JP2015172102A - Novel cyanine compound, optical filter and device using optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide cyanine compounds that can improve defects of conventional optical filters such as near-infrared cut filters and provide optical filters having excellent heat resistance, and optical filters using the cyanine compounds and devices using the optical filters.SOLUTION: A cyanine compound according to the present invention is characterized in that an anion has a HOMO value of -3.4 eV or less. The anion is preferably represented by formula (1). An optical filter according to the present invention comprises a transparent resin substrate comprising the cyanine compound according to the present invention, and a near-infrared reflective film formed on at least one face of the substrate.

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 heat stability and may not achieve the heat resistance required for solid-state imaging device applications.

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

  An object of the present invention is to improve a defect that an optical filter such as a conventional near-infrared cut filter has, and to provide an optical filter having excellent heat resistance, an optical filter using the cyanine compound, and an optical filter using the cyanine compound 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 heat 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 counterion conjugate composed of an anion and a cation, and the anion has a HOMO value of −3.4 eV or less.
[2] The cyanine compound according to item [1], wherein the anion is represented by the following general formula (I).

式（Ｉ）中、Ｙ₁〜Ｙ₂₀は、それぞれ独立に水素原子、フッ素原子、トリフルオロメチル基もしくはシアノ基を示す。ただし、Ｙ₁〜Ｙ₅、Ｙ₆〜Ｙ₁₀、Ｙ₁₁〜Ｙ₁₅及びＹ₁₆〜Ｙ₂₀の各群における少なくとも１つのＹは、フッ素原子、トリフルオロメチル基もしくはシアノ基である。

In formula (I), Y _{1 to} Y ₂₀ each independently represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, or a cyano group. Provided that at least one Y in each group of _{Y 1 ~Y 5, Y 6 ~Y} 10, Y 11 ~Y 15 and Y ₁₆ to Y ₂₀ is a fluorine atom, a trifluoromethyl group or a cyano group.

  [3] The cyanine compound according to item [1] or [2], wherein the cation is represented by any one of the following general formulas (II-1) to (II-4).

式（ＩＩ−１）〜（ＩＩ−４）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、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
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-4),
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 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 ) The _C 3-14 heterocyclic group Z _{a to} Z _c and Y _{a to} Y _d which may have the substituent L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a 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 (L ^{1 to} L ⁴ have the same meanings as L ^{1 to} L ⁴ in 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−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), 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 defined in II-4) The amino group, amide group, imide group and silyl group may have the substituent L.

  [4] A transparent resin substrate containing the cyanine compound according to any one of items [1] to [3], and a near-infrared reflective film formed on at least one surface of the substrate. Optical filter characterized by.

  [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 4. The optical filter according to Item [4], which is at least one resin selected from the group consisting of allyl ester curable resins and silsesquioxane ultraviolet curable resins.

[6] The optical filter according to item [4] or [5], wherein the near-infrared reflective film is formed on both surfaces of the substrate.
[7] The optical filter according to any one of items [4] to [6], which is for a solid-state imaging device.

[8] A solid-state imaging device comprising the optical filter according to any one of items [4] to [7].
[9] A camera module comprising the optical filter according to any one of items [4] to [7].

  [10] The cyanine compound according to any one of items [1] to [3], a cyclic olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate. Resin, polyamide resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified ) A resin composition comprising at least one resin selected from the group consisting of acrylic resins, epoxy resins, allyl ester curable resins, and silsesquioxane ultraviolet curable resins.

  According to the present invention, an optical filter having excellent heat resistance can be provided.

Hereinafter, the present invention will be specifically described.
The optical filter according to the present invention includes a transparent resin substrate containing the cyanine compound of the present invention (hereinafter also referred to as “cyanine compound (A)” or “compound (A)”), and at least one of the substrates described later. 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). It may be a configuration in which an overcoat layer or the like 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 800 nm, more preferably 705 to 750 nm. The transmittance at the absorption maximum wavelength is preferably 10% or less, and more preferably 8% or less. When 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 on the surface of the transparent resin substrate. When the film is formed, it is possible to reduce the incident angle dependency of the optical characteristics in the vicinity of the visible wavelength to the near infrared wavelength region.

