel column to obtain compound c. The yield of compound c was 51%. Moreover, the result of NMR measurement is shown below.

¹ H NMR (DMSO-d ₆ ) d 1.33 (t, J = 7.0 Hz, 6H), 1.87 (brs, 2H), 1.91 (s, 12H), 2.73 (t, J = 5.9 Hz, 4H), 4.36 ( q, J = 7.0 Hz, 4H), 6.32 (d, J = 14.3 Hz, 2H), 7.49 (t, J = 7.7 Hz, 2H), 7.63 (t, J = 7.6 Hz, 2H), 7.76 (d, J = 9.0 Hz, 2H), 8.03 (d, J = 8.1 Hz, 2H), 8.06 (d, J = 9.0 Hz, 2H), 8.25 (d, 8.5 Hz 2H), 8.32 (d, J = 14.3 Hz) .

  (2) Next, the reaction scheme of the second stage in this synthesis example is shown below.

  The obtained compound c (1 mmol) was dissolved in acetonitrile substituted with nitrogen, ethylamine (4 mmol) and diisopropylethylamine (2 mmol) were added, and the mixture was heated to reflux for 1 hour. The reaction solution was added to diethyl ether (200 ml), and the precipitated solid was collected by suction filtration and purified by silica gel column chromatography (dichloromethane: methanol = 20: 1). The obtained compound was dissolved in dichloromethane substituted with nitrogen, and trifluoroacetic anhydride (0.7 mmol) and diisopropylethylamine (3 mmol) were added and reacted at 0 ° C. Thereafter, the reaction solution was added to diethyl ether (100 ml), and the precipitated solid was collected by suction filtration and purified by silica gel column chromatography (dichloromethane: methanol = 30: 1). The yield of the obtained compound d was 53%.

  (3) Next, the reaction scheme of the third step in this synthesis example is shown below.

The obtained compound d was dissolved in acetone, the corresponding metal boron salt was added, and salt exchange was performed at room temperature to obtain compound e (hereinafter also referred to as “cyanine compound 1”). The yield of compound e was 60%. Moreover, the result of NMR measurement is shown below.
¹ H NMR (CDCl ₃ ) d 1.47 (m, 9H), 1.90 (s, 6H), 1.96 (s, 6H), 2.64 (m, 4H), 3.95 (q, J = 7.2 Hz, 2H), 4.16 ( q, J = 7.0 Hz, 4H), 6.15 (d, J = 13.8 Hz, 2H), 7.35 (d, J = 7.4 Hz, 2H), 7.50 (t, J = 7.6 Hz, 2H), 7.63 (t, J = 7.6 Hz, 2H), 7.70 (d, J = 13.8 Hz, 2H), 7.96 (d, J = 8.7 Hz, 4H), 8.10 (d, J = 8.7 Hz, 2H).

<Cyanine compound synthesis example 2>
Cyanine compound 2 represented by the following formula was obtained in the same manner as in cyanine compound synthesis example 1 except that ethylamine was changed to monofluoroethylamine hydrochloride in the second stage of cyanine compound synthesis example 1.

<Cyanine Compound Synthesis Example 3>
Cyanine compound 3 represented by the following formula was obtained in the same manner as in cyanine compound synthesis example 1 except that trifluoroacetic anhydride was changed to acetyl chloride in the second stage of cyanine compound synthesis example 1.

<Cyanine Compound Synthesis Example 4>
A cyanine compound 4 represented by the following formula was obtained in the same manner as in the cyanine compound synthesis example 1 except that the compound a was changed to the following compound f in the first stage of the cyanine compound synthesis example 1.

<Cyanine compound synthesis example 5>
Cyanine compound 5 represented by the following formula was obtained in the same manner as in cyanine compound synthesis example 4 except that ethylamine was changed to monofluoroethylamine hydrochloride in the second stage of cyanine compound synthesis example 4.

[Example 1]
Resin A (100 parts by weight) obtained in Resin Synthesis Example 1, Cyanine Compound 1 (0.08 parts by weight) obtained in Cyanine Compound Synthesis Example 1, and methylene chloride were added to the container, and the resin concentration was 20 weights. % Solution was obtained. Next, the obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours to form a coating film, and then the coating film was peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. The spectral transmittance of this substrate was measured to obtain λa of the resin substrate, which was 843 nm. Further, when the light resistance of this substrate was evaluated, the dye residual ratio was 96.0%. The results are shown in Table 1.

