JP2012007038A - Near infrared ray absorption pigment and near infrared ray absorption pigment-containing adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near infrared ray absorption pigment and/or a near infrared ray absorption pigment-containing adhesive having excellent shielding function to near infrared rays generated from an electronic display screen and excellent durability, and in particular, to provide the near infrared ray absorption pigment and/or the near infrared ray absorption pigment-containing adhesive having excellent durability, wherein the near infrared ray absorption pigment has absorption in a relatively long wavelength region in the near infrared ray wavelength region.SOLUTION: The near infrared ray absorption pigment is represented by general formula (1).

Description

  The present invention relates to a near-infrared absorbing dye, a pressure-sensitive adhesive containing the same, and a near-infrared absorbing filter having a layer of the pressure-sensitive adhesive.

  In principle, plasma display panels emit strong near-infrared rays and electromagnetic waves. This near-infrared ray causes a malfunction by acting on a peripheral electronic device such as a cordless phone or a video deck using a near-infrared remote controller, particularly in a wavelength region of 750 nm to 1200 nm. Therefore, the near infrared ray in the range of 750 nm to 1200 nm. There is a demand for a plasma display panel having a function of shielding light.

  For shielding near infrared rays, conventionally, those containing metal ions such as copper and iron, nitroso compounds and their metal complexes, cyanine compounds, squarylium compounds, dithiol metal complex compounds, aminothiophenol metal complex compounds, phthalocyanines Various studies including near-infrared absorbing dyes such as compounds, naphthalocyanine compounds, triallylmethane compounds, immonium compounds, diimmonium compounds, naphthoquinone compounds, anthraquinone compounds, amino compounds, and aminium salt compounds Has been.

  The near-infrared absorbing dye as described above cannot cover the above-mentioned range of 750 nm to 1200 nm with only one kind of dye. Usually, a plurality of types of dyes, specifically, a dye that absorbs a near-infrared ray having a relatively short wavelength among the near-infrared rays and a dye that absorbs a near-infrared ray having a relatively long wavelength are usually used in combination.

  As usage forms, (a) a transparent polymer film prepared by kneading a near-infrared absorbing dye in a resin, (b) a near-infrared absorbing dye is dispersed in a concentrated resin solution in which a resin or a resin monomer is dissolved in an organic solvent. Or a polymer film dissolved and cast by a casting method, (c) a pigment added to a resin binder and a solvent and coated on a transparent polymer film, (d) a near-infrared absorbing pigment contained in an adhesive, Etc. are considered.

  Of these, a plurality of layers are generally bonded to form a product by the methods (a) to (c). However, in consideration of the labor, cost, and light transmittance at the time of manufacture, the more layers are stacked, the higher the cost and the lower the light transmittance are. Therefore, in order to further reduce the cost and improve the light transmittance, it is desirable to reduce the number of layers.

  Therefore, if a pigment is blended in the pressure-sensitive adhesive used for adhesion between layers by the method (d), the number of plastic film layers used may be reduced, leading to cost reduction and light transmittance improvement. This method has been studied so far, and a front filter for plasma display using a colored adhesive containing a methine dye or a visible light absorbing dye such as a tetraazaporphyrin dye is known (for example, Patent Document 1). ~ 3).

  In addition, it has been proposed that diimmonium dyes or nickel dithiol dyes, which are conventional near-infrared absorbing dyes preferably used for a front filter for plasma displays, be blended in an adhesive (Patent Documents 4 to 8). ).

  However, even a nickel dithiol dye excellent in various performances as a near infrared absorbing dye, particularly as a near infrared absorbing dye for an adhesive, has a relatively long wavelength range in the near infrared range of 750 nm to 1200 nm. The thing with an absorption region had the problem that durability was inferior. Therefore, a dye having an absorption maximum in a relatively long wavelength region in the near infrared region and excellent in durability has been desired.

JP 2004-107566 A JP 2002-040233 A JP 2002-372619 A JP-A-9-230134 Japanese Patent Laid-Open No. 10-156991 JP 2001-207142 A International Publication WO 2006/118277 Pamphlet International Publication WO 2008/050725 Pamphlet

  Among the near-infrared absorbing dyes proposed in Patent Documents 4 to 8 above, those having an absorption maximum at a relatively long wavelength can be blended in the pressure-sensitive adhesive, but the durability is actually deteriorated and fading occurs. This has caused problems such as the inability to shield near infrared rays. Therefore, it has not been put into practical use by blending and using a near-infrared absorbing dye having absorption over the entire wavelength range of 750 nm to 1200 nm in the adhesive.

  The present invention has been made in view of the above-mentioned background art, and its problem is that it has an excellent shielding function against near infrared rays generated from an electronic display screen such as a plasma display panel and has excellent durability. An object of the present invention is to provide an infrared-absorbing dye and / or a near-infrared-absorbing dye-containing pressure-sensitive adhesive. In particular, a near-infrared absorbing dye having absorption in a relatively long wavelength region in the near-infrared wavelength region of 750 nm to 1200 nm, and a near-infrared absorbing dye and / or a near-infrared absorbing dye-containing adhesive having excellent durability It is to provide an agent.

  As a result of intensive studies to solve the above problems, the present inventor has good heat resistance, moist heat resistance, light resistance, etc. even when a metal complex having a specific structure is mixed with an adhesive. I found. Moreover, it discovered that the adhesive which can interrupt | block the near infrared ray of a required area | region effectively can be provided by combining a some near-infrared absorption pigment | dye. Furthermore, it is possible to provide a near-infrared absorbing dye and / or a near-infrared-absorbing dye-containing pressure-sensitive adhesive that can achieve both excellent absorption and relatively long wavelength absorption in the near-infrared wavelength region of 750 nm to 1200 nm. As a result, the present invention has been completed.

［一般式（１）中、
Ｒ^１及びＲ^２は、それぞれ独立して、置換基を有していてもよい複素環基を示す。
Ｘ^１及びＸ^２は、それぞれ独立して、炭素原子、酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計４以上有する１価の基を示し、Ｘ^１及びＸ^２は連結基を介して互いに結合していてもよい。
Ｍは金属原子を示す。
ベンゼン環Ａは、Ｘ^１以外に、それぞれ異なっていてもよい置換基Ｒ^ｆを有していてもよく、隣り合うＲ^ｆは連結基を介して結合していてもよく、結合して縮合環を形成していてもよい。
Ｒ^ｆ同士が結合して縮合環を形成していないときは、ｍは０〜４の整数であり、Ｒ^ｆ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。
ベンゼン環Ｂは、Ｘ^２以外に、それぞれ異なっていてもよい置換基Ｒ^ｇを有していてもよく、隣り合うＲ^ｇは連結基を介して結合していてもよく、結合して縮合環を形成していてもよい。
Ｒ^ｇ同士が結合して縮合環を形成していないときは、ｎは０〜４の整数であり、Ｒ^ｇ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。］ That is, the gist of the present invention resides in the following [1] to [18].
[1] A near-infrared absorbing dye, which is represented by the following general formula (1).

[In general formula (1),
R ¹ and R ² each independently represents a heterocyclic group which may have a substituent.
X ¹ and X ^2, each independently represents a monovalent group having at least one atom for a total of 4 or more selected from the group consisting of carbon atom, oxygen atom, nitrogen atom and a silicon atom, X ¹ and X ² may be bonded to each other via a linking group.
M represents a metal atom.
The benzene ring A may have a substituent R ^f which may be different from each other in addition to X ¹ , and adjacent R ^f may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^f is bonded to each other to form a condensed ring, m is an integer of 0 to 4, and when R ^f is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent.
The benzene ring B may have a substituent R ^g which may be different from each other in addition to X ² , and adjacent R ^gs may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^g is bonded to form a condensed ring, n is an integer of 0 to 4. When R ^g is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]

[2] In the general formula (1), X ¹ and X ² are each independently —OR ^a (R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms). The near-infrared absorbing dye according to [1], characterized in that
[3] In the general formula (1), R ¹ and R ² are each independently at least one selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may have a substituent. The near-infrared absorbing dye according to [1] or [2], which is a heterocyclic group having the following atoms:
[4] The near-infrared absorption according to [3], wherein in the general formula (1), R ¹ and R ² are each independently a thienyl group which may have a substituent. Pigment.

[5] In the general formula (1), the substituent R ^f and the substituent R ^g are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group, or an alkyl group having 1 to 1 carbon atoms. The near-infrared absorbing dye according to any one of [1] to [4], which is 10 aralkyl groups or a linear or branched alkoxy group having 1 to 10 carbon atoms.

［一般式（２ａ）及び（２ｂ）中、
Ｒ^３は置換基を有していてもよいチエニル基を示す。
Ｒ^ａは炭素数３〜１０の直鎖又は分岐アルキル基を示す。
Ｒ^ｂは炭素数１〜１０の直鎖若しくは分岐アルキル基、シクロアルキル基、又は、炭素数１〜６の直鎖若しくは分岐アルコキシ基を示す（ただし、Ｒ^ｂが分岐アルコキシ基である場合は、Ｒ^ｂは、ＯＲ^ａと同じ基である）。
Ｍ^１は金属原子を示す。］ [6] The near-infrared absorbing dye represented by the general formula (1) is a near-infrared absorbing dye represented by the following general formula (2a) or (2b) [1] to [5] ] The near-infrared absorptive pigment | dye in any one of.

[In the general formulas (2a) and (2b),
R ³ represents a thienyl group which may have a substituent.
R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms.
R ^b represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms (provided that when R ^b is a branched alkoxy group, R ^b is the same group as OR ^a ).
M ¹ represents a metal atom. ]

[7] The near-infrared absorbing dye according to any one of [1] to [6], wherein the maximum absorption wavelength is in the range of 850 nm to 1200 nm.

[8] A near-infrared absorbing dye-containing pressure-sensitive adhesive comprising the near-infrared absorbing dye according to any one of [1] to [7].
[9] The near-infrared absorbing dye-containing adhesive according to [8], further comprising a second near-infrared absorbing dye having a maximum absorption wavelength in the range of 750 nm to 1200 nm.
[10] The maximum absorption wavelength is shorter than the near-infrared absorbing dye according to any one of [1] to [7] contained in the adhesive, and the maximum absorption wavelength is in the range of 750 nm to 950 nm. The near-infrared absorbing dye-containing adhesive according to [9], comprising a second near-infrared absorbing dye.

［一般式（３）中、
Ｘ及びＹは、それぞれ独立して、硫黄原子、酸素原子、又は、置換基を有していてもよい窒素原子を示す。
Ｍ^２は金属原子を示す。
（Ａ）Ｘが置換基を有する窒素原子の場合；
窒素原子の置換基は、下記一般式（４ａ）で表される化合物であり、

（一般式（４ａ）中、
Ｒは、炭素原子、酸素原子、硫黄原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計３以上有する１価の置換基を示し、Ｒの末端が一般式（３）のベンゼン環に結合していてもよい。
Ｒ’は、任意の１価の置換基を示し、Ｒ’同士は結合して縮合環を形成していてもよい。
Ｒ’同士が結合して縮合環を形成していないときは、ｎ’は０〜４の整数であり、Ｒ’同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。）
Ｒ^Ｘ及びＲ^Ｙは、それぞれ独立して１価の置換基を示し、連結基を介して結合していてもよく、Ｒ^Ｘ及びＲ^Ｙが結合して縮合環を形成していてもよい。）
（Ｂ）Ｘが酸素原子又は硫黄原子の場合；
Ｒ^Ｙは１価の置換基を示す。
Ｒ^Ｘは下記一般式（４ｂ）で表される化合物である。

（一般式（４ｂ）中、
Ｘ^ｈは、炭素原子、酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計３以上有する１価の基を示す。
Ｒ^ｈは、任意の１価の置換基を示し、Ｒ^ｈ同士は結合して縮合環を形成していてもよい。
Ｒ^ｈ同士が結合して縮合環を形成していないときは、ｐは０〜４の整数であり、Ｒ^ｈ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。）］ [11] The near-infrared absorbing dye-containing adhesive according to [10], wherein the second near-infrared absorbing dye is a near-infrared absorbing dye represented by the following general formula (3).

[In general formula (3),
X and Y each independently represent a sulfur atom, an oxygen atom, or a nitrogen atom that may have a substituent.
M ² represents a metal atom.
(A) when X is a nitrogen atom having a substituent;
The substituent of the nitrogen atom is a compound represented by the following general formula (4a),

(In the general formula (4a),
R represents a monovalent substituent having a total of 3 or more of at least one kind selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, and the terminal of R is represented by the general formula (3) It may be bonded to the benzene ring.
R ′ represents an arbitrary monovalent substituent, and R ′ may be bonded to each other to form a condensed ring.
When R ′ is not bonded to form a condensed ring, n ′ is an integer of 0 to 4, and when R ′ is bonded to form a condensed ring, the condensed ring is arbitrary. May have a monovalent substituent. )
R ^X and R ^Y each independently represent a monovalent substituent, and may be bonded via a linking group, or R ^X and R ^Y may be bonded to form a condensed ring. )
(B) when X is an oxygen atom or a sulfur atom;
R ^Y represents a monovalent substituent.
R ^X is a compound represented by the following general formula (4b).

(In the general formula (4b),
X ^h represents a monovalent group having a total of 3 or more of at least one kind of atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom.
R ^h represents an arbitrary monovalent substituent, and R ^h may be bonded to each other to form a condensed ring.
When R ^h is bonded to form a condensed ring, p is an integer of 0 to 4, and when R ^h is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]]

［一般式（５）において、
Ｒ^４は、水素原子；炭素数１〜５の直鎖又は分岐アルキル基；アルキル基、アルコキシ基、置換アミノ基又はハロゲン原子を置換基として有していてもよいフェニル基；アルキル基、アルコキシ基、置換アミノ基又はハロゲン原子を置換基として有していてもよいフェニルチオ基を示す。
Ｒ^６は、炭素数３〜１０の直鎖又は分岐アルキル基を示す。
Ｒ^５は、炭素数１〜１０の直鎖若しくは分岐アルキル基、又は、炭素数１〜６の直鎖若しくは分岐アルコキシ基（ただし、Ｒ^５が分岐アルコキシ基である場合は、Ｒ^５は、ＯＲ^６と同じ基である）。
Ｍ^４は金属原子を表す。］ [12] The second near infrared absorbing dye represented by the general formula (3) is a second near infrared absorbing dye represented by the following general formula (5). The near-infrared absorbing dye-containing pressure-sensitive adhesive described

[In general formula (5),
R ⁴ represents a hydrogen atom; a linear or branched alkyl group having 1 to 5 carbon atoms; an alkyl group, an alkoxy group, a substituted amino group, or a phenyl group optionally having a halogen atom as a substituent; an alkyl group or an alkoxy group Represents a phenylthio group optionally having a substituted amino group or a halogen atom as a substituent.
R ⁶ represents a linear or branched alkyl group having 3 to 10 carbon atoms.
R ⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms (provided that when R ⁵ is a branched alkoxy group, R ⁵ is OR ⁶ and the same group).
M ⁴ represents a metal atom. ]

［一般式（６）中、
Ｒ^７及びＲ^８は、置換基を有していてもよい炭化水素基、置換基を有していてもよいカルボニル基、シアノ基、ハロゲン原子、又は、水素原子を示す。
Ｒ^９及びＲ^１０は、置換基を有していてもよいアルキル基、又は、置換基を有していてもよいアリール基を示す。
Ｍ^５は金属原子を示す。］
［１４］更に、（メタ）アクリル系樹脂を含有することを特徴とする［８］ないし［１３］の何れかに記載の近赤外線吸収色素含有粘着剤。 [13] The near-infrared absorbing dye-containing adhesive according to [9] or [10], wherein the second near-infrared absorbing dye is a near-infrared absorbing dye represented by the following general formula (6) .