  Depending on the use such as a camera module, in a 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 includes 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. Can be contained. 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, the absorption band waveform can be further sharpened, and the optical field of view is wide. A filter 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).

[Cyanine compound (A)]
The cyanine compound (A) of the present invention is a counter ion conjugate comprising an anion and a cyanine cation (hereinafter also referred to as “cation (II)”), and the anion has a HOMO value of −3.4 eV or less. It is characterized by having. When the HOMO value of the anion is in the above range, the heat resistance of the cyanine compound can be improved. Examples of such an anion having a specific HOMO value include an anion represented by the following formula (I) (hereinafter also referred to as “anion (I)”).

  ≪Anion (I) ≫

式（Ｉ）中、Ｙ₁〜Ｙ₂₀は、それぞれ独立に水素原子、フッ素原子もしくはトリフルオロメチル基を示す。ただし、Ｙ₁〜Ｙ₅、Ｙ₆〜Ｙ₁₀、Ｙ₁₁〜Ｙ₁₅及びＹ₁₆〜Ｙ₂₀の各群における少なくとも１つのＹは、フッ素原子、トリフルオロメチル基もしくはシアノ基である。

In formula (I), Y _{1 to} Y ₂₀ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group. Provided that at least one Y in each group of _{Y 1 ~Y 5, Y 6 ~Y} 10, Y 11 ~Y 15 and Y ₁₆ to Y ₂₀ is a fluorine atom, a trifluoromethyl group or a cyano group.

≪Cation (II) ≫
The cation (II) is not particularly limited as long as it is a cyanine compound cation, but is represented by any of the following formulas (II-1) to (II-4) from the viewpoint of heat resistance and light resistance. Those are preferred.

式（ＩＩ−１）〜（ＩＩ−４）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、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
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-4),
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 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 ) The _C 3-14 heterocyclic group Z _{a to} Z _c and Y _{a to} Y _d which may have the substituent L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a 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 (L ^{1 to} L ⁴ have the same meanings as L ^{1 to} L ⁴ in 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−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), 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 defined in II-4) 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).

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 _{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.

<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 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 (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 independently in the formulas (II-1) to (II-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（ＩＩ−１）〜（ＩＩ−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 represents ¹ or -NR ^e R ^f group, adjacent R ^d together may form a ring which may have a substituent linked; L ^a ~L ^e, L ¹ is the formula (II -1) ~ (II-4) has the same meaning as that defined the 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 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 further contains 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. May be. 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.

  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 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 700 to 800 nm, it can efficiently absorb near-infrared light. By combining with the near-infrared reflective film, the incident angle can be reduced. An optical filter with less dependency 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.

[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. “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.

<Evaluation of heat resistance of cyanine compounds>
The resin substrate was exposed to a high temperature of 150 ° C., and the heat resistance of the cyanine compound contained in the resin was evaluated. The heat resistance is a high temperature at a wavelength at which the resin substrate has the highest absorption intensity (hereinafter referred to as “λa”. When the resin substrate has a plurality of absorption maxima, λa is the wavelength at which the absorption intensity is highest among them). The dye residual ratio (%) was calculated from the change in absorbance before and after the exposure and evaluated. The pigment remaining rate after exposure at 150 ° C. is preferably 95% or more, more preferably 99% or more.

<HOMO value of anion of cyanine compound>
The HOMO value is a numerical value obtained by the density inverse function method B3LYP / LANL2DZ (Gaussian 09) under the conditions assuming vacuum.

[Synthesis example]
The cyanine compounds other than the compound (A), squarylium compound, phthalocyanine compound and compound (A) used in the following examples can be synthesized by a generally known method. For example, Japanese Patent No. 336697 No. 2, Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, Japanese Patent Laid-Open No. 1-228960, Japanese Patent No. 4081149. Gazette, JP-A-63-124054, "phthalocyanine -chemistry and function-" (IPC, 1997), JP-A 2007-169315, JP-A 2009-108267, JP-A 2010-241873. , Japanese Patent No. 3699464, Japanese Patent No. 4740631, etc. It can be synthesized with reference to the method described.

