JP2015040895A - Optical filter, and apparatus using optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical filter which improves defects that an optical filter such as a conventional near-infrared cut filter has, and is excellent in transmittance characteristics and light resistance, and an apparatus using the optical filter.SOLUTION: An optical filter has a transparent resin substrate containing a compound (A) which includes anion and cyanine-based cation and is represented by the formula (I), and a near-infrared ray reflecting film formed on at least one surface of the substrate.

Description

  The present invention relates to an optical filter and an apparatus using the optical filter. Specifically, the present invention relates to an optical filter containing a specific solvent-soluble dye compound, and a solid-state imaging device and a camera module 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 provide an optical filter excellent in transmittance characteristics and light resistance, and an apparatus using the optical filter, by improving the drawbacks of conventional optical filters such as a near infrared cut filter. .

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an optical filter excellent in transmittance characteristics and light resistance can be obtained by applying a cyanine compound having an anion having a specific structure. The headline and the present invention were completed. Examples of embodiments of the present invention are shown below.

  [1] A transparent resin substrate containing a compound (A) comprising an anion represented by the following formula (I) and a cyanine cation, and a near-infrared reflective film formed on at least one surface of the substrate An optical filter comprising:

式（Ｉ）中、Ｍ_Iは遷移金属を表し、ｎ_Iは１〜２の整数を表し、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃およびＲ₀₄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、−ＳＯ₂−Ｌ¹、−Ｎ（Ｌ¹）₂または−ＳＯ₂−Ｎ（Ｌ¹）₂を表し、
Ｌ¹は
（Ｌ^a）置換基Ｌを有してもよい炭素数１〜９の脂肪族炭化水素基、
（Ｌ^b）置換基Ｌを有してもよい炭素数１〜９のハロゲン置換アルキル基、
（Ｌ^c）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）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）置換基Ｌを有してもよい炭素数３〜１４の複素環基、
（Ｌ^f）置換基Ｌを有してもよい炭素数１〜９のアルコキシ基、
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜９のアシル基、または
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜９のアルコキシカルボニル基
を表し、置換基Ｌは、炭素数１〜９の脂肪族炭化水素基、炭素数１〜９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種であり、前記Ｌ^a〜Ｌ^hは、さらにハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基およびアミノ基からなる群より選ばれる少なくとも１種の原子もしくは基を有していてもよい。

In formula (I), M _I represents a transition metal, n _I represents an integer of 1 to 2, and R ₀₁ , R ₀₂ , R ₀₃ and R ₀₄ are each independently a hydrogen atom, a halogen atom, a sulfo group, It represents a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid ^{_{group, -L 1, -SO 2 -L 1}} , a -N (L ¹⁾ ₂ or ^{_{-SO 2 -N (L 1) 2}} ,
L ¹ is an aliphatic hydrocarbon group having 1 to 9 carbon atoms that may have ^a (L ^a ) substituent L;
(L ^b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms that may have a substituent L;
(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L,
(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms that may have a substituent L,
(L ^e ) an optionally substituted heterocyclic group having 3 to 14 carbon atoms,
(L ^f ) an alkoxy group having 1 to 9 carbon atoms that may have a substituent L,
(L ^g ) represents a C 1-9 acyl group which may have a substituent L, or (L ^h ) represents a C 1-9 alkoxycarbonyl group which may have a substituent L. L is an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. And at least one selected from the group consisting of heterocyclic groups having 3 to 14 carbon atoms, wherein the L ^{a to} L ^h are a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, and phosphoric acid. It may have at least one atom or group selected from the group consisting of a group and an amino group.

[2] The optical filter according to item [1], wherein the compound (A) has an absorption maximum in a wavelength region of 600 nm to 1000 nm.
[3] The optical filter according to item [1] or [2], wherein M _I in the formula (I) is Cu, Co, Ni, Fe, Pd, or Pt.

  [4] The optical according to any one of items [1] to [3], wherein the cyanine cation is represented by any of the following formulas (II-1) to (II-3): filter.

式（ＩＩ−１）〜（ＩＩ−３）中、
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およびＲ_hとＲ_i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、請求項１に記載の式（Ｉ）において定義した置換基Ｌを有してもよく、
Ｌ¹は、前記式（Ｉ）において定義したＬ¹と同義であり、
Ｌ²は、水素原子または前記式（Ｉ）において定義したＬ^a〜Ｌ^eのいずれかを表し、
Ｌ³は、水素原子または前記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ⁴は、前記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｚ_a〜Ｚ_cおよびＹ_a〜Ｙ_d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（Ｌ¹〜Ｌ⁴は、前記Ｒ_a〜Ｒ_iにおけるＬ¹〜Ｌ⁴と同義である。）、あるいは、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含んでもよい５乃至６員環の脂環式炭化水素基、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、炭素数６〜１４の芳香族炭化水素基、または、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成され、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含む、炭素数３〜１４の複素芳香族炭化水素基を表し、これらの脂環式炭化水素基、芳香族炭化水素基および複素芳香族炭化水素基は、炭素数１〜９の脂肪族炭化水素基またはハロゲン原子を有してもよい。