[In general formula (6),
R ⁷ and R ⁸ represent a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a cyano group, a halogen atom or a hydrogen atom.
R ⁹ and R ¹⁰ represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
M ⁵ represents a metal atom. ]
[14] The near-infrared absorbing dye-containing pressure-sensitive adhesive according to any one of [8] to [13], further comprising a (meth) acrylic resin.

[15] A near-infrared absorption filter comprising a layer of the near-infrared-absorbing dye-containing adhesive according to any one of [8] to [14].
[16] A front filter for a plasma display, comprising the near-infrared absorption filter according to [15].
[17] A plasma display comprising the front filter for plasma display according to [16].

［一般式（１）中、
Ｒ^１及びＲ^２は、それぞれ独立して、置換基を有していてもよい複素環基を示す。
Ｘ^１及びＸ^２は、それぞれ独立して、炭素原子、酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計４以上有する１価の基を示し、Ｘ^１及びＸ^２は連結基を介して互いに結合していてもよい。
Ｍは金属原子を示す。
ベンゼン環Ａは、Ｘ^１以外に、それぞれ異なっていてもよい置換基Ｒ^ｆを有していてもよく、隣り合うＲ^ｆは連結基を介して結合していてもよく、結合して縮合環を形成していてもよい。
Ｒ^ｆ同士が結合して縮合環を形成していないときは、ｍは０〜４の整数であり、Ｒ^ｆ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。
ベンゼン環Ｂは、Ｘ^２以外に、それぞれ異なっていてもよい置換基Ｒ^ｇを有していてもよく、隣り合うＲ^ｇは連結基を介して結合していてもよく、結合して縮合環を形成していてもよい。
Ｒ^ｇ同士が結合して縮合環を形成していないときは、ｎは０〜４の整数であり、Ｒ^ｇ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。］ [18] A near-infrared absorbing dye represented by the following general formula (1) and a second near-infrared absorbing dye having a maximum absorption wavelength in the range of 750 nm to 950 nm. Dye mixture for near infrared absorption filter.

[In general formula (1),
R ¹ and R ² each independently represents a heterocyclic group which may have a substituent.
X ¹ and X ^2, each independently represents a monovalent group having at least one atom for a total of 4 or more selected from the group consisting of carbon atom, oxygen atom, nitrogen atom and a silicon atom, X ¹ and X ² may be bonded to each other via a linking group.
M represents a metal atom.
The benzene ring A may have a substituent R ^f which may be different from each other in addition to X ¹ , and adjacent R ^f may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^f is bonded to each other to form a condensed ring, m is an integer of 0 to 4, and when R ^f is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent.
The benzene ring B may have a substituent R ^g which may be different from each other in addition to X ² , and adjacent R ^gs may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^g is bonded to form a condensed ring, n is an integer of 0 to 4. When R ^g is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]

  According to the present invention, the dye is hardly deteriorated by mixing with the pressure-sensitive adhesive, and is excellent in light resistance, heat resistance, moist heat resistance, and the like, and if necessary, by combining a plurality of near-infrared absorbing dyes, It is possible to provide a near-infrared absorbing dye that shields the near-infrared region in a wide range and a pressure-sensitive adhesive containing the same.

  Further, according to the present invention, a near-infrared absorbing dye having absorption in a relatively long wavelength region, for example, in the range of 850 nm to 1200 nm, and having durability in the near-infrared wavelength region, and The adhesive which contains can be provided.

  According to the present invention, it can be used as a part of a filter for an electronic display such as a filter for an optical plasma display panel by being attached to a layer having another function such as an antireflection layer or an electromagnetic wave shielding layer. Cost reduction and light transmittance can be improved by reducing the layers of the filter for electronic display and reducing the bonding process.

It is a spectral transmission spectrum measurement result of the near-infrared absorption pigment | dye 1. FIG. It is a spectral transmission spectrum measurement result of the near-infrared absorbing dye 2. It is a spectral transmission spectrum measurement result of the near-infrared absorption pigment | dye 3. FIG. It is a spectral transmission spectrum measurement result of the near-infrared absorbing dye 4. It is a spectral transmission spectrum measurement result of the near-infrared absorption pigment | dye 5. FIG. It is a spectral transmission spectrum measurement result of the near-infrared absorption pigment | dye 6. FIG. It is a spectral transmission spectrum measurement result of the near-infrared absorption pigment | dye 7. FIG. It is a spectral transmission spectrum measurement result of the near-infrared absorbing dye 8. It is a spectral-transmission-spectrum measurement result of the near-infrared absorption pigment | dye manufactured by the comparative example 1. It is a spectral transmission spectrum measurement result of the near-infrared absorbing dye 1 before and after the wet heat resistance test. From the bottom of the spectrum, the measurement results are 480 hours before the test. It is a spectral transmission spectrum measurement result of the near-infrared absorbing dye 1 before and after the heat resistance test. From the bottom of the spectrum, the measurement results are 480 hours before the test. It is a spectral-transmission-spectrum measurement result before and behind a heat-and-moisture resistance test of the near-infrared absorption pigment | dye manufactured by the comparative example 1. From the bottom of the spectrum, the measurement results are 480 hours before the test. It is a spectral-transmission-spectrum measurement result before and behind a heat resistance test of the near-infrared absorption pigment | dye manufactured by the comparative example 1. From the bottom of the spectrum, the measurement results are 480 hours before the test.

  Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.

［一般式（１）中、
Ｒ^１及びＲ^２は、それぞれ独立して、置換基を有していてもよい複素環基を示す。
Ｘ^１及びＸ^２は、それぞれ独立して、炭素原子、酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計４以上有する１価の基を示し、Ｘ^１及びＸ^２は連結基を介して互いに結合していてもよい。
Ｍは金属原子を示す。
ベンゼン環Ａは、Ｘ^１以外に、それぞれ異なっていてもよい置換基Ｒ^ｆを有していてもよく、隣り合うＲ^ｆは連結基を介して結合していてもよく、結合して縮合環を形成していてもよい。
Ｒ^ｆ同士が結合して縮合環を形成していないときは、ｍは０〜４の整数であり、Ｒ^ｆ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。
ベンゼン環Ｂは、Ｘ^２以外に、それぞれ異なっていてもよい置換基Ｒ^ｇを有していてもよく、隣り合うＲ^ｇは連結基を介して結合していてもよく、結合して縮合環を形成していてもよい。
Ｒ^ｇ同士が結合して縮合環を形成していないときは、ｎは０〜４の整数であり、Ｒ^ｇ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。］ <Near-infrared absorbing dye of the present invention>
The near-infrared absorbing dye of the present invention is represented by the following general formula (1).

[In general formula (1),
R ¹ and R ² each independently represents a heterocyclic group which may have a substituent.
X ¹ and X ^2, each independently represents a monovalent group having at least one atom for a total of 4 or more selected from the group consisting of carbon atom, oxygen atom, nitrogen atom and a silicon atom, X ¹ and X ² may be bonded to each other via a linking group.
M represents a metal atom.
The benzene ring A may have a substituent R ^f which may be different from each other in addition to X ¹ , and adjacent R ^f may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^f is bonded to each other to form a condensed ring, m is an integer of 0 to 4, and when R ^f is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent.
The benzene ring B may have a substituent R ^g which may be different from each other in addition to X ² , and adjacent R ^gs may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^g is bonded to form a condensed ring, n is an integer of 0 to 4. When R ^g is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]

In the general formula (1), R ¹ and R ² each independently represents a heterocyclic group which may have a substituent. Further, preferred examples of atoms other than carbon (heteroatom) that form a heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic ring may be a single ring or a condensed ring composed of 2 to 4 rings. Each ring of a single ring or a condensed ring may be any number of rings, but is preferably a 5-membered ring or a 6-membered ring, and the heterocyclic ring is preferably an aromatic ring. Furthermore, it is particularly preferable that R ¹ and R ² are each independently a heterocyclic group having a sulfur atom, which may have a substituent.

Specific examples of the heterocyclic ring of “optionally substituted heterocyclic group” include pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, Isothiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, pyran ring, quinoline ring, benzofuran ring, benzothiophene ring, indole ring, isobenzofuran ring, isobenzothiophene ring, 5- to 6-membered monocyclic ring or 2-4 condensed ring derived from isoindole ring, benzimidazole ring, benzothiazole ring, purine ring, isoquinoline ring, quinoxaline ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring, acridine ring, etc. Aromatic heterocyclic group having a conjugated electron donating property Preferable from the surface. Among them, a thiophene ring is particularly preferable in terms of near infrared absorption performance, durability, compound solubility, stability, and the like. That is, it is particularly preferable that R ¹ and R ² are each independently a thienyl group which may have a substituent.

Examples of the substituent bonded to the heterocyclic group include a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a halogen atom such as F, Cl and Br, -SR ^t ( R ^t is an alkyl group having 1 to 15 carbon _{atoms), - CH 2 - (OCH} 2 CH 2) q -OCH 2 CH 3 and ethylene oxide chain-containing group, an acetyl group, an acyl group such as propionyl group, a phenyl group, Aromatic ring group such as thienyl group, aralkyl group such as benzyl group, α-phenethyl group, β-phenethyl group, nitrile group, amino group optionally having substituent, alkoxy optionally having substituent Examples thereof include a carbonyl group, an aryloxycarbonyl group which may have a substituent, and an alkyl group having a fluorine group. The alkyl group may be linear or branched, and substituents bonded to the heterocyclic group may be bonded to each other via a linking group.

Further, as the substituent of the heterocyclic group, in order to finely adjust the absorption maximum to a longer wavelength, the Hammett's substituent constant σ _p is preferably −0.9 ≦ σ _p ≦ 0.0. . On the other hand, as the substituent of the heterocyclic group, in order to finely adjust the absorption maximum to a shorter wavelength, the Hammett's substituent constant σ _p is preferably 0.0 ≦ σ _p ≦ 0.9. A more preferable range depends on the wavelength of the absorption maximum and the ease of synthesis of the compound, and can be appropriately selected according to the required characteristics.

  In particular, from the viewpoint of ease of synthesis, the substituent is preferably a hydrogen atom, and is preferably an alkyl group having 1 to 5 carbon atoms. In addition, the case where the substituent is a halogen atom is also preferable because of the effect of attracting electrons of the heterocyclic group. Among these, a hydrogen atom and an alkyl group having 1 to 3 carbon atoms are preferable as the substituent of the heterocyclic group from the viewpoint of increasing the absorbance per mass, and from the viewpoint of near infrared absorption performance, durability, and the like.

As used herein, “Hammett's substituent constant σ _p ” means “chemical structure-activity relationship, page 96-103 (published by Nanedo)”, “Hansch, C. et, al., J” .Med.Chem., 16,1207 (1973) "," Hansch, C. et, al. , J.Med.Chem., 20,304 (1977) "has been of Hammett substituent constants sigma _p according to such Therefore, σ _p can be measured by a known method.

  Further, the number of substituents bonded to the heterocyclic group is not particularly limited, but is preferably 1 to 2. Further, the position at which the substituent is bonded to the heterocyclic group is not particularly limited, and may be α-position or β-position with respect to the hetero atom. The substituents bonded to the heterocyclic group may be bonded to each other through a linking group.

In the general formula (1), X ¹ and X ² are each independently a monovalent group having a total of 4 or more of at least one kind selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom. Indicates. The at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, and a silicon atom is not particularly limited, but it is preferable to have only one in X ¹ and X ² . Further, the atom directly bonded to the benzene ring A or the benzene ring B may be any of a carbon atom, an oxygen atom, a nitrogen atom, or a silicon atom. X ¹ and X ² each preferably have 2 to 18 carbon atoms, and particularly preferably 3 to 16 carbon atoms. If the number of carbon atoms is too small, the solubility may be lowered. On the other hand, if the number of carbon atoms is too large, the melting point may be lowered and it may be difficult to isolate the compound. The chain of carbon atoms may be a straight chain or may have a branch, but it is preferable to have a branch in terms of imparting appropriate solubility.

Examples of X ¹ and X ² include an optionally substituted hydrocarbon group, an optionally substituted carbonyl group, an optionally substituted hydrocarbon thio group, an optionally substituted silyl group, and a substituted group. And an optionally substituted hydrocarbon amino group and an optionally substituted hydrocarbon oxy group.

(A) Hydrocarbon group Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aryl group, and an aralkyl group.
Examples of the aliphatic hydrocarbon group include n-butyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, 2-ethylbutyl group, 2-butyl group, cyclohexyl group, and 3-pentyl group. Examples include chain, branched chain, or cyclic alkyl groups; alkenyl groups such as 2-butenyl group, 3-butenyl group, and 2,4-pentadienyl group; and alkynyl groups such as 2-hexyne group. Among these, an aliphatic hydrocarbon group having about 4 to 12 carbon atoms is preferable, and a branched chain aliphatic hydrocarbon group having about 4 to 12 carbon atoms is particularly preferable.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, an azulenyl group, and a metallocene ring group. Of these, a monocyclic or condensed bicyclic aryl group having about 6 to 12 carbon atoms is preferred.

  Examples of the aralkyl group include a group in which the above aliphatic hydrocarbon group and aryl group are bonded.

(B) Heterocyclic group Examples include a thienyl group, a furyl group, a pyrrolyl group, a pyridyl group, an imidazolyl group, a pyrazolyl group, an indolyl group, a quinoxalinyl group, an acridinyl group, a thiazolyl group, and a pyrazinyl group. Of these, a monocyclic or bicyclic heterocyclic group having 3 to 12 carbon atoms is preferable.

(C) Carbonyl group An acyl group (—COR), a carbamoyl group (—CONRR ′), an alkoxycarbonyl group (—C (O) OR), an aryloxycarbonyl group, and a heterocyclic oxycarbonyl group are exemplified. Specifically, R in the acyl group (—COR) is the same as the specific examples of the aliphatic hydrocarbon group, aryl group, and heterocyclic group described above, in addition to an n-propyl group and a 2-propenyl group. Etc. Further, R and R ′ of the carbamoyl group (—CONRR ′) are the same as the specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group described above, in addition to an ethyl group, an n-propyl group, A 2-propenyl group, an ethynyl group, etc. are mentioned. R of the alkoxycarbonyl group (—C (O) OR) is the same as the specific examples of the aliphatic hydrocarbon group mentioned above, but also an ethyl group, an n-propyl group, a 2-propenyl group, an ethynyl group, etc. Is mentioned. Further, R of the aryloxycarbonyl group (—C (O) OR) is the same as the specific examples of the aryl group described above, and R of the heterocyclic oxycarbonyl group (—C (O) OR) is Examples thereof are the same as the specific examples of the heterocyclic group mentioned above.

(D) Hydrocarbon thio group R in the hydrocarbon thio group (-SR) is the same as the specific examples of the hydrocarbon group, aryl group and heterocyclic group described above, in addition to n-propyl group, 2- A propenyl group, an ethynyl group, etc. are mentioned.
(E) Silyl group As the silyl group, there are silyl groups such as t-butyldiphenylsilyl group, n-butyldimethylsilyl group, dimethylpropylsilyl group, dimethylphenylsilyl group, dimethylisopropylsilyl group, triisopropylpropylsilyl group and the like. Can be mentioned. Preferably, it is an alkylsilyl group having about 3 to 18 carbon atoms.