<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。得られた反応溶液（水素添加重合体溶液）を冷却した後、水素ガスを放圧した。この反応溶液を大量のメタノール中に注いで凝固物を分離回収し、これを乾燥して、水素添加重合体（以下「樹脂Ａ」ともいう。）を得た。得られた樹脂Ａは、数平均分子量（Ｍｎ）が３２，０００、重量平均分子量（Ｍｗ）が１３７，０００であり、ガラス転移温度（Ｔｇ）が１６５℃であった。

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.

<Cyanine compound synthesis example 1>
The reaction scheme in this synthesis example is shown below.

窒素置換したジメチルホルムアミド（ＤＭＦ）に、上記反応スキームに示した化合物ａ（２．９ｍｍｏｌ）および化合物ｂ（５．８ｍｍｏｌ）を添加し、１２０℃で３時間撹拌して反応させた。生成物をジエチルエーテルで抽出し、シリカゲルカラムにて精製を行い、化合物ｃを得た。化合物ｃの収率は５１％であった。化合物ｃのアニオンのＨＯＭＯ値は−０．０ｅＶであった。また、ＮＭＲ測定の結果を以下に示す。
¹H NMR(DMSO-d₆) 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) 。

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%. The HOMO value of the anion of compound c was −0.0 eV. 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) .

<Cyanine compound synthesis example 2>
The reaction scheme in this synthesis example is shown below.

化合物ｃをアセトンに溶解させ、対応する金属ホウ素塩を加え、室温で塩交換を行うことで化合物ｅを得た。化合物ｅの収率は６７％であった。化合物ｅのアニオンのＨＯＭＯ値は−５．４ｅＶであった。また、ＮＭＲ測定の結果を以下に示す。
¹H NMR (methonol-d₄) d 1.45 (t, J = 7.2 Hz, 6H), 1.92 (brs, 2H), 2.01 (s, 12H), 2.75 (t, J = 7.0 Hz, 4H), 4.32 (t, J = 7.2 Hz, 4H), 6.29 (d, J = 14.4 Hz, 2H), 7.47 (m, 2H), 7.60 (m, 2H), 7.97 (d, J = 8.1 Hz, 2H), 8.02 (d, J = 9.3 Hz, 4H), 8.23 (d, J = 8.5 Hz, 2H), 8.53 (d, J = 14.4 Hz, 2H) 。

Compound e was obtained by dissolving compound c in acetone, adding a corresponding metal boron salt, and performing salt exchange at room temperature. The yield of compound e was 67%. The HOMO value of the anion of compound e was −5.4 eV. Moreover, the result of NMR measurement is shown below.
¹ H NMR (methonol-d ₄ ) d 1.45 (t, J = 7.2 Hz, 6H), 1.92 (brs, 2H), 2.01 (s, 12H), 2.75 (t, J = 7.0 Hz, 4H), 4.32 ( t, J = 7.2 Hz, 4H), 6.29 (d, J = 14.4 Hz, 2H), 7.47 (m, 2H), 7.60 (m, 2H), 7.97 (d, J = 8.1 Hz, 2H), 8.02 ( d, J = 9.3 Hz, 4H), 8.23 (d, J = 8.5 Hz, 2H), 8.53 (d, J = 14.4 Hz, 2H).

<Cyanine Compound Synthesis Example 3>
The reaction scheme in this synthesis example is shown below.