In formulas (II-1) to (II-3),
A plurality of D 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 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, Amide group, imide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , or 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, and R _h and R _i are combined in the following formulas (A) to (H): Represents at least one group selected from the group consisting of the groups represented;
The amino group, amide group, imide group and silyl group may have a substituent L defined in formula (I) according to claim 1,
L ¹ has the same meaning as L ¹ defined in Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydrogen atom or the L ^a ~L ^e,
L ⁴ are, represents any of the L ^a ~L ^e,
Z _{a to} Z _c and Y _{a to} Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy 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 (L 1 ~L 4 has the same meaning as L ¹ ~L ⁴ in the R _a to R _i. ) Or
A 5- or 6-membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding Z or Y selected from two adjacent to each other;
An aromatic hydrocarbon group having 6 to 14 carbon atoms, formed by bonding Z or Y selected from two adjacent to each other; or
Z or Y selected from two adjacent ones are bonded to each other, and represent a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, These alicyclic hydrocarbon group, aromatic hydrocarbon group and heteroaromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

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およびＲ_hとＲ_i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（ＩＩ−１）〜（ＩＩ−３）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), 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 and R It is a combination of _h and R _i,
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 (II-1) ~ (L 1 ~L 4 as defined in II-3) The amino group, amide group, imide group and silyl group may have the substituent L.

  [5] The transparent resin constituting the substrate made of transparent resin is a cyclic olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, poly Allylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin Item 5. The optical filter according to any one of Items [1] to [4], which is at least one resin selected from the group consisting of allyl ester curable resins and silsesquioxane ultraviolet curable resins.

  [6] The transparent resin substrate is at least one selected from the group consisting of squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, dithiol compounds, diimonium compounds, and porphyrin compounds. Item 6. The optical filter according to any one of Items [1] to [5], further containing a species of near-infrared absorbing dye (X).

[7] The optical filter according to any one of items [1] to [6], wherein the near-infrared reflective film is formed on both surfaces of the substrate.
[8] The optical filter according to any one of items [1] to [7], which is for a solid-state imaging device.

[9] A solid-state imaging device comprising the optical filter according to any one of items [1] to [7].
[10] A camera module comprising the optical filter according to any one of items [1] to [7].

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

FIG. 1A is a schematic diagram showing a method for measuring the transmittance when measured from the vertical direction of the optical filter. FIG. 1B is a schematic diagram illustrating a method of measuring the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter.

Hereinafter, the present invention will be specifically described.
The optical filter according to the present invention includes a transparent resin substrate containing a counterion conjugate (compound (A)) composed of a metal dithiolate complex anion having a specific structure and a cyanine cation, and at least one surface of the substrate. And a near-infrared reflective film formed on the surface.

[Transparent resin substrate]
The transparent resin substrate (hereinafter also referred to as “resin substrate”) constituting the optical filter of the present invention may be a single layer or a multilayer (in the case of a multilayer, for example, a cured resin on a base resin substrate). A structure in which an overcoat layer or the like is laminated), which contains at least one compound (A) as a near-infrared absorbing dye, and has an absorption maximum of 600 to 1000 nm, more preferably 600 to 800 nm. It is desirable to be in range. If the absorption maximum wavelength of the substrate is within such a range, the substrate can selectively and efficiently cut near infrared rays.

  When such a resin substrate is used for an optical filter such as a near-infrared cut filter, the wavelength value at which the transmittance is 50% when measured from the vertical direction of the optical filter in the wavelength range of 560 to 800 nm. The absolute value of the difference between (Xa) and the wavelength value (Xb) at which the transmittance is 50% when measured from an angle of 30 ° with respect to the vertical direction of the optical filter is reduced, and the incident angle of the absorption wavelength An optical filter having a small dependency and a wide viewing angle can be obtained. The absolute value of the difference between (Xa) and (Xb) is preferably less than 20 nm, more preferably less than 15 nm, and particularly preferably less than 10 nm.

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

  The thickness of the resin substrate can be appropriately selected according to the 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, and more preferably. Is 30 to 250 μm, more preferably 40 to 200 μm, and particularly preferably 50 to 150 μm.

  When the thickness of the resin 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 resinous substrate is used in a lens unit such as a camera module, it is preferable because a low-profile lens unit can be realized.

  In addition to the compound (A), the resin substrate further comprises a squarylium compound, a phthalocyanine compound, a cyanine compound, a naphthalocyanine compound, a croconium compound, a dithiol compound, a diimonium compound, and a porphyrin compound. It may contain at least one kind of near-infrared absorbing dye (X) selected from the above. By using such a resin substrate, the incident angle dependency in the visible wavelength region to the near infrared wavelength region can be further reduced, and an optical filter having a wide viewing angle 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, both the compound (A) and the near-infrared absorbing dye (X) can be included in the same resin substrate, 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 resin-made board | substrates 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).

<Compound (A)>
The compound (A) is a counter ion conjugate composed of an anion represented by the following formula (I) (hereinafter also referred to as “anion (I)”) and a cyanine cation.