(F) Hydrocarbon amino group R and R 'of the hydrocarbon amino group (-NRR') are the same as the specific examples of the hydrocarbon group, aryl group and heterocyclic group described above, and n-propyl. Group, 2-propenyl group, ethynyl group and the like.
(G) Hydrocarbonoxy group R of the hydrocarbonoxy group (-OR) is the same as the specific examples of the hydrocarbon group, aryl group and heterocyclic group described above, in addition to n-propyl group, 2- A propenyl group, an ethynyl group, etc. are mentioned.

When the above groups (a) to (g) have a substituent, the type of the substituent is not particularly limited as long as it does not affect the stability of the dye and the dispersion / solubility in the adhesive resin. .
For example, halogen atom, hydroxyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio Group, amino group, acyl group, aminoacyl group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, aryl Examples include groups selected from the group consisting of sulfonyl groups, heteroarylsulfonyl groups, imide groups, silyl groups, and the like.

  Specifically, an alkyl group having about 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having about 1 to 6 carbon atoms such as an ethynyl group or a propylenyl group; an alkynyl group having about 1 to 6 carbon atoms such as an acetylenyl group An aryl group having about 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a heteroaryl group having about 3 to 20 carbon atoms such as a thienyl group, a furyl group or a pyridyl group; 1 to 1 carbon atoms such as an ethoxy group or a propoxy group; Alkoxy groups of about 6; aryloxy groups of about 6 to 20 carbon atoms such as phenoxy groups and naphthoxy groups; heteroaryloxy groups of about 3 to 20 carbon atoms such as pyridyloxy groups and thienyloxy groups; methylthio groups and ethylthio groups An alkylthio group having about 1 to 6 carbon atoms such as phenylthio group and an arylthio group having about 6 to 20 carbon atoms such as naphthylthio group; pyridylthio group, A heteroarylthio group having about 3 to 20 carbon atoms such as an nylthio group; an amino group optionally having a substituent having about 1 to 20 carbon atoms such as a dimethylamino group and a diphenylamino group; an acetyl group, a pivaloyl group and the like An acyl group having about 2 to 20 carbon atoms; an acylamino group having about 2 to 20 carbon atoms such as an acetylamino group and a propionylamino group; a ureido group having about 2 to 20 carbon atoms such as a 3-methylureido group; methanesulfonamide A sulfonamide group having about 1 to 20 carbon atoms such as a benzenesulfonamide group; a carbamoyl group having about 1 to 20 carbon atoms such as a dimethylcarbamoyl group and an ethylcarbamoyl group; 1 to 20 carbon atoms such as an ethylsulfamoyl group A sulfamoyl group of about 1 to 20 carbon atoms such as a dimethylsulfamoylamino group; An alkoxycarbonyl group having about 2 to 6 carbon atoms such as a carbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group having about 7 to 20 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group; 6 carbon atoms such as a pyridyloxycarbonyl group A heteroaryloxycarbonyl group of about -20; an alkylsulfonyl group of about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group and a trifluoromethanesulfonyl group; a carbon number of 6 to 6 such as a benzenesulfonyl group and a monofluorobenzenesulfonyl group An arylsulfonyl group having about 20 carbon atoms; a heteroarylsulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide group having about 4 to 20 carbon atoms such as phthalimide; a substituent selected from the group consisting of an alkyl group and an aryl group The three-substituted Examples include a tolyl group.

  Preferred are an alkyl group, an alkoxy group, an alkylthio group, an amino group having a substituent, a fluorine atom, and a chlorine atom.

Particularly preferably, X ¹ and X ² each independently represent —OR ^a (R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms) or —N (R ^a ) _2. (R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms.), More preferably —OR ^a (R ^a is a linear or branched alkyl group having 3 to 10 carbon atoms. Is shown).

Here, R ^a represents a linear, branched or cycloalkyl group having 3 to 10 carbon atoms, more preferably a linear, branched or cycloalkyl group having 4 to 9 carbon atoms, particularly preferably carbon. It is a linear, branched or cycloalkyl group having a number of 5 to 8. Branched alkyl groups are more preferred for the reasons described above.

Specifically, R ^a is, for example, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group. 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3- Dimethylbutyl, 5-methylhexyl, 6-methylheptyl, 2-ethylhexyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cycl Penchirumechiru group, cyclopentylethyl group, a cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cyclohexylmethyl group, a cyclohexyl ethyl group or the like.

R ^a may have a substituent such as a phenyl group, a cyclohexyl group, a naphthyl group, an anthracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a cyclohexyl group, a cyclopentyl group, a benzyl group, and a phenethyl group.

X ¹ and X ² may be bonded to each other via a linking group. Examples of the “linking group” include a simple bond “—”, —O—, —NH—, —OCH ₂ CH ₂ O—, —S—, —SO—, —SO ₂ —, —CONR—, —SS—. Phenylene group, naphthylene group, anthranyl group, biphenyl group, ester group and the like.

  In the general formula (1), M represents a metal atom. M is not particularly limited as long as it is a metal atom that can take a tetracoordinate form. Preferably, Group 10 metal atoms such as Ni, Pd, Pt; Co; Fe; Cu; Ag; Au; More preferred is a group 10 metal atom, and particularly preferred is Ni or Pd.

In the general formula (1), the benzene ring A may have a different substituent R ^f in addition to X ¹ . Adjacent R ^f may be bonded via a linking group or may be bonded to form a condensed ring. When R ^f is bonded to each other and does not form a condensed ring, m is an integer of 0 to 4. When R ^f is bonded to each other to form a condensed ring, the condensed ring may have 1 to 10, preferably 1 to 5 arbitrary monovalent substituents.

Also, the benzene ring B, X ² addition, which may have a substituent R ^g to be different from each other. Further, adjacent R ^gs may be bonded via a linking group, or may be bonded to form a condensed ring. When R ^g together do not form a condensed ring attached, n is an integer from 0 to 4. When R ^g together form a condensed ring by bonding, 1-10 is condensed rings, preferably may have 1-5 arbitrary monovalent substituent.

Here, the substituent R ^f and the substituent R ^g are each independently an arbitrary substituent, and particularly if they do not adversely affect the stability of the near-infrared absorbing dye, the solubility in the adhesive resin, and the like. It is not limited.

Specifically, the substituent R ^f and the substituent R ^g are each independently, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, Aralkyl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group, acyl group, aminoacyl group, ureido group, sulfonamide group, carbamoyl group, sulfamoyl A group selected from the group consisting of a group, a sulfamoylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an imide group, and a silyl group Can be mentioned.

The substituent R ^f and the substituent R ^g may have a substituent. Specific examples of the substituent that the substituent R ^f and the substituent R ^g have include, for example, independently a halogen atom such as a fluorine atom and a chlorine atom; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and the like. Can be mentioned.

  Specifically, an alkyl group having about 1 to 10 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having about 1 to 10 carbon atoms such as an ethynyl group or a propylenyl group; an alkynyl group having about 1 to 10 carbon atoms such as an acetylenyl group An aryl group having about 6 to 20 carbon atoms, such as a phenyl group or a naphthyl group; an aralkyl group having 1 to 10 carbon atoms in an alkyl group; a heteroaryl group having about 3 to 20 carbon atoms, such as a thienyl group, a furyl group, or a pyridyl group; An alkoxy group having about 1 to 6 carbon atoms such as an ethoxy group and a propoxy group; an aryloxy group having about 6 to 20 carbon atoms such as a phenoxy group and a naphthoxy group; 3 to 20 carbon atoms such as a pyridyloxy group and a thienyloxy group; Heteroaryloxy group of about; alkylthio group of about 1 to 6 carbon atoms such as methylthio group and ethylthio group; carbon number of phenylthio group and naphthylthio group An arylthio group having about 20 carbon atoms; a heteroarylthio group having about 3-20 carbon atoms such as a pyridylthio group and a thienylthio group; and a substituent having about 1-20 carbon atoms such as a dimethylamino group and a diphenylamino group Good amino group; acyl group having about 2 to 20 carbon atoms such as acetyl group and pivaloyl group; acylamino group having about 2 to 20 carbon atoms such as acetylamino group and propionylamino group; and 2 carbon atoms such as 3-methylureido group A ureido group having about 20 to 20; a sulfonamide group having about 1 to 20 carbon atoms such as a methanesulfonamide group and a benzenesulfonamide group; a carbamoyl group having about 1 to 20 carbon atoms such as a dimethylcarbamoyl group and an ethylcarbamoyl group; Sulfamoyl group having 1 to 20 carbon atoms such as famoyl group; charcoal such as dimethylsulfamoylamino group A sulfamoylamino group having about 1 to 20 carbon atoms; an alkoxycarbonyl group having about 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; an aryl having about 7 to 20 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group Oxycarbonyl group; heteroaryloxycarbonyl group having about 6 to 20 carbon atoms such as pyridyloxycarbonyl group; alkylsulfonyl group having about 1 to 6 carbon atoms such as methanesulfonyl group, ethanesulfonyl group and trifluoromethanesulfonyl group; benzenesulfonyl Group, an arylsulfonyl group having about 6 to 20 carbon atoms such as a monofluorobenzenesulfonyl group; a heteroarylsulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide group having about 4 to 20 carbon atoms such as phthalimide; Alkyl group and aryl group And a silyl group that is trisubstituted with a substituent selected from the group consisting of. The specific group preferably has the above-described substituent.

  Preferably, “an alkyl group, an aryl group, an aralkyl group, an alkoxy group, or an alkylthio group, which may have a substituent such as a halogen atom such as a fluorine atom or a chlorine atom, or a cycloalkyl group such as a cyclohexyl group”; An amino group having a substituent; a fluorine atom; a chlorine atom;

More preferably, the substituent R ^f and the substituent R ^g are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom such as a fluorine atom, or aryl. A linear or branched alkoxy group having 1 to 10 carbon atoms which may be substituted with a halogen atom such as a fluorine atom or the like, and a particularly preferred substituent R ^f And the substituent R ^g is R ^b described later with respect to the general formula (2a) and the general formula (2b).

Adjacent R ^f may be bonded via a linking group or may be bonded to form a condensed ring. Here, examples of the “linking group” include the same as those described above. The ring formed by connection may be an aliphatic ring or an aromatic ring. That is, they may combine to form a condensed ring. Examples of the condensed ring include rings having about 6 to 20 carbon atoms such as a benzene ring (becomes a naphthalene ring together with the benzene ring A) and a naphthalene ring.

When R ^f is bonded to each other and does not form a condensed ring, m is preferably an integer of 0 to 4, more preferably an integer of 1 to 3, and an integer of 1 to 2. Is particularly preferred and 1 is most preferred. If m is 0, there is a possibility of forming a mixture at the time of synthesis or a decrease in the compatibility of the dye molecules, and if m is too large, the molecular weight increases and the extinction coefficient may decrease.

When R ^f is bonded to each other to form a condensed ring, the condensed ring may have an arbitrary monovalent substituent. That is, it may have an arbitrary monovalent substituent regardless of m atoms forming the condensed ring.

The substitution position of the substituent R ^{f on} the benzene ring is not particularly limited, but in the general formula (2a) and the general formula (2b), it may be substituted at the substitution position as shown as R ^b. It is preferable from the point of obtaining a simple substance in the structure.

The R ^f that is the substituent of the benzene ring A has been described above, but the same applies to R ^g that is the substituent of the benzene ring B.

  The near-infrared absorbing dye represented by the general formula (1) is a near-infrared absorbing dye represented by the following general formula (2a) or (2b). (Maximum absorption wavelength); durability such as heat resistance, heat and humidity resistance, light resistance; stability in pressure-sensitive adhesives; good dispersion and good solubility in pressure-sensitive adhesive resins;

［一般式（２ａ）及び（２ｂ）中、
Ｒ^３は置換基を有していてもよいチエニル基を示す。
Ｒ^ａは炭素数３〜１０の直鎖又は分岐アルキル基を示す。
Ｒ^ｂは炭素数１〜１０の直鎖若しくは分岐アルキル基、シクロアルキル基、又は、炭素数１〜６の直鎖若しくは分岐アルコキシ基を示す（ただし、Ｒ^ｂが分岐アルコキシ基である場合は、Ｒ^ｂは、ＯＲ^ａと同じ基である）。
Ｍ^１は金属原子を示す。］

[In the general formulas (2a) and (2b),
R ³ represents a thienyl group which may have a substituent.
R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms.
R ^b represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms (provided that when R ^b is a branched alkoxy group, R ^b is the same group as OR ^a ).
M ¹ represents a metal atom. ]

R ³ represents a thienyl group which may have a substituent, and the substituent here is as described above. R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ^a is as described above. It is as described above with regard M ¹ of a metal atom.

R ^b represents a linear or branched alkyl group, a cycloalkyl group, or a linear or branched alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 10 carbon atoms. Specific examples of R ^b include, for example, methyl group; ethyl group; n-propyl group, isopropyl group; n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group; n- Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group; n-hexyl group, 1-methyl Pentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethyl Examples thereof include a butyl group and a 2,3-dimethylbutyl group.

Examples of R ^b include those exemplified as preferred groups in R ^f and R ^g of the general formula (1), and the same applies to preferred substituents for the groups.

In addition, when R ^b is an alkoxy group, the alkyl group in the alkoxy group is specifically an n-heptyl group except for the methyl group and ethyl group among the groups described above as R ^b , Methylhexyl group, ethylpentyl group, dimethylpentyl group; n-octyl group, methylheptyl group, ethylhexyl group, dimethylhexyl group; n-nonyl group, methyloctyl group, ethylheptyl group, dimethylheptyl group; n-decyl group, And a group obtained by adding a methylnonyl group, an ethyloctyl group, a dimethyloctyl group, and the like.

  The near-infrared absorbing dye represented by the general formula (1) of the present invention exhibits a shielding effect in the wavelength region of 750 nm to 1200 nm, and further has a maximum absorption wavelength in the range of 850 nm to 1200 nm. Particularly preferred. That is, the near-infrared absorbing dye of the present invention is excellent in durability such as heat resistance, moist heat resistance, and light resistance, and at the same time, the maximum absorption wavelength region can be on the long wavelength side (850 nm to 1200 nm). In order to take advantage of the performance compatibility, the near-infrared absorbing dye of the present invention preferably has a maximum absorption wavelength in the range of 850 nm to 1200 nm, more preferably in the range of 880 nm to 1100 nm, more preferably 900 nm to Those in the range of 1000 nm are particularly preferred.

Here, the near-infrared absorbing dye represented by the general formula (1) of the present invention preferably has a ligand (ligand) moiety having a molecular weight of 1000 or less, particularly preferably 700 or less.
Moreover, the molar extinction coefficient of the near-infrared absorbing dye represented by the general formula (1) of the present invention is usually 5000 or more, preferably 8000 or more.

  The solubility of the near-infrared absorbing dye represented by the general formula (1) of the present invention in an aromatic hydrocarbon solvent such as toluene, an ether solvent such as tetrahydrofuran and dimethoxyethane, and a ketone solvent such as methyl ethyl ketone is usually 0. .1% or more, preferably 0.5% or more.

<< Specific Examples of Near-Infrared Absorbing Dye of the Present Invention >>
Preferred examples of the near-infrared absorbing dye represented by the general formula (1) of the present invention are illustrated below.

<< Method for Synthesizing Near-Infrared Absorbing Dye of the Present Invention >>
Although the preferable manufacturing method of the near-infrared absorption pigment | dye represented by General formula (1) of this invention is not specifically limited, For example, it is as follows. That is, first, using a substituted phenol, a substituted aniline or the like as a starting material, using a hydroxyl group or amino group as a base with KOH, NaOH, K ₂ CO ₃ , Na ₂ CO ₃ , Cs ₂ CO ₃ or the like, a phase transfer catalyst (tetra Etherification or N, N-alkylation with an alkyl halide in the presence of an alkyl ammonium salt).