[Example 2] and [Reference Example 1]
In Example 1, an optical filter having a thickness of 0.1 mm was produced in the same manner as in Example 1 except that the cyanine compound shown in Table 1 was used instead of cyanine compound 1. The evaluation results are shown in Table 1.

  The optical filter of the present invention is a digital still camera, a mobile phone camera, a digital video camera, a personal computer camera, a surveillance camera, an automobile camera, a television, an in-vehicle device for a car navigation system, a portable information terminal, a video game machine, a mobile phone. It can be suitably used for game machines, fingerprint authentication system devices, digital music players, and the like. Furthermore, it can be suitably used as a heat ray cut filter or the like attached to glass or the like of automobiles and buildings.

Claims (9)

A cyanine compound, which is a counterion conjugate comprising an anion and a cation, wherein the cation is represented by any one of the following general formulas (I-1) to (I-6).

[In the formulas (I-1) to (I-6),
m and n each represent an integer of 0 to 5, and a plurality of Ds independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom,
A plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i , and R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl ^{group, -L 1, -S-L 2} , -SS-L 2, -SO 2 -L 3, -N = N -L ⁴ or at least of R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , R _h and R _i, and R ₁ and R ₂ Represents at least one group selected from the group consisting of groups represented by the following formulas (A) to (H) to which one combination is bonded;
The amino group, amide group, imide group and silyl group are an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, And may have at least one substituent L selected from the group consisting of an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms,
L ¹ represents any of the following L ^a ~L ^e,
L ² represents either a hydrogen atom or the following L ^a ~L ^e,
L ³ represents either a hydroxyl group or the following L ^a ~L ^e,
L ⁴ are, represents one of the following L ^a ~L ^e,
(L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms that may have the substituent L (L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms that may have the substituent L ( L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have the substituent L (L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have the substituent L (L ^e ) A C 3-14 heterocyclic group that may have the substituent L Q ₁ represents the following general formula (q1), and Q ₂ represents any of the following general formulas (q2) to (q4). Represents the structure represented by ]

[In the formulas (A) to (H), the combination of R _x and R _y is R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h , A combination of R _h and R _i and R ₁ and R ₂ ;
Plural R _{A to} R _L are each independently a hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -SL ^{2. _{, -SS-L 2, -SO 2}} -L 3 or ^{-N = N-L 4 (L} 1 ~L 4 , the formula (I-1) ~ (L 1 ~L 4 defined in I-4) The amino group, amide group, imide group and silyl group may have the substituent L. ]
-C (= O) C _a X _{2a + 1} (q1)
-C _b Y _{2b + 1} (q2)
_{-C c Y 2c -OC d Y 2d} + 1 (q3)

[In Formula (q1), a represents an integer of 1 to 5, X represents a hydrogen atom or a halogen atom, and a plurality of Xs may be the same or different.
In formulas (q2) and (q3), b to d each represent an integer of 1 to 5, Y represents a hydrogen atom or a halogen atom, and a plurality of Y may be the same or different.
In formula (q4), p represents an integer of _{1 to 5} , and T _{1 to} T ₅ are each independently a hydrogen atom, a halogen atom, —OCZ ₃ or —OC _e Z _2e CZ ₃ (e is 1 to 5). Represents an integer, Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be the same or different.
However, at least one of X, Y and Z is a halogen atom. ] The cyanine compound according to claim 1, wherein the anion is represented by the following general formula (II).

[In Formula (II), Y _{1 to} Y ₂₀ are all fluorine atoms, or Y ₂ , Y ₄ , Y ₇ , Y ₉ , Y ₁₂ , Y ₁₄ , Y ₁₇ , Y ₁₉ are trifluoromethyl groups. And the remaining Y is a hydrogen atom. ]   An optical filter comprising a substrate including a transparent resin layer containing the cyanine compound according to claim 1 and a near-infrared reflective film formed on at least one surface of the substrate.   The transparent resin constituting the transparent resin layer is a cyclic olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin The optical filter according to claim 3, wherein the optical filter is at least one resin selected from the group consisting of a curable resin and a silsesquioxane-based ultraviolet curable resin.   The optical filter according to claim 3 or 4, wherein the near-infrared reflective film is formed on both surfaces of the substrate.   The optical filter according to any one of claims 3 to 5, which is used for a solid-state imaging device.   A solid-state imaging device comprising the optical filter according to claim 3.   A camera module comprising the optical filter according to claim 3.   The cyanine compound according to claim 1, a cyclic olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, and a polyarylate resin , Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester A resin composition containing at least one resin selected from the group consisting of a system curable resin and a silsesquioxane ultraviolet curable resin.