  ≪Anion (I) ≫

式（Ｉ）中、Ｍ_Iは遷移金属を表し、ｎ_Iは１〜２の整数を表し、Ｒ₀₁、Ｒ₀₂、Ｒ₀₃およびＲ₀₄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、−ＳＯ₂−Ｌ¹、−Ｎ（Ｌ¹）₂または−ＳＯ₂−Ｎ（Ｌ¹）₂を表し、
Ｌ¹は、
（Ｌ^a）置換基Ｌを有してもよい炭素数１〜９の脂肪族炭化水素基、
（Ｌ^b）置換基Ｌを有してもよい炭素数１〜９のハロゲン置換アルキル基、
（Ｌ^c）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）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）置換基Ｌを有してもよい炭素数３〜１４の複素環基、
（Ｌ^f）置換基Ｌを有してもよい炭素数１〜９のアルコキシ基、
（Ｌ^g）置換基Ｌを有してもよい炭素数１〜９のアシル基、または
（Ｌ^h）置換基Ｌを有してもよい炭素数１〜９のアルコキシカルボニル基
を表し、置換基Ｌは、炭素数１〜９の脂肪族炭化水素基、炭素数１〜９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種であり、前記Ｌ^a〜Ｌ^hは、さらにハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基およびアミノ基からなる群より選ばれる少なくとも１種の原子もしくは基を有していてもよい。

In formula (I), M _I represents a transition metal, n _I represents an integer of 1 to 2, and R ₀₁ , R ₀₂ , R ₀₃ and R ₀₄ are each independently a hydrogen atom, a halogen atom, a sulfo group, It represents a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid ^{_{group, -L 1, -SO 2 -L 1}} , a -N (L ¹⁾ ₂ or ^{_{-SO 2 -N (L 1) 2}} ,
L ¹ is
(L ^a ) an aliphatic hydrocarbon group having 1 to 9 carbon atoms that may have a substituent L,
(L ^b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms that may have a substituent L;
(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L,
(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms that may have a substituent L,
(L ^e ) an optionally substituted heterocyclic group having 3 to 14 carbon atoms,
(L ^f ) an alkoxy group having 1 to 9 carbon atoms that may have a substituent L,
(L ^g ) represents a C 1-9 acyl group which may have a substituent L, or (L ^h ) represents a C 1-9 alkoxycarbonyl group which may have a substituent L. L is an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. And at least one selected from the group consisting of heterocyclic groups having 3 to 14 carbon atoms, wherein the L ^{a to} L ^h are a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, and phosphoric acid. It may have at least one atom or group selected from the group consisting of a group and an amino group.

The total number of carbon atoms including L ^{a to} L ^h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. 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.

Examples of M _I include transition metals such as Cu, Co, Ni, Fe, Pd, Pt, Ti, V, Zn, Ru, Rh, and Zr. Among these, ions with cyanine cations are included. Cu, Co, Ni, Fe, Pd, and Pt are preferable, and Cu and Ni are particularly preferable because the combined body has excellent light resistance and visible transmittance.

The n _I is preferably 1.
The aliphatic hydrocarbon group having 1 to 9 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), alkyl groups such as pentyl group, hexyl group, octyl group and nonyl group; vinyl group Alkenyl groups such as 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 ethynyl group, Examples thereof include alkynyl groups such as propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group, and octynyl group.

Examples of the halogen-substituted alkyl group having 1 to 9 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.

Examples of the alkoxy group having 1 to 9 carbon atoms in L ^f include, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methoxyethoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group. Can be mentioned.

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

Examples of the alkoxycarbonyl group having 1 to 9 carbon atoms in L ^h include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-methoxyethoxycarbonyl group, and a pentyloxycarbonyl group. Hexyloxycarbonyl group and octyloxycarbonyl group.

As the L ^a, the aforementioned "aliphatic hydrocarbon group having 1 to 9 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, and tert-butyl group.

Examples of L ^b include the above-mentioned “halogen-substituted alkyl group having 1 to 9 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.

Examples of the L ^f include the above-mentioned “C 1 -C 9 alkoxy group” and those having the alkoxy group further having the substituent L, preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group. , Butoxy group, 2-methoxyethoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group, hexyloxy group, octyloxy group, more preferably methoxy group, An ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

Examples of L ^g include the above-mentioned “acyl group having 1 to 9 carbon atoms”, and those in which the acyl group further has the substituent L, preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, A benzoyl group and a 4-propylbenzoyl group, more preferably an acetyl group, a propionyl group, and a benzoyl group.

Examples of the L ^h include the above-mentioned “C1-C9 alkoxycarbonyl group” and those in which the alkoxycarbonyl group further has the substituent L, preferably a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl. Group, isopropoxycarbonyl group, butoxycarbonyl group, 2-trifluoromethylethoxycarbonyl group and 2-phenylethoxycarbonyl group, more preferably methoxycarbonyl group and ethoxycarbonyl group.

The L ^{a to} L ^h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, 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.

≪Cyanine cation≫
The cyanine cation is not particularly limited as long as it is a cation of a cyanine compound, but those represented by any one of the following formulas (II-1) to (II-3) are preferable.