  For the obtained ether form or N, N-dialkylaniline, see, for example, Chem. Rev. 106, 2126-2208 (2006), Friedel-Crafts acylation is carried out in the presence of an acid. Examples of the acid include aluminum chloride, tin chloride, lanthanoid triflate, zeolite, protonic acid (sulfuric acid, phosphoric acid, etc.), iron chloride, zinc chloride, polyphosphoric acid, and the like.

  Subsequently, α-hydrogen next to the carbonyl group is selectively selected from quaternary ammonium tribromide (eg, benzyltrimethylammonium tribromide, tetrabutylammonium tribromide, trimethylphenylammonium tribromide, etc.) or pyridinium tribromide. Monobrominated only at the α-position.

  Next, bromo group is converted to —SC (S) OEt group or —SC (S) O-isoPr group (where Et is an ethyl group, and isoPr is an isopropyl group) by potassium ethoxyxanthate or potassium isopropoxyxanthate). And a ring closure reaction in hydrobromic acetic acid solution (HBr-AcOH) to obtain a precursor 1,3-dithiol-2-one derivative. Here, a halogenated solvent (for example, methylene chloride, chloroform, dichloroethane, etc.) may coexist in the hydrobromic acid solution.

  Furthermore, for example, Mol. Cryst. Liq. Crst. Lett, 56, 249 (1980) and the like can be synthesized by forming a metal-containing complex by a known method.

<< Novelty of near-infrared absorbing dye of the present invention >>
The near-infrared absorbing dye of the present invention is one in which R ¹ and R ² have a heterocyclic group in the general formula (1). For a compound in which R ¹ or R ² in the conventionally known general formula (1) is a benzene ring, the following bromination method using bromine / acetic acid (Br ₂ / AcOH) is known as a general method. It ’s just that.

On the other hand, in the case where R ¹ and R ² in the general formula (1) are heterocyclic rings, the reactivity at the site at the α-position with respect to the hetero atom is usually high. It was difficult to synthesize a ligand (ligand) moiety that is a precursor of a near-infrared absorbing dye represented by: This is also clear from the method of Condition 1 of Synthesis Example 1-2 in the examples described later. That is, as shown in the following reaction formula, when the heterocyclic ring is a thiophene ring (that is, when R ¹ and R ² are thienyl groups in the general formula (1)), Br reacts with the thiophene ring in the bromination step. Therefore, the α-hydrogen next to the carbonyl group could not be selectively replaced with Br ₂ .

According to the present invention, as described above, quaternary ammonium tribromide (eg, benzyltrimethylammonium tribromide, tetrabutylammonium tribromide, trimethylphenylammonium tribromide, etc.), pyridinium tribromide, instead of bromine (Br ₂ ) of the conventional method. By using tribromides such as bromide, the α-hydrogen next to the carbonyl group could be selectively monobrominated for the first time. This is also apparent from the method of Condition 2 of Synthesis Example 1-2 in the examples described later.

  Further, in the above reaction formula, when the position where Br is bonded is already substituted with an alkyl group or the like, Br cannot react at that position. Therefore, the compound of the present invention can also be synthesized by the above conventional method. There seems to be, but actually, it is necessary to replace the benzene ring with the α-alkylthiophene ring from the stage of the second step (Friedel-Crafts acylation), which is not realistic. As is clear from Synthesis Examples [2-1] to [2-3] in Examples described later, the near-infrared absorbing dye represented by the general formula (1) of the present invention can be synthesized for the first time by the production method of the present invention. It became possible.

Japanese Patent Application Laid-Open Nos. 2004-069952 and 2008-308622 describe cases where R ¹ and R ² are thienyl groups. However, the invention described therein is a group in which X ¹ and X ² are short, and is a requirement of the general formula (1) “X ¹ and X ² are each independently a carbon atom, oxygen atom, nitrogen atom And a monovalent group having a total of 4 or more of at least one kind of atom selected from the group consisting of silicon atoms. In the case where X ¹ and X ² are short groups, they can be synthesized by a method using Hg or the like. In these publications, it is considered that the method was used, but in such methods, a long group X ¹ , The ligand part of the near-infrared absorbing dye represented by the general formula (1) of the present invention having X ² cannot be synthesized.

<Near-infrared absorbing dye-containing adhesive>
The near-infrared absorbing dye represented by the general formula (1) of the present invention can exhibit high stability even when contained in an adhesive. It is not necessary to form a layer for each dye, and the near-infrared absorbing dye of the present invention is excellent in that an adhesive can be prepared by mixing dyes. Another embodiment of the present invention is a pressure-sensitive adhesive containing a near-infrared absorbing dye. In the near-infrared absorbing dye-containing pressure-sensitive adhesive, the above-mentioned near-infrared absorbing dye of the present invention can be used alone or in combination of two or more.

<Near-infrared absorbing dye mixture>
Moreover, the near-infrared absorbing dye represented by the general formula (1) of the present invention is a near-infrared absorbing dye mixture obtained by mixing one or more of the near-infrared absorbing dyes represented by the general formula (1). Can be used. In addition, it can be used as a near-infrared absorbing dye mixture by mixing with one or more second near-infrared absorbing dyes having a maximum absorption wavelength described later in the range of 750 nm to 1200 nm, preferably 750 nm to 950 nm. . The near-infrared absorbing dye mixture of the present invention may be a mixture of solid near-infrared absorbing dyes or a solution obtained by dissolving or dispersing a near-infrared absorbing dye in a solvent. The near-infrared absorbing dye mixture of the present invention can be suitably used for a near-infrared absorbing filter.

<< second near infrared absorbing dye >>
The above-mentioned near-infrared absorbing dye-containing pressure-sensitive adhesive (hereinafter sometimes simply referred to as “pressure-sensitive adhesive”) has a maximum absorption wavelength of 750 nm to 1200 nm in addition to the “near infrared absorbing dye of the present invention”. It is preferable to contain a second near-infrared absorbing dye in the range in order to broaden the absorption wavelength range.

  Examples of the second near-infrared absorbing pigment include general pigments such as inorganic pigments, organic pigments, organic dyes, and pigments. Examples of inorganic pigments include cobalt compounds, iron compounds, and chromium compounds. Examples of organic pigments include azo, indolinone, quinacridone, vat, phthalocyanine, and naphthalocyanine.

  Moreover, as organic dyes and pigments, metal complex systems such as near infrared absorbing pigments represented by the general formula (3) described later, azine systems, azo systems, nickel azo complex systems, azomethine systems, anthraquinone systems, indigoid systems, Indiananiline, oxazine, oxonol, xanthene, quinophthalone, cyanine, squarylium, stilbene, tetraazaporphyrin, triphenylmethane, naphthoquinone, pyrarozone, pyromethene, dipyrromethene, benzylidene, Examples include polymethine series, methine series, and chromium complex salts.

  The above-mentioned “near infrared absorbing dye represented by the general formula (1) of the present invention” is a long wavelength side (for example, 850 nm to 1200 nm, among 750 nm to 1200 nm required as the maximum absorption wavelength of the near infrared absorbing dye). The maximum absorption wavelength of the “second near-infrared absorbing dye” to be further contained in the pressure-sensitive adhesive is in the range of 750 nm to 950 nm on the relatively short wavelength side in the near-infrared region. Is preferred. As a result of mixing (combination), it has a shielding effect in a wide wavelength range, and in principle, emits strong near infrared rays. For example, even around plasma display panels, cordless phones, near infrared remote controls, It is possible to prevent malfunctions of certain other electronic devices.

  That is, the “second near-infrared absorbing dye” is at a shorter wavelength than the above-described “near-infrared absorbing dye represented by the general formula (1) of the present invention” in which the maximum absorption wavelength is contained in the adhesive. And it is preferable that the maximum absorption wavelength is in the range of 750 nm to 950 nm.

  Examples of the second near-infrared absorbing dye having a maximum absorption wavelength in the range of 750 nm to 950 nm, which are used in combination in the preparation of the pressure-sensitive adhesive, include those described above. Particularly preferably, the following general formula (3) It is a near-infrared absorbing dye represented by

［一般式（３）中、
Ｘ及びＹは、それぞれ独立して、硫黄原子、酸素原子、又は、置換基を有していてもよい窒素原子を示す。
Ｍ^２は金属原子を示す。
（Ａ）Ｘが置換基を有する窒素原子の場合；
窒素原子の置換基は、下記一般式（４ａ）で表される化合物であり、

［一般式（４ａ）中、
Ｒは、炭素原子、酸素原子、硫黄原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計３以上有する１価の置換基を示し、Ｒの末端が一般式（３）のベンゼン環に結合していてもよい。
Ｒ’は、任意の１価の置換基を示し、Ｒ’同士は結合して縮合環を形成していてもよい。
Ｒ’同士が結合して縮合環を形成していないときは、ｎ’は０〜４の整数であり、Ｒ’同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。
Ｒ^Ｘ及びＲ^Ｙは、それぞれ独立して１価の置換基を示し、連結基を介して結合していてもよく、Ｒ^Ｘ及びＲ^Ｙが結合して縮合環を形成していてもよい。］

[In general formula (3),
X and Y each independently represent a sulfur atom, an oxygen atom, or a nitrogen atom that may have a substituent.
M ² represents a metal atom.
(A) when X is a nitrogen atom having a substituent;
The substituent of the nitrogen atom is a compound represented by the following general formula (4a),

[In the general formula (4a),
R represents a monovalent substituent having a total of 3 or more of at least one kind selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, and the terminal of R is represented by the general formula (3) It may be bonded to the benzene ring.
R ′ represents an arbitrary monovalent substituent, and R ′ may be bonded to each other to form a condensed ring.
When R ′ is not bonded to form a condensed ring, n ′ is an integer of 0 to 4, and when R ′ is bonded to form a condensed ring, the condensed ring is arbitrary. May have a monovalent substituent.
R ^X and R ^Y each independently represent a monovalent substituent, and may be bonded via a linking group, or R ^X and R ^Y may be bonded to form a condensed ring. ]

［一般式（４ｂ）中、
Ｘ^ｈは、炭素原子、酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種類の原子を合計３以上有する１価の基を示す。
Ｒ^ｈは、任意の１価の置換基を示し、Ｒ^ｈ同士は結合して縮合環を形成していてもよい。
Ｒ^ｈ同士が結合して縮合環を形成していないときは、ｐは０〜４の整数であり、Ｒ^ｈ同士が結合して縮合環を形成しているときは、該縮合環は任意の１価の置換基を有していてもよい。］ (B) when X is an oxygen atom or a sulfur atom;
R ^Y represents a monovalent substituent.
R ^X is a compound represented by the following general formula (4b).

[In general formula (4b),
X ^h represents a monovalent group having a total of 3 or more of at least one kind of atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom.
R ^h represents an arbitrary monovalent substituent, and R ^h may be bonded to each other to form a condensed ring.
When R ^h is bonded to form a condensed ring, p is an integer of 0 to 4, and when R ^h is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]

  Hereinafter, the general formula (3) will be described in detail.

In the general formula (3), M ² is not particularly limited as long as it is a metal atom that can take a tetracoordinate form. Preferably, a Group 10 metal atom of Ni, Pd or Pt; Co; Fe; Cu; Ag; Au; More preferred is a group 10 metal atom, and particularly preferred is Ni or Pd.

  X and Y each independently represent a sulfur atom, an oxygen atom, or a nitrogen atom having a substituent.

(1) In the case where X is a nitrogen atom having a substituent The substituent of the nitrogen atom is a group represented by the following general formula (4a).

The compound represented by the general formula (1) has two Rs as a whole compound, but Rs may be bonded to each other via a linking group. Moreover, (4a) may form a condensed ring.
In the general formula (4a), R ′ is an arbitrary substituent, and R ′ may be bonded to each other to form a condensed ring. n ′ is 0 to 4 in the case of a single ring and 0 to 10 in the case of a condensed ring.

  R represents a monovalent substituent having a total of 3 or more of at least one atom selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom.

  The monovalent substituent having 3 or more in total of at least one kind selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom is an optionally substituted hydrocarbon group, An optionally substituted carbonyl group, an optionally substituted hydrocarbon thio group, an optionally substituted silyl group, an optionally substituted hydrocarbon amino group, and an optionally substituted hydrocarbon oxy group. .

(A) Hydrocarbon group Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aryl group, and an aralkyl group.
Examples of the aliphatic hydrocarbon group include n-butyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, 2-ethylbutyl group, 2-butyl group, cyclohexyl group, and 3-pentyl group. Examples include chain, branched chain, or cyclic alkyl groups; alkenyl groups such as 2-butenyl group, 3-butenyl group, and 2,4-pentadienyl group; and alkynyl groups such as 2-hexyne group. Among these, an aliphatic hydrocarbon group having about 4 to 12 carbon atoms is preferable, and a branched chain aliphatic hydrocarbon group having about 4 to 12 carbon atoms is particularly preferable.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, an azulenyl group, and a metallocene ring group. Of these, a monocyclic or condensed bicyclic aryl group having about 6 to 12 carbon atoms is preferred. Examples of the aralkyl group include those in which the above-described aliphatic hydrocarbon group and the above-described aryl group are bonded.

(B) Heterocyclic group Examples include a thienyl group, a furyl group, a pyrrolyl group, a pyridyl group, an imidazolyl group, a pyrazolyl group, an indolyl group, a quinoxalinyl group, an acridinyl group, a thiazolyl group, and a pyrazinyl group. Of these, a monocyclic or bicyclic 5-membered heterocyclic group having about 3 to 12 carbon atoms is preferred.

(C) Carbonyl group An acyl group (—COR), a carbamoyl group (—CONRR ′), an alkoxycarbonyl group (—C (O) OR), an aryloxycarbonyl group, and a heterocyclic oxycarbonyl group are exemplified. Specifically, R in the acyl group (—COR) is the same as the specific examples of the aliphatic hydrocarbon group, aryl group, and heterocyclic group described above, in addition to an n-propyl group and a 2-propenyl group. Etc. Further, R and R ′ of the carbamoyl group (—CONRR ′) are the same as the specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group described above, in addition to an ethyl group, an n-propyl group, A 2-propenyl group, an ethynyl group, etc. are mentioned. R of the alkoxycarbonyl group (—C (O) OR) is the same as the specific examples of the aliphatic hydrocarbon group mentioned above, but also an ethyl group, an n-propyl group, a 2-propenyl group, an ethynyl group, etc. Is mentioned. Further, R of the aryloxycarbonyl group (—C (O) OR) is the same as the specific examples of the aryl group described above, and R of the heterocyclic oxycarbonyl group (—C (O) OR) is Examples thereof are the same as the specific examples of the heterocyclic group mentioned above.

(D) Hydrocarbon thio group R in the hydrocarbon thio group (-SR) is the same as the specific examples of the hydrocarbon group, aryl group and heterocyclic group described above, in addition to n-propyl group, 2- A propenyl group, an ethynyl group, etc. are mentioned.

(E) Silyl group As the silyl group, there are silyl groups such as t-butyldiphenylsilyl group, n-butyldimethylsilyl group, dimethylpropylsilyl group, dimethylphenylsilyl group, dimethylisopropylsilyl group, triisopropylpropylsilyl group and the like. Can be mentioned. Preferably, it is an alkylsilyl group having about 3 to 18 carbon atoms.