対応する金属ホウ素塩をＬｉＢ（Ｃ₆Ｆ₅）₄に変えたこと以外は、合成例２と同様の方法で化合物ｆを得た。化合物ｆの収率は７７％であった。化合物ｆのアニオンのＨＯＭＯ値は−５．８ｅＶであった。また、ＮＭＲ測定の結果を以下に示す。
¹H NMR (DMSO-d₆) d 1.48 (t, J = 7.4 Hz, 6H), 2.01 (m, 2H), 2.04 (s, 12H), 2.77 (t, J = 6.0 Hz, 4H), 4.44 (q, J = 7.2 Hz, 4H), 6.43 (d, J = 14.4 Hz, 2H), 7.52 (m, 2H), 7.63 (m, 2H), 7.70 (d, J = 9.0 Hz, 2H), 8.05 (m, 4H), 8.30 (d, J = 8.5 Hz, 2H), 8.52 (d, J = 14.4 Hz, 2H) 。

Compound f was obtained in the same manner as in Synthesis Example 2, except that the corresponding metal boron salt was changed to LiB (C ₆ F ₅ ) ₄ . The yield of compound f was 77%. The HOMO value of the anion of compound f was −5.8 eV. Moreover, the result of NMR measurement is shown below.
¹ H NMR (DMSO-d ₆ ) d 1.48 (t, J = 7.4 Hz, 6H), 2.01 (m, 2H), 2.04 (s, 12H), 2.77 (t, J = 6.0 Hz, 4H), 4.44 ( q, J = 7.2 Hz, 4H), 6.43 (d, J = 14.4 Hz, 2H), 7.52 (m, 2H), 7.63 (m, 2H), 7.70 (d, J = 9.0 Hz, 2H), 8.05 ( m, 4H), 8.30 (d, J = 8.5 Hz, 2H), 8.52 (d, J = 14.4 Hz, 2H).

<Cyanine Compound Synthesis Example 4>
The reaction scheme in this synthesis example is shown below.

対応する金属ホウ素塩をＮａＢ（Ｃ₆Ｈ₅）₄に変えたこと以外は、合成例２と同様の方法で化合物ｇを得た。化合物ｇの収率は７５％であった。化合物ｇのアニオンのＨＯＭＯ値は−２．７ｅＶであった。また、ＮＭＲ測定の結果を以下に示す。
¹H NMR (CDCl₃) d 1.29 (t, J = 7.2 Hz, 6H), 1.92 (m, 2H), 1.98 (s, 12H), 2.57 (t, J = 6.0 Hz, 4H), 3.76 (q, J = 7.2 Hz, 4H), 5.93 (d, J = 14.4 Hz, 2H), 6.85 (t, J = 7.2 Hz, 4H), 7.01 (t, J = 7.4 Hz, 8H), 7.13 (d, J = 8.5 Hz, 2H), 7.47 (m, 1, 0), 7.63 (t, J = 7.4 Hz, 2H), 7.89 (m, 4H), 8.09 (d, J = 8.5 Hz, 2H), 8.42 (d, J = 14.4 Hz, 2H)。

Compound g was obtained in the same manner as in Synthesis Example 2, except that the corresponding metal boron salt was changed to NaB (C ₆ H ₅ ) ₄ . The yield of compound g was 75%. The HOMO value of the anion of compound g was −2.7 eV. Moreover, the result of NMR measurement is shown below.
¹ H NMR (CDCl ₃ ) d 1.29 (t, J = 7.2 Hz, 6H), 1.92 (m, 2H), 1.98 (s, 12H), 2.57 (t, J = 6.0 Hz, 4H), 3.76 (q, J = 7.2 Hz, 4H), 5.93 (d, J = 14.4 Hz, 2H), 6.85 (t, J = 7.2 Hz, 4H), 7.01 (t, J = 7.4 Hz, 8H), 7.13 (d, J = 8.5 Hz, 2H), 7.47 (m, 1, 0), 7.63 (t, J = 7.4 Hz, 2H), 7.89 (m, 4H), 8.09 (d, J = 8.5 Hz, 2H), 8.42 (d, J = 14.4 Hz, 2H).

<Cyanine compound synthesis example 5>
The reaction scheme in this synthesis example is shown below.