式（ＩＩ−１）〜（ＩＩ−３）中、
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およびＲ_hとＲ_i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、請求項１に記載の式（Ｉ）において定義した置換基Ｌを有してもよく、
Ｌ¹は、前記式（Ｉ）において定義したＬ¹と同義であり、
Ｌ²は、水素原子または前記式（Ｉ）において定義したＬ^a〜Ｌ^eのいずれかを表し、
Ｌ³は、水素原子または前記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｌ⁴は、前記Ｌ^a〜Ｌ^eのいずれかを表し、
Ｚ_a〜Ｚ_cおよびＹ_a〜Ｙ_d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（Ｌ¹〜Ｌ⁴は、前記Ｒ_a〜Ｒ_iにおけるＬ¹〜Ｌ⁴と同義である。）、あるいは、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含んでもよい５乃至６員環の脂環式炭化水素基、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成される、炭素数６〜１４の芳香族炭化水素基、または、
隣接した二つから選ばれるＺ同士もしくはＹ同士が相互に結合して形成され、窒素原子、酸素原子もしくは硫黄原子を少なくとも１つ含む、炭素数３〜１４の複素芳香族炭化水素基を表し、これらの脂環式炭化水素基、芳香族炭化水素基および複素芳香族炭化水素基は、炭素数１〜９の脂肪族炭化水素基またはハロゲン原子を有してもよい。

In formulas (II-1) to (II-3),
A plurality of D 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 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, Amide group, imide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , or 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, and R _h and R _i are combined in the following formulas (A) to (H): Represents at least one group selected from the group consisting of the groups represented;
The amino group, amide group, imide group and silyl group may have a substituent L defined in formula (I) according to claim 1,
L ¹ has the same meaning as L ¹ defined in Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydrogen atom or the L ^a ~L ^e,
L ⁴ are, represents any of the L ^a ~L ^e,
Z _{a to} Z _c and Y _{a to} Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy 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 (L 1 ~L 4 has the same meaning as L ¹ ~L ⁴ in the R _a to R _i. ) Or
A 5- or 6-membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding Z or Y selected from two adjacent to each other;
An aromatic hydrocarbon group having 6 to 14 carbon atoms, formed by bonding Z or Y selected from two adjacent to each other; or
Z or Y selected from two adjacent ones are bonded to each other, and represent a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, These alicyclic hydrocarbon group, aromatic hydrocarbon group and heteroaromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

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およびＲ_hとＲ_i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）および（ＩＩ−１）〜（ＩＩ−３）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), 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 and R It is a combination of _h and R _i,
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 to} L ⁴ are L defined in the above formulas (I) and (II-1) to (II-3)) ^{1 to} L ^4. ), And the amino group, amide group, imide group and silyl group may have the substituent L.

A 5- to 6-membered ring which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding Z or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d Examples of the alicyclic hydrocarbon group include compounds exemplified by the alicyclic hydrocarbon group and the heterocyclic ring in the substituent L (excluding the heteroaromatic hydrocarbon group).

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y in Z _{a to} Z _c and Y _{a to} Y _d include, for example, the substituent L The compound illustrated by the aromatic hydrocarbon group is mentioned.

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d include, for example, the substituent L And the compounds exemplified as the heterocyclic group (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom).

In R _{a to} R _i and R _{A to} R _L , 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 _{A to} R _L , 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 _{A to} R _L , an 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 _{A to} R _L , 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 R _{a to} R _i and R _{A to} R _L , -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 _{A to} R _L , -SS-L ² includes disulfide group, methyl disulfide group, ethyl disulfide group, propyl disulfide group, butyl disulfide group, isobutyl disulfide group, 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 _{A to} R _L , 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 _{A to} R _L , examples of —N═N—L ⁴ include a methylazo group, a phenylazo group, a p-methylphenylazo group, and a p-dimethylaminophenylazo group.

  Specific examples of the compound (A) are not particularly limited as long as the conditions described in the above formula (1) are satisfied. For example, the anions described in Table 1 having a basic skeleton represented by the following formula (I-1) Examples include compounds formed from (a-1 to a-15) and cyanine cations (b-1 to b-19) described in Table 2 below. The combination is arbitrary.

化合物（Ａ）は、一般的に知られている方法で合成すればよく、例えば、特公平１−３４４６５号公報や特許第３５４０３２７号公報等に記載されている方法等を参照して合成することができる。

Compound (A) may be synthesized by a generally known method. For example, compound (A) may be synthesized by referring to the methods described in Japanese Patent Publication No. 1-334565 and Japanese Patent No. 3540327. Can do.

  In the resin substrate, the content of the compound (A) is preferably 0.01 to 5.0 parts by weight, more preferably 0.02 to 3. parts by weight with respect to 100 parts by weight of the transparent resin used during the production of the resin substrate. 5 parts by weight, particularly preferably 0.03 to 2.5 parts by weight. When the content of the compound (A) is within the above range, both good near infrared absorption characteristics and high visible light transmittance can be achieved.

<Near-infrared absorbing dye (X)>
The near-infrared absorbing dye (X) is at least one selected from the group consisting of squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, dithiol compounds, diimonium compounds, and porphyrin compounds. It is particularly preferred that it is a seed and contains a squarylium-based compound. The absorption maximum wavelength of the near-infrared absorbing dye (X) is preferably 600 nm or more, more preferably 620 nm or more, particularly preferably 650 nm or more, and preferably less than 800 nm, more preferably 760 nm or less, particularly preferably 740 nm or less. It is. When the absorption maximum wavelength is in such a wavelength range, particularly when the absorption maximum wavelength of the compound (A) is 800 nm to 1000 nm, sufficient incident angle dependency improvement performance and visible light transmittance can be achieved at the same time. it can.