(F) Hydrocarbon amino group R and R 'of the hydrocarbon amino group (-NRR') are the same as the specific examples of the hydrocarbon group, aryl group and heterocyclic group described above, and n-propyl. Group, 2-propenyl group, ethynyl group and the like.

(G) Hydrocarbonoxy group R of the hydrocarbonoxy group (-OR) is the same as the specific examples of the hydrocarbon group, aryl group and heterocyclic group described above, in addition to n-propyl group, 2- A propenyl group, an ethynyl group, etc. are mentioned.

When the above groups (a) to (g) have a substituent, the type of the substituent is not particularly limited as long as it does not affect the stability of the dye and the dispersion / solubility in the adhesive resin. .
For example, halogen atom, hydroxyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio Group, amino group, acyl group, aminoacyl group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, aryl Examples include groups selected from the group consisting of sulfonyl groups, heteroarylsulfonyl groups, imide groups, silyl groups, and the like.

  Specifically, an alkyl group having about 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having about 1 to 6 carbon atoms such as an ethynyl group or a propylenyl group; an alkynyl group having about 1 to 6 carbon atoms such as an acetylenyl group An aryl group having about 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a heteroaryl group having about 3 to 20 carbon atoms such as a thienyl group, a furyl group or a pyridyl group; 1 to 1 carbon atoms such as an ethoxy group or a propoxy group; Alkoxy groups of about 6; aryloxy groups of about 6 to 20 carbon atoms such as phenoxy groups and naphthoxy groups; heteroaryloxy groups of about 3 to 20 carbon atoms such as pyridyloxy groups and thienyloxy groups; methylthio groups and ethylthio groups An alkylthio group having about 1 to 6 carbon atoms such as phenylthio group and an arylthio group having about 6 to 20 carbon atoms such as naphthylthio group; pyridylthio group, A heteroarylthio group having about 3 to 20 carbon atoms such as an nylthio group; an amino group optionally having a substituent having about 1 to 20 carbon atoms such as a dimethylamino group and a diphenylamino group; an acetyl group, a pivaloyl group and the like An acyl group having about 2 to 20 carbon atoms; an acylamino group having about 2 to 20 carbon atoms such as an acetylamino group and a propionylamino group; a ureido group having about 2 to 20 carbon atoms such as a 3-methylureido group; methanesulfonamide A sulfonamide group having about 1 to 20 carbon atoms such as a benzenesulfonamide group; a carbamoyl group having about 1 to 20 carbon atoms such as a dimethylcarbamoyl group and an ethylcarbamoyl group; 1 to 20 carbon atoms such as an ethylsulfamoyl group A sulfamoyl group of about 1 to 20 carbon atoms such as a dimethylsulfamoylamino group; An alkoxycarbonyl group having about 2 to 6 carbon atoms such as a carbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group having about 7 to 20 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group; 6 carbon atoms such as a pyridyloxycarbonyl group A heteroaryloxycarbonyl group of about -20; an alkylsulfonyl group of about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group and a trifluoromethanesulfonyl group; a carbon number of 6 to 6 such as a benzenesulfonyl group and a monofluorobenzenesulfonyl group An arylsulfonyl group having about 20 carbon atoms; a heteroarylsulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide group having about 4 to 20 carbon atoms such as phthalimide; a substituent selected from the group consisting of an alkyl group and an aryl group The three-substituted Examples include a tolyl group.

  Preferred are an alkyl group, an alkoxy group, an alkylthio group, an amino group having a substituent, a fluorine atom, and a chlorine atom.

R ′ is not particularly limited as long as it does not affect the stability of the dye and the dispersion / solubility in the adhesive resin, and is an arbitrary monovalent substituent.
For example, halogen atom, hydroxyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio Group, amino group, acyl group, aminoacyl group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, aryl Examples include groups selected from the group consisting of sulfonyl groups, heteroarylsulfonyl groups, imide groups, silyl groups, and the like.

  Specifically, an alkyl group having about 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having about 1 to 6 carbon atoms such as an ethynyl group or a propylenyl group; an alkynyl group having about 1 to 6 carbon atoms such as an acetylenyl group An aryl group having about 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a heteroaryl group having about 3 to 20 carbon atoms such as a thienyl group, a furyl group or a pyridyl group; 1 to 1 carbon atoms such as an ethoxy group or a propoxy group; Alkoxy groups of about 6; aryloxy groups of about 6 to 20 carbon atoms such as phenoxy groups and naphthoxy groups; heteroaryloxy groups of about 3 to 20 carbon atoms such as pyridyloxy groups and thienyloxy groups; methylthio groups and ethylthio groups An alkylthio group having about 1 to 6 carbon atoms such as phenylthio group and an arylthio group having about 6 to 20 carbon atoms such as naphthylthio group; pyridylthio group, A heteroarylthio group having about 3 to 20 carbon atoms such as an nylthio group; an amino group optionally having a substituent having about 1 to 20 carbon atoms such as a dimethylamino group and a diphenylamino group; an acetyl group, a pivaloyl group and the like An acyl group having about 2 to 20 carbon atoms; an acylamino group having about 2 to 20 carbon atoms such as an acetylamino group and a propionylamino group; a ureido group having about 2 to 20 carbon atoms such as a 3-methylureido group; methanesulfonamide A sulfonamide group having about 1 to 20 carbon atoms such as a benzenesulfonamide group; a carbamoyl group having about 1 to 20 carbon atoms such as a dimethylcarbamoyl group and an ethylcarbamoyl group; 1 to 20 carbon atoms such as an ethylsulfamoyl group A sulfamoyl group of about 1 to 20 carbon atoms such as a dimethylsulfamoylamino group; An alkoxycarbonyl group having about 2 to 6 carbon atoms such as a carbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group having about 7 to 20 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group; 6 carbon atoms such as a pyridyloxycarbonyl group A heteroaryloxycarbonyl group of about -20; an alkylsulfonyl group of about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group and a trifluoromethanesulfonyl group; a carbon number of 6 to 6 such as a benzenesulfonyl group and a monofluorobenzenesulfonyl group An arylsulfonyl group having about 20 carbon atoms; a heteroarylsulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide group having about 4 to 20 carbon atoms such as phthalimide; a substituent selected from the group consisting of an alkyl group and an aryl group The three-substituted Examples include a tolyl group.

  Preferred are an alkyl group, an alkoxy group, an alkylthio group, an amino group having a substituent, a fluorine atom, and a chlorine atom.

R ^X and R ^Y each independently represent a monovalent substituent, and R ^X and R ^Y may be bonded via a linking group. Preferably, a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted carbonyl group, an optionally substituted hydrocarbon thio group, an optionally substituted silyl group, an optionally substituted Examples thereof include a good hydrocarbon amino group, an optionally substituted hydrocarbon oxy group, a hydrocarbon carbonyl group, a cyano group, and a halogen atom. Specific examples of R ′ in the general formula (A) are applicable to these specific examples.

のような、単環、縮合環からなる構造が挙げられ、より好ましくは、 More preferably, it is a case where R ^X and R ^Y are bonded via a linking group, specifically,

And a structure composed of a single ring or a condensed ring, and more preferably

であり、特に好ましくは、

And particularly preferably,

である。

It is.

  These structures may have a monovalent substituent. Specifically, it is the same as that described as the substituent which may be substituted in (a). Among these, an alkyl group, an alkoxy group, an alkylthio group, a fluorine atom, and a chlorine atom are preferable, and a tertiary and secondary branched alkyl group is particularly preferable.

The structure in the case where R ^X and R ^Y are bonded via a linking group to form the above structure (benzene ring) is represented by the following formula (3a).

In general formula (3a), R ¹¹ and R ¹² are each a monovalent group having at least one atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom in total of 3 or more. R ¹¹ and R ¹² may be bonded via a linking group.
Z represents an oxygen atom, a sulfur atom, or a nitrogen atom that may have a substituent.

The aromatic ring may have an arbitrary substituent, and adjacent groups may be bonded to each other through a linking group, or may further form a condensed ring.
M ² represents a metal atom.
Here, Z of the general formula (3a) is, Y in the general formula (3), ^{M 2} in the general formula (3a) corresponds to ^{M 2} in the general formula (3). Further, R ¹¹ and R ¹² in the general formula (3a) correspond to R in the general formula (a).

More preferable examples include the following (1)-(i) to (iii).
(1)-(i) This is a case where X is a nitrogen atom having a substituent, Y is an oxygen atom, and R ^x and R ^y are bonded via a linking group. In particular, when a benzene ring is formed, it is desirable that two or more benzene rings formed by combining R ^x and R ^y are substituted with branched alkyl groups. As R in the above formula (4a), which is a nitrogen atom substituent, a linear or branched alkyl group which may have a substituent having about 3 to 10 carbon atoms, or 2 to 10 carbon atoms. An alkoxy group optionally having a substituent, an alkylthio group, or a substituted amino group. Rs may be bonded via a linking group.

(1)-(ii) This is a case where X is a nitrogen atom having a substituent, Y is a sulfur atom, and R ^x and R ^y are bonded via a linking group. In particular, when a benzene ring is formed, the benzene ring formed by combining R ^x and R ^y has an alkyl group, an alkoxy group, an alkylthio group, a cyano group, or a halogen atom as a substituent. Is preferred. As R in the above formula (4a), which is a nitrogen atom substituent, a linear or branched alkyl group which may have a substituent having about 3 to 10 carbon atoms, or 2 to 10 carbon atoms. An alkoxy group, an alkylthio group, or a substituted amino group which may have a certain degree of substituents is preferred. Rs may be bonded via a linking group.

(1)-(iii) This is a case where X is a nitrogen atom having a substituent, Y is a nitrogen atom having hydrogen, and R ^x and R ^y are bonded via a linking group. In particular, when a benzene ring is formed, the substituent of the benzene ring formed by combining R ^x and R ^y is preferably an alkyl group, an alkoxy group, an alkylthio group, a cyano group, or a halogen atom. . As R in the above formula (4a) which is a substituent of the nitrogen atom X, in particular, a linear or branched alkyl group which may have a substituent having about 3 to 10 carbon atoms, or 2 to 2 carbon atoms. An alkoxy group which may have about 10 substituents, an alkylthio group, or a substituted amino group is preferable. Rs may be bonded via a linking group.

(2) When X is an oxygen atom or a sulfur atom R ^X is a group represented by the following general formula (4b).

The compound represented by the general formula (3) has two Rs as a whole compound, but Rs may be bonded to each other via a linking group.
In formula (4b), X ^h has at least one kind of atoms total 4 or more selected from a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom, a monovalent substituent. X ^h is an optionally substituted hydrocarbon group, an optionally substituted carbonyl group, an optionally substituted hydrocarbon thio group, an optionally substituted silyl group, or an optionally substituted. Examples thereof include a hydrocarbon amino group and an optionally substituted hydrocarbon oxy group. Specifically, it has a total of 4 or more of at least one atom selected from carbon atom, oxygen atom, nitrogen atom and silicon atom among R in the general formula (4a) of the general formula (3).

R ^h is an arbitrary substituent, and R ^h may be bonded to each other to form a condensed ring. p is 0 to 4 in the case of a single ring. When a condensed ring is formed, the substituent of the substituent R ^h is 0-10.
^Rh is not particularly limited as long as the type of the substituent does not affect the stability of the dye and the decomposition / solubility in the adhesive resin.

  For example, halogen atom, hydroxyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio Group, amino group, acyl group, aminoacyl group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, aryl Examples include groups selected from the group consisting of sulfonyl groups, heteroarylsulfonyl groups, imide groups, silyl groups, and the like. Specifically, it is the same as the specific example of R ′ in the general formula (4a) in the general formula (3).

R ^Y represents a monovalent substituent. R ^Y includes a hydrogen atom, an optionally substituted hydrocarbon group, an optionally substituted carbonyl group, an optionally substituted hydrocarbon thio group, an optionally substituted silyl group, and a substituted And an optionally substituted hydrocarbon amino group, an optionally substituted hydrocarbon oxy group, a hydrocarbon carbonyl group, a cyano group, or a halogen atom. Specifically, it is the same as the specific example of R ′ in the general formula (4a) of the general formula (3).

In the above description, a more preferable example is as follows. A case where X and Y are sulfur atoms and R ^X has the general formula (4a). The structure at this time is represented by the following formula (3b).

In General Formula (3b), R ¹³ and R ¹⁴ each independently represent a monovalent substituent.
X ¹¹ and X ¹² are each independently a monovalent group having a total of 4 or more of at least one kind of atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom. X ¹¹ and X ¹² may be bonded via a linking group.

The aromatic ring may have an arbitrary substituent, and adjacent groups may be bonded via a linking group.
M ³ represents a metal atom.

Here, R ¹³ and R ¹⁴ in the general formula (3b) correspond to R ^{X in} the general formula (3), and M ^{3 in the} general formula (3b) corresponds to M ² in the general formula (3). X ¹¹ and X ^{12 in} the general formula (3b) correspond to R in the general formula (a).

  Of the compounds represented by the general formula (3b), the compound represented by the following general formula (5) is used as a second near-infrared absorbing dye that is mixed with an adhesive resin and used in a near-infrared absorbing adhesive. Particularly preferred can be used.

［一般式（５）において、
Ｒ^４は、水素原子；炭素数１〜５の直鎖又は分岐アルキル基；アルキル基、アルコキシ基、置換アミノ基又はハロゲン原子を置換基として有していてもよいフェニル基；アルキル基、アルコキシ基、置換アミノ基又はハロゲン原子を置換基として有していてもよいフェニルチオ基を示す。
Ｒ^６は、炭素数３〜１０の直鎖又は分岐アルキル基を示す。
Ｒ^５は、炭素数１〜１０の直鎖若しくは分岐アルキル基、又は、炭素数１〜６の直鎖若しくは分岐アルコキシ基（ただし、Ｒ^５が分岐アルコキシ基である場合は、Ｒ^５は、ＯＲ^６と同じ基である）。
Ｍ^４は金属原子を表す。］

[In general formula (5),
R ⁴ represents a hydrogen atom; a linear or branched alkyl group having 1 to 5 carbon atoms; an alkyl group, an alkoxy group, a substituted amino group, or a phenyl group optionally having a halogen atom as a substituent; an alkyl group or an alkoxy group Represents a phenylthio group optionally having a substituted amino group or a halogen atom as a substituent.
R ⁶ represents a linear or branched alkyl group having 3 to 10 carbon atoms.
R ⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms (provided that when R ⁵ is a branched alkoxy group, R ⁵ is OR ⁶ and the same group).
M ⁴ represents a metal atom. ]

R ⁴ in the general formula (5) corresponds to R ^Y in the general formula (3), and R ⁵ in the general formula (5) corresponds to R ^h in the general formula (4b) in the general formula (3). In the general formula (5), “—OR ⁶ ” corresponds to “—X ^h ” in the general formula (4b) in the general formula (3), and M ⁴ in the general formula (5) represents the general formula (3). corresponding to the ^{M 2.} M ⁴ is particularly preferably Ni.

［一般式（６）中、
Ｒ^７及びＲ^８は、置換基を有していてもよい炭化水素基、置換基を有していてもよいカルボニル基、シアノ基、ハロゲン原子、又は、水素原子を示す。
Ｒ^９及びＲ^１０は、置換基を有していてもよいアルキル基、又は、置換基を有していてもよいアリール基を示す。
Ｍ^５は金属原子を示す。］ Moreover, as a 2nd near-infrared absorption pigment | dye, the near-infrared absorption pigment | dye represented by following General formula (6) is also preferable.