対応する金属ホウ素塩をＮａＢ（Ｃ₆Ｈ₄−４−Ｆ）₄に変えたこと以外は、合成例２と同様の方法で化合物ｇを得た。化合物ｇの収率は８２％であった。化合物ｃのアニオンのＨＯＭＯ値は−３．３ｅＶであった。また、ＮＭＲ測定の結果を以下に示す。
¹H NMR (methonol-d₄) d 1.41 (t, J = 7.4 Hz, 6H), 1.92 (m, 2H), 2.00 (s, 12H), 2.60 (t, J = 5.55 Hz, 4H), 4.01 (q, J = 7.2 Hz, 4H), 6.01 (d, J = 14.3 Hz, 2H), 6.74 (m, 8H), 7.25 (m,10H), 7.49 (m, 2H), 7.62 (m, 2H), 7.93 (t, J = 8.3 Hz, 4H), 8.10 (d, J = 8.6 Hz, 2H), 8.47 (d, J = 13.9 Hz, 2H)。

Other than changing the corresponding metal boron salt _{NaB (C 6 H 4 -4-} F) 4, to yield compound g in the same manner as in Synthesis Example 2. The yield of compound g was 82%. The HOMO value of the anion of compound c was −3.3 eV. Moreover, the result of NMR measurement is shown below.
¹ H NMR (methonol-d ₄ ) d 1.41 (t, J = 7.4 Hz, 6H), 1.92 (m, 2H), 2.00 (s, 12H), 2.60 (t, J = 5.55 Hz, 4H), 4.01 ( q, J = 7.2 Hz, 4H), 6.01 (d, J = 14.3 Hz, 2H), 6.74 (m, 8H), 7.25 (m, 10H), 7.49 (m, 2H), 7.62 (m, 2H), 7.93 (t, J = 8.3 Hz, 4H), 8.10 (d, J = 8.6 Hz, 2H), 8.47 (d, J = 13.9 Hz, 2H).

[Example 1]
100 parts by weight of the resin A obtained in Resin Synthesis Example 1, 0.08 part by weight of Compound e obtained in Cyanine Compound Synthesis Example 2, and methylene chloride are added to a container to obtain a solution having a resin concentration of 20% by weight. It was. 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 828 nm. Further, when the heat resistance of this substrate was evaluated, the dye residual ratio was 99% or more. The results are shown in Table 1.

[Example 2] and [Comparative Example 1] to [Comparative Example 3]
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 employed. The evaluation results are shown in Table 1.

  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.

Claims (10)

  A cyanine compound, which is a counterion conjugate comprising an anion and a cation, and the anion has a HOMO value of -3.4 eV or less. The cyanine compound according to claim 1, wherein the anion is represented by the following general formula (I).

[In Formula (I), Y _{1 to} Y ₂₀ each independently represent a hydrogen atom, a fluorine atom, a trifluoromethyl group, or a cyano group. Provided that at least one Y in each group of _{Y 1 ~Y 5, Y 6 ~Y} 10, Y 11 ~Y 15 and Y ₁₆ to Y ₂₀ is a fluorine atom, a trifluoromethyl group or a cyano group. ] The cyanine compound according to claim 1 or 2, wherein the cation is represented by any one of the following general formulas (II-1) to (II-4).

[In the formulas (II-1) to (II-4),
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 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 ) The _C 3-14 heterocyclic group Z _{a to} Z _c and Y _{a to} Y _d which may have the substituent L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a 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 (L ^{1 to} L ⁴ have the same meanings as L ^{1 to} L ⁴ in 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 defined in II-4) The amino group, amide group, imide group and silyl group may have the substituent L. ]   An optical filter comprising: a transparent resin substrate 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 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 claim 4, which is at least one resin selected from the group consisting of a system curable resin and a silsesquioxane ultraviolet curable resin.   The optical filter according to claim 4 or 5, wherein the near-infrared reflective film is formed on both surfaces of the substrate.   The optical filter according to claim 4, which is for a solid-state imaging device.   The solid-state imaging device which comprises the optical filter of any one of Claims 4-7.   A camera module comprising the optical filter according to claim 4.   The cyanine compound according to any one of claims 1 to 3, 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. , Polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy A resin composition containing at least one resin selected from the group consisting of a resin, an allyl ester curable resin, and a silsesquioxane ultraviolet curable resin.