  In the resin substrate, the content of the near-infrared absorbing dye (X) is preferably 0.01 to 5.0 parts by weight, more preferably 0.02 with respect to 100 parts by weight of the transparent resin used when the resin substrate is manufactured. -3.5 parts by weight, particularly preferably 0.03-2.5 parts by weight. When the content of the near-infrared absorbing dye is within the above range, both good near-infrared absorption characteristics and high visible light transmittance can be achieved.

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

式（ＩＶ−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 (IV-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 .
Wherein ^{L 1, L a, L b} , L c, L d, L e is, L ¹ defined in independent to the formula ^{(I), L a, L} b, L c, L d, and L ^e It is synonymous.

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（ＩＶ−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；Ｌ¹およびＬ^a〜Ｌ^eは前記式（Ｉ）にて定義したＬ¹およびＬ^a〜Ｌ^eと同義であり、Ｒ^eおよびＲ^fは、前記条件（ｉ）に記載のＲ^eおよびＲ^fと同義である。

In formula (IV-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 represents ¹ or -NR ^e R ^f group, R ^d adjacent may form a ring which may have a substituent linked; L ¹ and L ^a ~L ^e is the formula (I ) have the same meanings as the defined L ¹ and L ^a ~L ^e at, R ^e and R ^f have the same meanings as R ^e and R ^f according to the condition (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》
The phthalocyanine compound is preferably a compound represented by the following formula (V).

式（Ｖ）中、Ｍは、２個の水素原子、２個の１価の金属原子、２価の金属原子、または３価もしくは４価の金属原子を含む置換金属原子を表し、
複数あるＲ_a、Ｒ_b、Ｒ_cおよびＲ_d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_aとＲ_b、Ｒ_bとＲ_cおよびＲ_cとＲ_d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、同じ芳香環に結合したＲ_a、Ｒ_b、Ｒ_cおよびＲ_dのうち少なくとも１つが水素原子ではない。

In formula (V), M represents a substituted metal atom containing two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom,
A plurality of R _a , R _b , R _c and R _d 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 , -S-L ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , or R _a and R _b , R _b and R _c, and R _c and R _d R _a , R _b , R _c, and 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, bonded to the same aromatic ring, and At least one of R _d is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I), and L ^{1 to} L ⁴ represent the formulas (I) and (II-1). it is synonymous with L ¹ ~L ⁴ as defined in ~ (II-3).

式（Ａ）〜（Ｈ）中、Ｒ_xとＲ_yの組み合わせは、Ｒ_aとＲ_b、Ｒ_bとＲ_cまたはＲ_cとＲ_d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、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を有してもよく、Ｌ¹〜Ｌ⁴は前記式（Ｉ）および前記式（ＩＩ−１）〜（ＩＩ−３）において定義したＬ¹〜Ｌ⁴と同義である。

In formulas (A) to (H), the combination of R _x and R _{y is} a combination of R _a and R _b , R _b and R _c, or R _c and R _d ,
A plurality of R _{A to} R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl 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, represents the -N = N-L ^4,
The amino group, amide group, imide group and silyl group may have the substituent L, and L ^{1 to} L ⁴ represent the formula (I) and the formulas (II-1) to (II-3). it is synonymous with L ¹ ~L ⁴ defined in.

  The phthalocyanine compound may be synthesized by a generally known method. For example, a method described in Japanese Patent No. 4081149 or “phthalocyanine-chemistry and function” (IPC, 1997) is used. It can be synthesized by reference.

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

<Transparent resin>
The resin 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 resin substrate may further contain additives such as a near-ultraviolet absorber, an antioxidant, a fluorescence quencher, and a metal complex compound as long as the effects of the present invention are not impaired. Moreover, when manufacturing a resin-made board | substrate by cast shaping | molding mentioned later, manufacture of a resin-made 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.

  These additives may be mixed with a resin or the like when producing a resin substrate, or may be added when producing 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.

<Manufacturing method of resin substrate>
The resin substrate can be formed by, for example, melt molding or cast molding, and if necessary, is 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. be able to.

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

≪Cast molding≫
The resin substrate is a method of removing a solvent by casting a resin composition containing a near-infrared absorbing dye, a resin and a solvent on an appropriate base material; an antireflection agent, a hard coat agent and / or an antistatic agent, etc. A method of casting a resin composition comprising a coating 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 a near-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 resin 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 is not peeled from the base material. It is good.

  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 resin substrate can also be formed directly on the component.

  The amount of residual solvent in the resin 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 resin substrate. When the amount of residual solvent is in the above range, a resin substrate can be obtained in which the deformation and characteristics are hardly changed and a desired function can be easily exhibited.

[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 resin 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 that the optical filter has a smaller warp. Therefore, it is preferable to provide a near-infrared reflective film on both surfaces of the resin substrate.