[In general formula (6),
R ⁷ and R ⁸ represent a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a cyano group, a halogen atom or a hydrogen atom.
R ⁹ and R ¹⁰ represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
M ⁵ represents a metal atom. ]

In General Formula (6), R ⁷ and R ⁸ represent a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a cyano group, a halogen atom, or a hydrogen atom. Show. R ⁹ and R ¹⁰ represent an alkyl group which may have a substituent or an aryl group which may have a substituent. M ⁵ may be any metal as long as it has a planar tetradentate configuration.
M ⁵ is preferably Ni, Pd, Pt, Co, Fe, Cu, Au, Cr, or Mn. More preferred is Ni or Pd, and most preferred is Ni.

Examples of the hydrocarbon group for R ⁷ and R ⁸ include the following groups.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a 2-methylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a cyclohexylmethyl group, a neopentyl group, and 2-ethylbutyl. A linear, branched or cyclic alkyl group such as a group, isopropyl group, 2-butyl group, cyclohexyl group, 3-pentyl group, tert-butyl group, 1,1-dimethylpropyl group; 2-propenyl group, Examples thereof include alkenyl groups such as 2-butenyl group, 3-butenyl group and 2,4-pentadienyl group; and alkynyl groups such as ethynyl group. Of these, a branched alkyl group having 10 or less carbon atoms is preferred.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, an azulenyl group, and a metallocene ring group. Among these, a monocyclic or condensed bicyclic aryl group having 12 or less carbon atoms is preferable. More preferably, it is a phenyl group.

  Examples of the heterocyclic group include thienyl group, furyl group, pyrrolyl group, pyridyl group, imidazolyl group, pyrazolyl group, indoleyl group, quinoxalinyl group, acridinyl group, thiazolyl group, pyrazinyl group and the like. Of these, a thienyl group is particularly preferable.

  Examples of the carbonyl group which may have a substituent include an acyl group (—COR), a carbamoyl group (—CONRR ′), an alkoxycarbonyl group (—C (O) OR), an aryloxycarbonyl group, and a heterocyclic oxy group. A carbonyl group is mentioned. More specifically, R of the acyl group (—COR) and R and R ′ of the carbamoyl group (—CONRR ′) are specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group mentioned above. The same thing is mentioned. Examples of R of the alkoxycarbonyl group (—C (O) OR) are the same as the specific examples of the aliphatic hydrocarbon group mentioned above. Examples of R of the aryloxycarbonyl group (—C (O) OR) are the same as the specific examples of the aryl group described above. Examples of R of the heterocyclic oxycarbonyl group (—C (O) OR) are the same as the specific examples of the heterocyclic group described above.

Among these, R ⁷ and R ⁸ are more preferably a phenyl group. R ⁹ and R ¹⁰ are preferably a branched alkyl group described for R ⁷ , particularly a secondary alkyl group, or a phenyl group which may have a substituent.

Particularly preferred combinations of R ⁷ and R ⁸ are the following (a) to (d).
(A) when R ⁷ and R ⁸ have a phenyl group which may be substituted at the p-position and / or the m-position;
The substituent of the phenyl group is a monovalent substituent, and the adjacent substituents may be bonded directly or via a linking group. For example, halogen atom, hydroxyl group, nitro group, cyano group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio Group, amino group, acyl group, aminoacyl group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfamoylamino group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylsulfonyl group, aryl Examples include a sulfonyl group, a heteroarylsulfonyl group, an imide group, and a silyl group.

  Specifically, an alkyl group having about 1 to 6 carbon atoms such as a methyl group or an ethyl group; an alkenyl group having about 1 to 6 carbon atoms such as an ethynyl group or a propylenyl group; an alkynyl group having about 1 to 6 carbon atoms such as an acetylenyl group An aryl group having about 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a heteroaryl group having about 3 to 20 carbon atoms such as a thienyl group, a furyl group or a pyridyl group; 1 to 1 carbon atoms such as an ethoxy group or a propoxy group; Alkoxy groups of about 6; aryloxy groups of about 6 to 20 carbon atoms such as phenoxy groups and naphthoxy groups; heteroaryloxy groups of about 3 to 20 carbon atoms such as pyridyloxy groups and thienyloxy groups; methylthio groups and ethylthio groups An alkylthio group having about 1 to 6 carbon atoms such as phenylthio group and an arylthio group having about 6 to 20 carbon atoms such as naphthylthio group; pyridylthio group, A heteroarylthio group having about 3 to 20 carbon atoms such as an nylthio group; an amino group optionally having a substituent having about 1 to 20 carbon atoms such as a dimethylamino group and a diphenylamino group; an acetyl group, a pivaloyl group and the like An acyl group having about 2 to 20 carbon atoms; an acylamino group having about 2 to 20 carbon atoms such as an acetylamino group and a propionylamino group; a ureido group having about 2 to 20 carbon atoms such as a 3-methylureido group; methanesulfonamide A sulfonamide group having about 1 to 20 carbon atoms such as a benzenesulfonamide group; a carbamoyl group having about 1 to 20 carbon atoms such as a dimethylcarbamoyl group and an ethylcarbamoyl group; 1 to 20 carbon atoms such as an ethylsulfamoyl group A sulfamoyl group of about 1 to 20 carbon atoms such as a dimethylsulfamoylamino group; An alkoxycarbonyl group having about 2 to 6 carbon atoms such as a carbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group having about 7 to 20 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group; 6 carbon atoms such as a pyridyloxycarbonyl group A heteroaryloxycarbonyl group of about -20; an alkylsulfonyl group of about 1 to 6 carbon atoms such as a methanesulfonyl group, an ethanesulfonyl group and a trifluoromethanesulfonyl group; a carbon number of 6 to 6 such as a benzenesulfonyl group and a monofluorobenzenesulfonyl group An arylsulfonyl group having about 20; a heteroarylsulfonyl group having about 3 to 20 carbon atoms such as a thienylsulfonyl group; an imide group having about 4 to 20 carbon atoms such as phthalimide; a substituent selected from the group consisting of an alkyl group or an aryl group The three-substituted Examples include a tolyl group.

  Particularly preferred are an alkyl group, an alkoxy group, an alkylthio group, an amino group for substituting an alkyl group, a fluorine atom, and a phenyl group having a chlorine atom.

(B) R ⁷ is a phenyl group having a substituent at least in the ortho position, and R ⁸ is a hydrogen atom;
It is particularly preferable that the ortho-position substituent is a monovalent substituent having a total of 4 or more of at least one kind selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom. Specifically, the hydrocarbon group includes the following (1) to (3).

(1) As an aliphatic hydrocarbon group, n-butyl group, 2-methylbutyl group, 3-methylbutyl group, cyclohexylmethyl group, neopentyl group, 2-ethylbutyl group, 2-butyl group, cyclohexyl group, 3-pentyl group Linear, branched or cyclic alkyl groups such as 2-alkenyl groups such as 2-butenyl group, 3-butenyl group and 2,4-pentadienyl group; and alkynyl groups such as 2-hexyne group. Of these, an aliphatic hydrocarbon group having about 4 to 12 carbon atoms is preferred, and a branched chain aliphatic hydrocarbon group having about 4 to 12 carbon atoms is particularly preferred.

(2) Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group, a fluorenyl group, a phenanthrenyl group, and an azulenyl group. Among these, a monocyclic or condensed bicyclic aryl group having 6 or more carbon atoms and 12 or less carbon atoms is preferable.

(3) Examples of the heterocyclic group include thienyl group, furyl group, pyrrolyl group, pyridyl group, imidazolyl group, pyrazolyl group, indoleyl group, quinoxalinyl group, acridinyl group, thiazolyl group, pyrazinyl group and the like. Among these, a monocyclic or bicyclic 5-membered heterocyclic group having 3 to 12 carbon atoms is preferable.

  Examples of the carbonyl group include an acyl group (—COR), a carbamoyl group (—CONRR ′), an alkoxycarbonyl group (—C (O) OR), an aryloxycarbonyl group, and a heterocyclic oxycarbonyl group. More specifically, R of the acyl group (—COR) is the same as the specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group described above, as well as n-propyl group, 2-propenyl. Groups and the like. R and R ′ of the carbamoyl group (—CONRR ′) are the same as the specific examples of the aliphatic hydrocarbon group, aryl group and heterocyclic group described above, but also an ethyl group, n-propyl group, 2- A propenyl group, an ethynyl group, etc. are mentioned. R of the alkoxycarbonyl group (—C (O) OR) is the same as the specific examples of the aliphatic hydrocarbon group mentioned above, but also an ethyl group, an n-propyl group, a 2-propenyl group, an ethynyl group, etc. Is mentioned. Examples of R of the aryloxycarbonyl group (—C (O) OR) are the same as the specific examples of the aryl group described above. Examples of R of the heterocyclic oxycarbonyl group (—C (O) OR) are the same as the specific examples of the heterocyclic group described above.

  As R of the hydrocarbon thio group (—SR), in addition to the same specific examples as the hydrocarbon group, aryl group and heterocyclic group described above, n-propyl group, 2-propenyl group, ethynyl group, etc. Is mentioned. As R and R ′ of the amino group (—NRR ′), in addition to the same specific examples as the hydrocarbon group, aryl group and heterocyclic group described above, n-propyl group, 2-propenyl group, ethynyl Groups and the like.

As R of the hydrocarbon oxy group (—OR), in addition to the same specific examples as the hydrocarbon group, aryl group and heterocyclic group described above, n-propyl group, 2-propenyl group, ethynyl group, etc. Is mentioned.
Examples of the silyl group include silyl groups such as t-butyldiphenylsilyl group, n-butyldimethylsilyl group, dimethylpropylsilyl group, dimethylphenylsilyl group, dimethylisopropylsilyl group, triisopropylpropylsilyl group, preferably An alkylsilyl group having 3 to 18 carbon atoms.

Among these, R ⁷ and R ⁸ are particularly preferably an alkyl group, an alkoxy group or an alkylthio group, and particularly preferably a branched alkyl group or a branched alkoxy group. Although it may have a substituent other than the ortho position, an alkyl group, an alkoxy group, an alkylthio group, a fluorine atom, a chlorine atom, or a cyano group is preferable.

(C) R ⁷ is a phenyl group in which the substituent is at least in the ortho position, and R ⁸ is a phenyl group having a substituent;
The substituent at the ortho position of R ⁷ is preferably a monovalent substituent having a total of 3 or more of at least one atom selected from a carbon atom, a sulfur atom, an oxygen atom, a nitrogen atom and a silicon atom. Particularly preferred are an alkyl group, an alkoxy group, and an alkylthio group. Although it may have a substituent other than the ortho position, an alkyl group, an alkoxy group, an alkylthio group, a fluorine atom, a chlorine atom, or a cyano group is preferable. The substituent of R ⁸ is preferably in the meta position and / or para position of the phenyl group, and is an arbitrary monovalent group, and particularly preferably an alkyl group, an alkoxy group, an alkylthio group, a fluorine atom, chlorine An atom or a cyano group.

(D) when R ⁷ and R ⁸ are phenyl groups where the substituent is at least in the ortho position;
The substituent at the ortho position of R ⁷ and R ⁸ is preferably a monovalent substituent having a total of 2 or more of at least one atom selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom. . Particularly preferred are an alkyl group, an alkoxy group, and an alkylthio group, and particularly preferred are a branched alkyl group or a branched alkoxy group. Although it may have a substituent other than the ortho position, an alkyl group, an alkoxy group, an alkylthio group, a fluorine atom, a chlorine atom, or a cyano group is preferable.

<<< Specific Example of Second Near-Infrared Absorbing Dye >>>
Preferred specific examples of the second near infrared absorbing dye are shown below.

<< Adhesive resin >>
The near-infrared absorbing dye-containing pressure-sensitive adhesive of the present invention contains the near-infrared absorbing dye represented by the general formula (1) of the present invention and an adhesive resin. Further, the near-infrared absorbing dye represented by the general formula (1) of the present invention, “the second near-infrared absorbing dye having a maximum absorption wavelength in the range of 750 nm to 1200 nm”, particularly preferably “the maximum absorption wavelength is Contains a second near-infrared absorbing dye having a shorter wavelength than the near-infrared absorbing dye of the present invention actually contained in the adhesive and having a maximum absorption wavelength in the range of 750 nm to 950 nm, and an adhesive resin. You may do. Hereinafter, the “near-infrared absorbing dye represented by the general formula (1) of the present invention” and the “second near-infrared absorbing dye” may be collectively referred to simply as “near-infrared absorbing dye”.

  The adhesive resin used in the adhesive of the present invention is a substance that binds two same or different solids and needs to have three characteristics. The first characteristic is that the two solids are brought into close contact with each other. The second characteristic is that each adherend has wettability and is firmly bonded to the adherend surface. The third characteristic is that the solid bonded through the pressure-sensitive adhesive does not peel off due to the destruction of the pressure-sensitive adhesive itself. For this reason, the glass transition temperature (Tg) of the adhesive resin (pressure-sensitive adhesive) needs to be low so that the fluidity is improved. Specifically, it is preferable that at least one component (resin) having a Tg of 10 ° C. or lower is included. In terms of adhesiveness, the ratio of the component (resin) having a Tg of 10 ° C. or less to the entire adhesive resin is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, and 50% by mass. % Or more is most preferable.

  Especially, it is preferable that Tg is 10 degrees C or less as the whole adhesive resin. Further, in order to improve the adhesion to the surface of the adherend, it is necessary to contain a functional group having an affinity for the surface of the adherend in the molecule. When the adhesive resin alone is not sufficient, it is necessary to react with a curing agent containing a polyfunctional group that reacts with the adhesive resin to increase the strength of the adhesive resin itself and prevent peeling.

  The acid value of the adhesive resin of the present invention is usually 0 mgKOH / g or more, usually 50 mgKOH / g or less, preferably 30 mgKOH / g or less, more preferably 20 mg / g or less. The hydroxyl value is usually 0 mgKOH / g or more, usually 20 mgKOH / g or less, preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less.

  The molecular weight of the adhesive resin is preferably a high molecular weight within a range that does not affect the adhesive properties. However, since the adhesive properties and the like may be reduced by increasing the molecular weight, the preferred molecular weight is a weight average molecular weight of 100,000 to It is 10 million, more preferably 1 million to 5 million. Further, durability and adhesive properties may be adjusted by mixing resins having different number average molecular weights.

  The adhesive resin of the present invention has a rubber-based resin, a (meth) acrylic resin, a silicon-based resin, a urethane-based resin, a polyvinyl butyral-based resin, and an ethylene-vinyl acetate-based resin (EVA) as long as there is a practical adhesive strength. , Polyvinyl ether resin, saturated amorphous polyester resin, melamine resin and the like may be used.

Depending on the purpose, the following may be added.
(1) As an anti-aging agent, phenol derivatives, amine derivatives, phosphorus derivatives, organic thioates and the like.

(2) As tackifying resin for improving tackiness, natural resins such as rosin and dammar, modified rosin, polyterpene resin, modified terpene, aliphatic hydrocarbon resin, cyclopentadiene resin, aromatic petroleum resin, Phenol resins, alkylphenol-acetylene resins, styrene resins, xylene resins, coumarone indene resins, vinyl toluene-α-methylstyrene copolymers, and the like.
(3) In order to improve low temperature characteristics, etc., phthalic acid plasticizers, phosphate ester plasticizers, adipic acid ester plasticizers, sebacic acid ester plasticizers, ricinoleic acid ester plasticizers, polyester plasticizers, Epoxy plasticizer.

  Many types of resin can be used as the adhesive resin, but many resins have low light transmittance of the resin itself, poor transparency, discoloration due to sunlight or heat, and adhesive resin. It may peel off due to its own alteration. Therefore, an acrylic resin-based adhesive resin having good optical properties, light resistance and heat resistance is preferable. Anti-aging agents, plasticizers, and the like may bleed after long-term use and gradually deteriorate in performance, so it is better not to use additives as much as possible.

  The pressure-sensitive adhesive of the present invention can be particularly preferably used for an optical filter. In that case, since visible light transmittance and light resistance are required, a (meth) acrylic resin is mainly used as the pressure-sensitive adhesive resin. It is preferable to use it.

  As the (meth) acrylic resin, a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group is a main component, and in order to add a functional group in the polymer, (meth) acrylic acid, 2- (Meth) acrylic resin copolymerized with functional group-containing monomers such as hydroxyethyl (meth) acrylate, or (meth) acrylic resin copolymerized with other copolymerizable monomers and oligomers Furthermore, a (meth) acrylic resin composition to which a crosslinking agent that reacts with a functional group of the (meth) acrylic resin is added can be used.

  Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl ( (Meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-decyl (meth) Examples include acrylate, iso-decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.

  Monomers having functional groups in the molecule include acrylic acid, methacrylic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 6-hydroxyhexyl. (Meth) acrylate etc. are mentioned.

  The cross-linking agent only needs to have at least two functional groups capable of reacting with the acrylic resin in the molecule, such as isocyanate compounds, epoxy compounds, amine compounds, aziridine compounds, melamine compounds, urea resins, and metal chelating agents. Are known.

  Of these, (meth) acrylic resins are preferable, and resins having butyl acrylate and 2-ethylhexyl acrylate as main components are particularly preferable. Furthermore, a pressure-sensitive adhesive containing a (meth) acrylic resin and a sheet-like adhesive is more preferable because of ease of workability. Moreover, in order to improve durability, you may use it, adding the said crosslinking agent.

  The pressure-sensitive adhesive of the present invention is obtained by mixing the near-infrared absorbing dye and the adhesive resin, but the content of the near-infrared absorbing dye is one kind of near-infrared absorption with respect to the solid content of the adhesive resin. The pigment is usually mixed so as to contain 0.001% by mass to 50% by mass. Preferably, they are mixed so as to contain 0.01 mass% to 40 mass%, more preferably 0.05 mass% to 30 mass%, particularly preferably 0.1 mass% to 20 mass%. When two or more kinds of near-infrared absorbing dyes of the present invention, or when containing two or more kinds of near-infrared absorbing dyes, the content of each near-infrared absorbing dye is , And mix so as to be in the above range.

  The pressure-sensitive adhesive of the present invention may be prepared by uniformly mixing a dye and a pressure-sensitive resin with a known stirrer or kneader, or after dispersing or dissolving a near-infrared absorbing dye in a solvent, the pressure-sensitive adhesive resin And may be mixed uniformly.

  Examples of the solvent for dispersing or dissolving the near-infrared absorbing dye include halogenated aliphatic hydrocarbons such as 1,2,3-trichloropropane, tetrachloroethylene, 1,1,2,2-tetrachloroethane, and 1,2-dichloroethane. Alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol and octanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, methyl propionate, methyl enanthate and methyl linoleate Esters such as methyl stearate; Aliphatic hydrocarbons such as cyclohexane, hexane, and octane; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, nitrobenzene, and squalane Sulfoxides such as dimethyl sulfoxide and sulfolane; amides such as N, N-dimethylformamide and N, N, N ′, N′-tetramethylurea; tetrahydrofuran (hereinafter referred to as “THF”), dioxane, dimethoxyethane, Ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monoethyl ether acetate; or a mixture thereof It is done.

In order to disperse the pigment in the solvent, a known dispersing device such as a paint shaker, a sand grind mill, a homomixer, or an ultrasonic disperser can be used.
The mixing of the dye and the adhesive resin may be performed by mixing the whole amount at a predetermined amount ratio at once, or by mixing the other stepwise. Usually, an adhesive resin and a pigment are mixed at a time.

  The pressure-sensitive adhesive of the present invention is preferably used as a sheet or liquid. A pressure-sensitive adhesive containing a near-infrared absorbing dye is dissolved in an organic solvent, molded by a coating apparatus, and a sheet-like pressure-sensitive adhesive layer can be formed through a drying process.

  Examples of the organic solvent for dissolving the pressure-sensitive adhesive include those similar to the above-mentioned “solvent for dispersing or dissolving the near-infrared absorbing dye” (that is, the solvent in the pressure-sensitive adhesive).

As the coating apparatus, a roll coater, a reverse coater, a comma coater, a lip coater, a die coater or the like is preferably used.
It is preferable to process so that the film thickness after drying may be 1 micrometer-1000 micrometers. More preferably, it is 10 to 100 μm from the viewpoint of maintaining the adhesive strength and ensuring the hardness.
Usually formed into a film on a film or laminate. Specifically, it is applied to a film substrate such as PET or TAC, a back surface of a functional film such as an antireflection film or an electromagnetic wave shielding film, glass, an acrylic plate, a polycarbonate plate, or an already laminated functional material. May be.

After the formation of the pressure-sensitive adhesive layer on the film substrate, it is possible to simplify the handling by laminating a release-treated resin film or paper with a laminator or the like.
In addition, the adhesive is applied to the release-treated film, and further dried, and then used as a double-sided adhesive film that does not have a film substrate by laminating a release film having a different peel strength from the release film. I can do it.

  Moreover, after apply | coating and drying the said adhesive to a film base material by the same method, the resin film or paper etc. which performed the peeling process are bonded together with a laminator. Thereafter, the pressure-sensitive adhesive is further applied to the back side of the film substrate and dried, and then a resin film or paper subjected to a release treatment is bonded with a laminator or the like, so that it can be used as a double-sided adhesive film with an equipment film.

  As a practical adhesive strength, an adhesive layer having a thickness of 25 μm is provided on a polyester film, aged for 7 days at a temperature of 23 ° C., and then bonded to a stainless steel plate. The adhesive strength by a 180-degree peeling method (pulling speed 300 mm / min, unit g / 25 mm width) is preferably 0.1 to 10,000 g / 25 mm. Especially, in the releasable adhesive layer, 1.0 g / 25 mm or more is preferable, 5.0 g / 25 mm or more is more preferable, and 10 g / 25 mm or more is still more preferable. In the pressure-sensitive adhesive layer that does not require re-peeling, 10 g / 25 mm or more is preferable, 50 g / 25 mm or more is more preferable, and 100 g / 25 mm or more is even more preferable.

<< Durability of near-infrared absorbing dye-containing adhesive >>
The durability of the near-infrared-absorbing dye-containing pressure-sensitive adhesive of the present invention, such as heat resistance, moist heat resistance, and light resistance, can be evaluated by the following method, for example.

  A coating liquid containing a near-infrared absorbing dye-containing pressure-sensitive adhesive is applied to a polyethylene terephthalate film using a Baker type applicator and dried to form a pressure-sensitive adhesive layer containing a near-infrared absorbing dye. Next, a polyethylene terephthalate film of the same thickness is pressure-bonded to the near-infrared-absorbing dye-containing pressure-sensitive adhesive layer side with a roller to produce a test piece of a laminate sandwiching the near-infrared-absorbing dye-containing pressure-sensitive adhesive layer. To do.

  Although the thickness of the pressure-sensitive adhesive layer containing the near-infrared absorbing dye after drying can be selected as appropriate, it is usually preferably 15 μm to 30 μm. The thickness of the polyethylene terephthalate film can also be selected as appropriate, but is usually 60 μm to 120 μm, preferably 70 μm to 100 μm. Furthermore, the conditions at the time of drying can also be suitably selected according to the adhesive resin etc. which are contained in an adhesive layer, and it is normally dried at 80 degreeC-120 degreeC for about 1 minute-10 minutes.

[Heat-resistant]
The test piece prepared by the above method is put in a high temperature (for example, temperature 70 ° C. to 100 ° C.) constant temperature bath, left for a long time (for example, 100 hours to 500 hours), and the absorption strength before standing (before the test). The heat resistance can be evaluated by determining the change in absorption intensity after standing (after the test).

  For example, in the present invention, in the heat resistance test in which the test piece prepared by the above method is placed in a constant temperature bath at a temperature of 80 ° C. and left for 120 hours, the absorption intensity at the maximum absorption wavelength of the near-infrared absorbing dye after the heat resistance test However, it is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more with respect to the absorption strength before the test.

  Among the above, in a heat resistance test that is placed in a constant temperature bath at a temperature of 80 ° C. and left for 240 hours, the absorption intensity at the maximum absorption wavelength of the near infrared absorbing dye after the heat resistance test is the absorption intensity before the test. Is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.

  Furthermore, among the above, more preferably, in a heat resistance test that is placed in a constant temperature bath at a temperature of 80 ° C. and left for 480 hours, the absorption intensity at the maximum absorption wavelength of the near-infrared absorbing dye after the heat resistance test is It is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more with respect to the absorption intensity.

  The near-infrared absorbing dye may exhibit maximum absorption in addition to the so-called near-infrared region, but in the heat resistance evaluation of the present invention, the absorption intensity at the maximum absorption wavelength in the range of 800 nm to 1050 nm which is the near-infrared absorption region. Measure changes. The same applies to durability evaluation such as moisture and heat resistance, which will be described later.

[Moisture and heat resistance]
The test piece produced by the above method is placed in a constant temperature and humidity chamber at a relatively high temperature (for example, temperature 50 ° C. to 70 ° C.) and high humidity (for example, relative humidity 80% to 95%) for a long time (for example, The wet heat resistance can be evaluated by determining the change in absorption intensity after standing (after the test) with respect to the absorption intensity before standing (before the test).

  For example, in the present invention, the near-infrared absorption after the moisture and heat resistance test is performed in the moisture and heat resistance test in which the test piece prepared by the above method is placed in a constant temperature and humidity chamber having a temperature of 60 ° C. and a relative humidity of 90%. The absorption intensity at the maximum absorption wavelength of the dye is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more with respect to the absorption intensity before the test.

  Among the above, in the heat and humidity resistance test that is placed in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 90% and left for 240 hours, the absorption intensity at the maximum absorption wavelength of the near-infrared absorbing dye after the heat resistance test is It is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more with respect to the absorption strength before the test.

  Furthermore, among the above, more preferably, the absorption at the maximum absorption wavelength of the near-infrared absorbing dye after the heat resistance test in a humidity and heat resistance test that is left in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 90% for 480 hours. The strength is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more with respect to the absorption strength before the test.

[Light resistance]
The light resistance can be evaluated by irradiating the test piece prepared by the above method with light having an irradiance of 64.5 W / m ² at a wavelength of 300 to 400 nm for 160 hours. The light used for the light resistance test is light having an irradiance of 64.5 W / m ² at a wavelength of 300 to 400 nm, preferably 0.55 W / m ² at a wavelength of 340 nm, which is an indicator of performance properties of light resistance, 1.38 W / ^{m 2} at a wavelength of 420nm, 64.5W / ^{m 2} at a wavelength of 300 to 400 nm, with respect to xenon light irradiation intensity of 605.4W / ^{m 2} at a wavelength of 300 to 800 nm, the light cutting UV light It is good to use.

For example, in the present invention, in a light resistance test in which light having an irradiance of 64.5 W / m ² at a wavelength of 300 to 400 nm is irradiated for 160 hours to the test piece prepared by the above method, The absorption intensity at the maximum absorption wavelength of the near-infrared absorbing dye is usually 50% or more, preferably 60% or more, more preferably 70% or more with respect to the absorption intensity before the test, 80 % Or more is more preferable.

  The durability of the near-infrared absorbing dye of the present invention, such as heat resistance, moist heat resistance and light resistance, can also be evaluated according to the above method.

<Near infrared absorption filter>
The near-infrared absorption filter having the above-mentioned near-infrared-absorbing dye-containing pressure-sensitive adhesive layer is excellent in durability and excellent in that it has absorption over the entire wavelength region of 750 nm to 1200 nm. The near-infrared absorption filter can be produced by forming a pressure-sensitive adhesive layer on a base material with a pressure-sensitive adhesive containing the near-infrared absorption dye of the present invention, and bonding various layers according to the purpose. According to the present invention, the near-infrared absorbing layer can be omitted, and the manufacturing process of the optical filter can be simplified.

<< manufacturing method of near-infrared absorption filter >>
As a manufacturing method of the near-infrared absorbing filter of the present invention, a method for coating a transparent substrate with a coating solution containing a near-infrared absorbing dye and an adhesive resin, a film formed by melting and kneading the near-infrared absorbing dye and the adhesive resin And the like. Among these, a method of coating the coating liquid is preferable in order to reduce the load on the near infrared absorbing dye.

  Below, the method of apply | coating the coating liquid containing a near-infrared absorption pigment | dye and adhesive resin to a transparent substrate and manufacturing a near-infrared absorption filter is demonstrated in detail.

(Transparent substrate)
The transparent substrate constituting the near-infrared absorption filter of the present invention is not particularly limited as long as it is substantially transparent and does not have large absorption and scattering. Specific examples include glass, polyolefin resin, amorphous polyolefin resin, polyester resin, polycarbonate resin, poly (meth) acrylate resin, polystyrene, polyvinyl chloride, polyvinyl acetate, poly Examples include arylate resin and polyethersulfone resin. Among these, amorphous polyolefin resin, polyester resin, polycarbonate resin, poly (meth) acrylate resin, polyarylate resin, and polyethersulfone resin are particularly preferable.

  These resins are blended with known additives such as phenol-based and phosphorus-based antioxidants, halogen-based and phosphoric acid-based flame retardants, heat aging inhibitors, ultraviolet absorbers, lubricants, antistatic agents and the like. be able to.

  The transparent substrate used is a resin molded into a film using a molding method such as injection molding, T-die molding, calender molding, compression molding, or a method of dissolving and casting in an organic solvent. It is done. The resin formed into a film may be stretched or unstretched. Moreover, the film which consists of a different material may be laminated | stacked.

The thickness of the transparent substrate is usually selected from the range of 10 μm to 5 mm depending on the purpose.
Further, the transparent substrate may be subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, or coating with an anchor coating agent or a primer. Good.

(Adhesive coating solution)
The pressure-sensitive adhesive coating solution containing a near-infrared absorbing dye can be prepared by dissolving or dispersing the near-infrared absorbing dye together with the adhesive resin in a solvent. Moreover, when making it disperse | distribute, a near-infrared absorption pigment | dye can be prepared by making a particle size into 0.1-3 micrometers normally using a dispersing agent as needed, and making it disperse | distribute to a solvent with adhesive resin.

At this time, the concentration of the total solid content such as near-infrared absorbing dye, dispersant, and adhesive resin dissolved or dispersed in the solvent is usually 5 to 50% by mass. Moreover, the density | concentration of the near-infrared absorptive pigment | dye with respect to the total solid is 0.1-50 mass% normally as a total amount of a near-infrared absorptive pigment | dye, Preferably it is 0.2-30 mass%.
As a matter of course, the concentration of the near-infrared absorbing dye relative to the adhesive resin also depends on the thickness of the near-infrared absorbing dye-containing pressure-sensitive adhesive. The concentration is lower than the above-mentioned concentration.

  Examples of the dispersant include polyvinyl butyral resin, phenoxy resin, rosin-modified phenol resin, petroleum resin, cured rosin, rosin ester, maleated rosin, and polyurethane resin. The usage-amount is 0-100 mass% normally with respect to a near-infrared absorption pigment | dye, Preferably it is 0-70 mass%.