  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 in which high-refractive index material layers and low-refractive index material layers are alternately laminated directly on a resin substrate by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A body multilayer 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 resin substrate is warped when the dielectric multilayer film is formed, in order to eliminate this, a dielectric multilayer film is formed on both surfaces of the resin substrate, or the dielectric of the resin substrate is formed. A method of irradiating an electromagnetic wave such as an ultraviolet ray on the surface on which the body multilayer film is formed can be employed. 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]
The optical filter of the present invention is within the range that does not impair the effects of the present invention, and between the resin substrate and the near-infrared reflective film such as a dielectric multilayer film, opposite to the surface of the resin substrate provided with the near-infrared reflective film. The surface of the resin substrate or near-infrared reflective film on the side opposite to the surface on which the resin substrate of the near-infrared reflective film is provided is improved in surface hardness, chemical resistance, antistatic and scratch-removing. For the purpose, a functional film such as an antireflection film, a hard coat film or an antistatic film can be appropriately provided.

  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 be produced by applying a curable composition containing the coating agent or the like on a resin substrate or an infrared reflective film with a bar coater or the like and then curing it by ultraviolet irradiation or the like.

  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 organic solvents 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 resin 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 resin substrate or the functional film is subjected to corona treatment or plasma. Surface treatment such as treatment may be performed.

[Characteristics etc. of optical filter]
The optical filter of the present invention has the resin substrate. For this reason, the optical filter of the present invention has excellent transmittance characteristics and is not restricted when used. Moreover, since the compound (A) contained in the resin substrate has an absorption maximum at a wavelength of 600 to 1000 nm, it can efficiently absorb near-infrared light. An optical filter with little angle dependency can be obtained.

[Use 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, PC cameras, surveillance cameras, automotive cameras, TVs, car navigation systems, personal digital assistants, personal computers, video games, portable game machines, fingerprint authentication systems, digital music players, etc. Useful for. 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. In the following description, “part” means “part 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.
In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
(C) A part of the polyimide resin solution was added to anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.
_{μ = {ln (t s /} t 0)} / C
t ₀ : Flowing time of solvent t _s : Flowing time of dilute polymer solution C: 0.5 g / dL

<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, the transmittance in each wavelength region, and (Xa) and (Xb) were measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

  Here, with respect to the transmittance when measured from the vertical direction of the optical filter, light transmitted perpendicularly to the filter was measured as shown in FIG. Further, with respect to the transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter, light transmitted at an angle of 30 ° with respect to the vertical direction of the filter was measured as shown in FIG.

  This transmittance is measured using the spectrophotometer under the condition that light is perpendicularly incident on the substrate and the filter, except when measuring (Xb). In the case of measuring (Xb), it is measured using the spectrophotometer under the condition that light is incident at an angle of 30 ° with respect to the vertical direction of the filter.

<Light resistance evaluation of near-infrared absorbing dye>
The resin 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 resistance is fluorescence at a wavelength with the highest absorption intensity of the resin substrate (hereinafter referred to as “λa”. When the resin substrate has a plurality of absorption maxima, λa is a wavelength with the highest absorption intensity among them). The pigment residual ratio (%) was calculated from the change in absorbance before and after exposure to the lamp and evaluated. The dye residual ratio after exposure with a fluorescent lamp for 500 hours is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.

[Synthesis example]
The compounds (A), squarylium compounds, phthalocyanine compounds, cyanine compounds, near ultraviolet absorbers, and other dyes used in the following examples can be synthesized by generally known methods, for example Japanese Patent Publication No. 01-34465, Japanese Patent No. 3540327, Japanese Patent No. 336697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP-A 2007-169315. JP, JP-A-2009-108267, JP-A 2010-24187 3 can be synthesized with reference to the methods described in Japanese Patent No. 3, Japanese Patent No. 3699464, Japanese Patent No. 4740631, and the like.

<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%.

このようにして得られた開環重合体溶液１，０００部をオートクレーブに仕込み、この開環重合体溶液に、ＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌して水素添加反応を行った。

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.

<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried overnight at 60 ° C. to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

<Resin synthesis example 3>
To a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean-Stark tube and a condenser tube, was added 1,4-bis (4-amino-α, α under a nitrogen stream. -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and γ-butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting solution was cooled to 5 ° C. using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst As a result, 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed. After completion of the reaction, the reaction mixture was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of N, N-dimethylacetamide, cooled with stirring, and 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. Got. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). The IR spectrum of the obtained resin C was measured, 1704 cm ^-1 characteristic of imido group, absorption of 1770 cm ^-1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C. and a logarithmic viscosity of 0.87.

<Resin synthesis example 4>
9.167 kg (20.90 mol) of 9,9-bis (4-2-2-hydroxyethoxy) phenyl) fluorene, 4.585 kg (20.08 mol) of bisphenol A, 9.000 kg (42.01 mol) of diphenyl carbonate, And 0.02066 kg (2.459 × 10 ⁻⁴ mol) of sodium hydrogen carbonate were put into a 50 L reactor equipped with a stirrer and a distillation apparatus, and heated and stirred at 215 ° C. over 1 hour under a nitrogen atmosphere at 760 Torr. did. Thereafter, the degree of vacuum was adjusted to 150 Torr over 15 minutes, and the mixture was held at 215 ° C. and 150 Torr for 20 minutes to conduct a transesterification reaction. Next, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./Hr, held at 240 ° C. and 150 Torr for 10 minutes, adjusted to 120 Torr over 10 minutes, held at 240 ° C. and 120 Torr for 70 minutes, Further, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 10 minutes. Thereafter, the polymerization reaction was carried out by stirring for 10 minutes under the conditions of 240 ° C. and 1 Torr or less at 40 ° C. over 1 Torr. After completion of the reaction, nitrogen was introduced into the reactor to be in a pressurized state, and the produced polycarbonate resin (hereinafter also referred to as “resin D”) was extracted while being pelletized. The obtained resin D had a weight average molecular weight of 41,000 and a glass transition temperature (Tg) of 152 ° C.

<Resin synthesis example 5>
To the reactor, 0.8 mol of 9,9-bis {4- (2-hydroxyethoxy) -3,5-dimethylphenyl} fluorene, 2.2 mol of ethylene glycol and 1.0 mol of dimethyl isophthalate were added and stirred. The mixture was gradually heated and melted to conduct a transesterification reaction. Next, 20 × 10 ⁻⁴ mol of germanium oxide was added, and ethylene glycol was removed while gradually increasing the temperature and reducing the pressure until reaching 290 ° C. and 1 Torr or less. Thereafter, the contents were taken out of the reactor to obtain pellets of polyester resin (hereinafter also referred to as “resin E”). The obtained resin E had a number average molecular weight of 40,000 and a glass transition temperature of 145 ° C.

<Resin synthesis example 6>
To a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer, 4,74′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (BPDE) 16.74 parts, 10.5 parts of 9-bis (4-hydroxyphenyl) fluorene (HF), 4.34 parts of potassium carbonate and 90 parts of DMAc were charged. The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was added into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated polyether ketone (hereinafter also referred to as “resin F”). The obtained resin F had a number average molecular weight of 71,000 and a glass transition temperature (Tg) of 242 ° C.

[Example 1]
To the container, 100 parts by weight of the resin A obtained in Resin Synthesis Example 1, 0.08 parts by weight of the compound (A) represented by the following formula (A-1), and methylene chloride are added to give a resin concentration of 20% by weight. Solution was obtained. Subsequently, the obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then 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 696 nm. Further, when the light resistance of this substrate was evaluated, the dye residual ratio was 96%. The results are shown in Table 3.

Subsequently, on one side of the obtained substrate, a multilayer deposition film [silica (SiO ₂ : film thickness 83 to 199 nm) layer and titania (TiO ₂ : film thickness 101 to 125 nm) layer reflecting near infrared rays at a deposition temperature of 100 ° C. And a multilayer deposited film [silica (SiO ₂ : film thickness 77˜) which reflects near infrared rays at a deposition temperature of 100 ° C. on the other surface of the substrate. 189 nm) layers and titania (TiO ₂ : film thickness 84 to 118 nm) layers were alternately stacked, and the number of layers 26] was formed to obtain an optical filter having a thickness of 0.105 mm. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated.

  The average value of transmittance at a wavelength of 430 to 580 nm was 90%, the average value of transmittance at a wavelength of 800 to 1000 nm was 1% or less, and the absolute value | Xa−Xb | was 5 nm. The results are shown in Table 3.

[Example 2] to [Example 15] and [Comparative Example 1] to [Comparative Example 3]
In Example 1, an optical filter having a thickness of 0.105 mm was produced in the same manner as in Example 1 except that the transparent resin, solvent, pigment, and film drying conditions shown in Table 3 were employed. The evaluation results are shown in Table 3. In Table 3, the number of added parts of the resin is 100 parts by weight, and the concentration of the resin solution is 20% by weight. The various compounds used in the examples and comparative examples are as follows.

<Transparent resin>
Resin A: Cyclic olefin resin (resin synthesis example 1)
Resin B: Aromatic polyether resin (resin synthesis example 2)
Resin C: Polyimide resin (resin synthesis example 3)
Resin D: Fluorene polycarbonate resin (resin synthesis example 4)
Resin E: Fluorene polyester resin (resin synthesis example 5)
Resin F: Fluorinated polyether ketone (resin synthesis example 6)
Resin G: Cyclic olefin resin “Zeonor 1420R” (manufactured by Nippon Zeon Co., Ltd.)
Resin H: Cyclic olefin resin “APEL # 6015” (manufactured by Mitsui Chemicals, Inc.)
Resin I: Polycarbonate resin “Pure Ace” (manufactured by Teijin Limited)
Resin J: Polyethersulfone resin “Sumilite FS-1300”
(Sumitomo Bakelite Co., Ltd.)
Resin K: Heat-resistant acrylic resin “ACRYPURE” (manufactured by Nippon Shokubai Co., Ltd.)

<Near-infrared absorbing dye>
<< Compound (A) >>
Compound (A-1): Compound represented by the following formula (A-1)

化合物（Ａ−２）：下記式（Ａ−２）で表される化合物

Compound (A-2): Compound represented by the following formula (A-2)

化合物（Ａ−３）：下記式（Ａ−３）で表される化合物

Compound (A-3): Compound represented by the following formula (A-3)

≪Near-infrared absorbing dye (X) ≫
Compound (X-1): A squarylium compound represented by the following formula (X-1)

化合物（Ｘ−２）：下記式（Ｘ−２）で表されるフタロシアニン系化合物

Compound (X-2): phthalocyanine compound represented by the following formula (X-2)

化合物（Ｘ−３）：下記式（Ｘ−３）で表されるシアニン系化合物

Compound (X-3): a cyanine compound represented by the following formula (X-3)

<Solvent>
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Ethyl acetate / toluene (weight ratio: 5/5)
Solvent (4): cyclohexane / xylene (weight ratio: 7/3)
Solvent (5): cyclohexane / methylene chloride (weight ratio: 99/1)
Solvent (6): N-methyl-2-pyrrolidone In Table 3, the film drying conditions of Examples and Comparative Examples are as follows. In addition, the coating film was peeled from the glass plate before drying under reduced pressure.

<Film drying conditions>
Condition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr
Condition (4): 40 ° C./4 hr → 60 ° C./4 hr → under reduced pressure 100 ° C./8 hr

  The optical filter of the present invention includes a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, an automobile camera, a TV, a car navigation system, a portable information terminal, a personal computer, a video game, a portable game machine, and a fingerprint authentication system. It can be suitably used for a digital music player or 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.

1: Optical filter 2: Spectrophotometer 3: Light

Claims (10)

It has a transparent resin substrate containing a compound (A) composed of an anion represented by the following formula (I) and a cyanine cation, and a near-infrared reflective film formed on at least one surface of the substrate. Features optical filter.

[In formula (I), M _I represents a transition metal, n _I represents an integer of 1 to 2, and R ₀₁ , R ₀₂ , R ₀₃ and R ₀₄ are each independently a hydrogen atom, a halogen atom, or a sulfo group. , A hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ , -SO ₂ -L ¹ , -N (L ¹ ) ₂ or -SO ₂ -N (L ¹ ) ₂ ;
L ¹ is an aliphatic hydrocarbon group having 1 to 9 carbon atoms that may have ^a (L ^a ) substituent L;
(L ^b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms that may have a substituent L;
(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L,
(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms that may have a substituent L,
(L ^e ) an optionally substituted heterocyclic group having 3 to 14 carbon atoms,
(L ^f ) an alkoxy group having 1 to 9 carbon atoms that may have a substituent L,
(L ^g ) represents a C 1-9 acyl group which may have a substituent L, or (L ^h ) represents a C 1-9 alkoxycarbonyl group which may have a substituent L. L is an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. And at least one selected from the group consisting of heterocyclic groups having 3 to 14 carbon atoms, wherein the L ^{a to} L ^h are a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, and phosphoric acid. It may have at least one atom or group selected from the group consisting of a group and an amino group. ]   The optical filter according to claim 1, wherein the compound (A) has an absorption maximum in a wavelength region of 600 nm to 1000 nm. 3. The optical filter according to claim 1, wherein M _I in the formula (I) is Cu, Co, Ni, Fe, Pd, or Pt. The optical filter according to any one of claims 1 to 3, wherein the cyanine cation is represented by any one of the following formulas (II-1) to (II-3).

[In the formulas (II-1) to (II-3),
A plurality of D 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 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, Amide group, imide group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , or 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, and R _h and R _i are combined in the following formulas (A) to (H): Represents at least one group selected from the group consisting of the groups represented;
The amino group, amide group, imide group and silyl group may have a substituent L defined in formula (I) according to claim 1,
L ¹ has the same meaning as L ¹ defined in Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydrogen atom or the L ^a ~L ^e,
L ⁴ are, represents any of the L ^a ~L ^e,
Z _{a to} Z _c and Y _{a to} Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy 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 (L 1 ~L 4 has the same meaning as L ¹ ~L ⁴ in the R _a to R _i. ) Or
A 5- or 6-membered alicyclic hydrocarbon group which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding Z or Y selected from two adjacent to each other;
An aromatic hydrocarbon group having 6 to 14 carbon atoms, formed by bonding Z or Y selected from two adjacent to each other; or
Z or Y selected from two adjacent ones are bonded to each other, and represent a heteroaromatic hydrocarbon group having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, These alicyclic hydrocarbon group, aromatic hydrocarbon group and heteroaromatic hydrocarbon group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom. ]

[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, and A combination of R _h and R _i ,
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 (II-1) ~ (L 1 ~L 4 as defined in II-3) The amino group, amide group, imide group and silyl group may have the substituent L. ]   The transparent resin constituting the transparent resin substrate 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 The optical filter according to any one of claims 1 to 4, which is at least one resin selected from the group consisting of a system curable resin and a silsesquioxane ultraviolet curable resin.   The transparent resin substrate is at least one kind selected from the group consisting of squarylium compounds, phthalocyanine compounds, cyanine compounds, naphthalocyanine compounds, croconium compounds, dithiol compounds, diimonium compounds and porphyrin compounds. The optical filter according to any one of claims 1 to 5, further comprising an infrared absorbing dye (X).   The optical filter according to claim 1, wherein the near-infrared reflective film is formed on both surfaces of the substrate.   The optical filter according to claim 1, which is for a solid-state imaging device.   A solid-state imaging device comprising the optical filter according to claim 1.   A camera module comprising the optical filter according to claim 1.

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