  Examples of the solvent include those similar to the above-mentioned “solvent for dispersing or dissolving the near-infrared absorbing dye” (that is, the solvent in the pressure-sensitive adhesive).

Coating on transparent base material with coating solution containing near-infrared absorbing dye and adhesive resin is dipping method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife It is performed by a known coating method such as a coating method.
The pressure-sensitive adhesive containing the near-infrared absorbing dye is applied so that the film thickness after drying is usually 0.1 μm or more, preferably 0.5 μm or more, usually 5000 μm or less, preferably 1000 μm or less, more preferably 100 μm or less. .

  In particular, when used as an adhesive for an electronic display, the transparency needs to be high, and in terms of flatness and processing efficiency, it is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, Usually, it is applied so as to be 200 μm or less, preferably 100 μm or less, more preferably 50 μm or less.

(UV cut layer)
The filter coated with the pressure-sensitive adhesive containing the infrared absorbing dye of the present invention can further improve the light resistance of the near infrared absorbing filter due to the synergistic effect with the near infrared absorbing dye by further providing an ultraviolet cut layer. The UV-cut layer may be adhered to the substrate with the pressure-sensitive adhesive of the present invention, or after the pressure-sensitive adhesive and another layer are bonded, the UV-cut layer may be further bonded with another pressure-sensitive adhesive.

The ultraviolet cut layer is capable of efficiently cutting ultraviolet rays having a wavelength of 400 nm or less, and preferably absorbs 70% or more of light having a wavelength of 350 nm. The type of the ultraviolet cut layer is not particularly limited, but a resin film (ultraviolet cut film) containing an ultraviolet absorber is preferable.
As an ultraviolet absorber used for the ultraviolet cut layer, any organic or inorganic compound can be used without particular limitation as long as it has a maximum absorption between 300 to 400 nm and can efficiently cut light in the region. be able to. For example, the organic UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylic acid ester UV absorbers, triazine UV absorbers, paraaminobenzoic acid UV absorbers, and cinnamic acid UV absorbers. Acrylate ultraviolet absorbers, hindered amine ultraviolet absorbers, and the like. Examples of the inorganic ultraviolet classifier include a titanium oxide ultraviolet absorber, a zinc oxide ultraviolet absorber, and a fine particle iron oxide ultraviolet absorber. However, in the case of inorganic ultraviolet absorbers, organic ultraviolet absorbers are preferred because they are present in the form of fine particles in the ultraviolet cut layer and may impair the efficiency of the near infrared absorption filter.

  As such an ultraviolet absorber, for example, Tinuvin P, Tinuvin P, Tinuvin 120, 213, 234, 320, 326, 327, 328, 329, 384, 400, 571 manufactured by Ciba Geigy, Sumitomo 250, 300 manufactured by Sumitomo Chemical Co., Ltd. 577, Biosorb 582, 550, 591, manufactured by Kyodo Pharmaceutical Co., Ltd., JF-86, 79, 78, 80 manufactured by Johoku Chemical Co., Ltd., Adeka Stub LA-32, LA-36, LA-34 manufactured by Asahi Denka Co., Ltd. Seasolve 100, 101, 101S, 102, 103, 501, 201, 202, 612NH manufactured by the company, RUVA93, 30M, 30S manufactured by Otsuka Chemical Co., Ltd.

These ultraviolet absorbers may be used alone or in combination. Further, fluorescent whitening agents such as Ubitex OB and OB-P manufactured by Ciba Geigy Inc. that absorb ultraviolet rays and convert the wavelength into the visible region can also be used.
Moreover, a commercially available UV cut filter can also be used for the ultraviolet cut film. For example, SC-38, SC-39, SC-42 manufactured by Fuji Film, and acrylene manufactured by Mitsubishi Rayon are listed. The UV cut filter, SC-39, and acrylene are both UV cut films that absorb 99% or more of the wavelength of 350 nm.

  Thus, the near-infrared absorption filter of the present invention provided with the ultraviolet absorption layer has a dye residual ratio of 50% or more, preferably 60% or more, more preferably 70 after the light resistance test by irradiating the Xe lamp for 160 hours. % Or more, more preferably 80% or more, most preferably 85% or more, and no new absorption peak appears in the visible light region. Here, the dye residual ratio is determined from the degree of decrease in absorption intensity before and after the test in the 800 to 1050 nm region.

The near-infrared absorption filter may be used as a laminate bonded with transparent glass or other transparent resin plate.
Moreover, the near-infrared absorption filter obtained by this invention can be used for wide uses, such as a heat ray blocking film, sunglasses, protective glasses, and a remote control light receiver, besides the display panel filter of this invention.

  Furthermore, the near-infrared absorption filter including the pressure-sensitive adhesive containing the near-infrared absorbing dye of the present invention as a pressure-sensitive adhesive layer can be used, if necessary, a color tone correction layer (visible light absorption layer), an electromagnetic wave cut layer, a fluorescent lamp to the surface An antireflection layer and a glare prevention layer (non-glare layer) for preventing the reflection of external light such as the like are provided, and can be used as a filter for an electronic display, more preferably a plasma display panel.

  When used as a filter for an electronic display, the transparency needs to be high, and from the viewpoint of flatness and processing efficiency, the film thickness after drying of the pressure-sensitive adhesive containing a near-infrared absorbing dye is usually 1 μm or more, preferably It is 5 μm or more, more preferably 10 μm or more, and is usually applied to be 200 μm or less, preferably 100 μm or less, more preferably 50 μm or less.

Furthermore, the film thickness of the pressure-sensitive adhesive of the present invention and the concentration of the near-infrared absorbing dye are adjusted so that the average light transmittance at 850 to 1100 nm is 20% or less, more preferably 15% or less, and still more preferably 10% or less. It is good to adjust.
The filter for an electronic display of the present invention is not particularly limited, except that the near-infrared absorption filter described above can be generally used in any configuration and manufacturing method.

The case where it is used as a filter for a plasma display panel will be described below as a representative example.
(1) Color tone adjustment layer (visible light absorption layer)
The emission of visible light in a normal plasma display has a peak at 450 nm, blue emission at 400 to 500 nm, green emission at 500 to 550 nm with a peak at 525 nm, and red emission at 595 nm, Sharp light emission exists at 610 nm and 625 nm.
Of these, the emission at 595 nm out of the red emission is the emission that turns the orange color of red when the plasma display is displaying red. Therefore, a dye having absorption in this region can be included in the front filter and cut. It is normal.

For these reasons, in plasma display applications, the transmittance of 450 nm, 525 nm, and 625 nm is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more, from the viewpoint of securing the brightness of the display screen. .
In general, the near-infrared absorption filter including the near-infrared absorption filter of the present invention is slightly greenish. When used for display applications such as plasma displays, it is preferable that the color is achromatic, so that the colorant has an absorption at 500 to 600 nm so as to be a complementary color of green to the extent that the luminance of the display is not significantly impaired. It is preferable to contain and neutralize.

  In addition, light bulbs, halogen bulbs, etc. have many red components in their emission spectra. Under a lighting such as a fluorescent lamp, it looks achromatic, but under a lighting such as a light bulb or a halogen bulb electric light, it is often reddish. In such a case, a coloring material that absorbs in the vicinity of 600 to 700 nm should be included so as not to greatly impair the luminance of the display so that the color becomes achromatic even under illumination such as a light bulb or a halogen bulb lamp. Is preferred.

Furthermore, when used as a filter for a plasma display, it is preferable to perform color correction by containing a colorant capable of absorbing 590 to 600 nm neon orange light emitted from the plasma display.
The layer containing these pigments may be prepared as a layer separate from the near infrared absorption layer and used as a laminate bonded to the near infrared absorption layer. Moreover, if there are no problems in various properties such as color developability and durability when mixed with the near-infrared absorbing layer, the same layer as the near-infrared absorbing layer may be used. Among these, the latter is preferable from the viewpoint of process simplification and cost reduction.

  Examples of the coloring material used here include general pigments such as inorganic pigments, organic pigments, organic dyes, and pigments. Examples of inorganic pigments include cobalt compounds, iron compounds, and chromium compounds. Examples of organic pigments include azo, indolinone, quinacridone, vat, phthalocyanine, and naphthalocyanine. Organic dyes and pigments include azine, azo, nickel azo complex, azomethine, anthraquinone, indigoid, indoaniline, oxazine, oxonol, xanthene, quinophthalone, cyanine, squarylium, Examples include stilbene, tetraazaporphyrin, triphenylmethane, naphthoquinone, pyrarozone, pyromethene, dipyrromethene, benzylidene, polymethine, methine, and chromium complex salts.

  Specific examples of coloring materials having absorption at 500 to 600 nm that are complementary to green include Aizen SOT Violet-1, Aizen SOT Blue-3, Aizen SOT Pink-1, Aizen SOT Red made by Hodogaya Chemical Co., Ltd. -1, Aizen SOT Red-2, Aizen SOT Red-3, Aizen Spilon Red BEH Special, Aizen Spilon Red GEH Special, Kayaset Blue AS, Kayaset Red 130, Kayaset Red AG, Kayaset Red 2G, Kayaset from Nippon Kayaku Red BR, Kayaset Red SF-4G, Kayaset Red SF-B, Kayaset Violet AR, Mitsubishi Chemical's Diamond Resin Blue-J, Diamond Resin Blue-G, Diamond Resin Violet-D, Diamond Resin Red H5B, Diamond Resin Red S, Diamond Resin Red A, Diamond Resin Red K, Diamond Resin Red Z.PTR63, Cio Specialty Chemicals Violet-RB, Red-G, Pink-5BGL, Red-BL, Red-2B, Red-3GL , Red-GR, Red-GA and the like. Among them, when the same layer as the near infrared absorbing dye is used, a nickel complex salt or a chromium complex salt system is preferable from the viewpoint of the stability of the near infrared absorbing layer.

  In addition, specific examples of color materials having absorption in the vicinity of 600 to 700 nm include Aizen SOT Blue-1, Aizen SOT Blue-2, Aizen SOT Blue-3, and Aizen SOT Blue-4 manufactured by Hodogaya Chemical Industry Co., Ltd. Aizen Spilon Blue 2BNH, Aizen Spilon Blue GNH, Nippon Kayaku Kayaset Blue N, Kayaset Blue FR, KAYASORB IR-750, Mitsubishi Chemical's Diamond Resin Blue-H3G, Diamond Resin Blue-4G, Diamond Resin Blue -LR, PTB31, PBN, PGC, KBN, KBFR, Blue-GN, Blue-GL, Blue-BL, Blue-R, CISolvent Blu3 63 manufactured by Ciba Specialty Chemicals.

  Specific examples of the coloring material having absorption at 560 to 600 nm include organic dyes described in JP-A Nos. 2000-258624, 2002-040233, and 2002-363434, JP-A-2004-505157, and JP-A-2004-233379. And organic pigments such as quinacridone described.

  By further including a visible light absorbing dye in the pressure sensitive adhesive of the present invention, or by using a pressure sensitive adhesive containing a visible light absorbing dye separately from the pressure sensitive adhesive of the present invention, the visible light absorbing layer can be further omitted. The manufacturing process of the electronic display filter can be further simplified.

  As the visible light-absorbing dye when mixed with the pressure-sensitive adhesive, pigment-based cobalt compounds, iron compounds, chromium compounds, azo-based, indolinone-based, quinacridone-based, bat-based, phthalocyanine-based, naphthalocyanine-based, and the like are preferable. In addition, dyes and pigments are more preferably anthraquinone, indoaniline, tetraazaporphyrin, and the like.

  At this time, the density | concentration of total solids, such as a visible light absorption pigment | dye and an adhesive, is 5-50 mass% normally. The density | concentration of the visible light absorption pigment | dye with respect to the total solid is 0.001-50 mass% normally as a total amount, Preferably it is 0.01-5 mass%. However, the concentration of the visible light absorbing dye relative to the adhesive naturally depends on the thickness of the visible light absorbing dye-containing adhesive.

  The adhesive coating solution containing a visible light absorbing dye can be prepared by dissolving or dispersing the visible light absorbing dye together with the adhesive resin in a solvent. Moreover, when making it disperse | distribute, it can also prepare by making a particle size into 0.1-3 micrometers microparticles normally using a dispersing agent as needed, and making it disperse | distribute to a solvent with adhesive resin. When the visible light absorbing dye is included together with the near infrared absorbing dye, the order of addition is not particularly determined, but it is preferable to add from the dye that requires more dissolution time and dispersion time.

The coating of the coating liquid containing the visible light absorbing dye and the adhesive resin on the transparent substrate is the same as the coating liquid containing the near infrared absorbing dye and the adhesive resin, the dipping method, the flow coating method, and the spray method. The coating is performed by a known coating method such as a bar coating method, a gravure coating method, a roll coating method, a blade coating method, or an air knife coating method.
As in the case of a coating solution containing a near-infrared absorbing dye and an adhesive resin, the film thickness is usually 0.1 μm or more, preferably 0.5 μm or more, usually 1000 μm or less, preferably 500 μm or less. .

(2) Electromagnetic wave cut layer The production of the electromagnetic wave cut layer used for the plasma display panel filter can be performed by vapor deposition of metal oxide or the like, a sputtering method, and the like. Usually, indium tin oxide (ITO) is generally used. Light of 1000 nm or more can also be cut by alternately laminating dielectric layers and metal layers on a substrate by sputtering or the like. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy. Usually, about 3, 5, 7 or 11 layers are sequentially stacked from the dielectric layer. As the base material, the near-infrared absorption filter of the present invention may be used as it is, or after being provided with an electromagnetic wave cut layer by vapor deposition or sputtering on a resin film or glass, it is bonded to the near-infrared absorption filter of the present invention. Also good.

(3) Antireflection layer The antireflection layer used in the plasma display panel filter of the present invention includes a metal oxide, fluoride, silicide, boron, in order to suppress surface reflection and improve the transmittance of the filter. Fluoride, carbide, nitride, sulfide and other inorganic materials, such as vacuum deposition, sputtering, ion plating, ion beam assist, etc., single layer or multilayer lamination, acrylic resin, fluorine resin, etc. There is a method of laminating resins having different rates in a single layer or multiple layers. Moreover, the film which gave the antireflection process can also be affixed on this filter.

(4) Non-glare layer In addition to the above-mentioned layers, an anti-glare layer (non-glare layer) may be provided. The non-glare layer may be formed by coating fine powders such as silica, melamine, and acryl on the surface in order to scatter transmitted light for the purpose of widening the viewing angle of the filter. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated film can be stuck on the filter. Further, if necessary, a hard coat layer can be provided.

<< Physical Properties of Near-Infrared Absorbing Filter Having the Adhesive of the Present Invention >>
The near-infrared absorption filter containing the near-infrared-absorbing dye-containing pressure-sensitive adhesive of the present invention is excellent in durability such as heat resistance, moist heat resistance, and light resistance.

[Light resistance]
One of the durability required as a filter for electronic displays is light resistance. It is very important in practice that there is no deterioration due to light emitted from the electronic display, irradiation light, and ambient light incident on the electronic display.

0.55 W / m ² at a wavelength of 340nm, 1.38W / m ² at a wavelength of 420nm, 64.5W / m ² at a wavelength of 300 to 400 nm, a xenon light irradiation intensity of 605.4W / m ² at a wavelength of 300~800nm Irradiating for 160 hours with UV light cut, and comparing the absorption intensity before and after irradiation at the maximum absorption wavelength before irradiation with the ratio calculated by “absorption intensity after irradiation ÷ absorption intensity before irradiation × 100” It is defined as “light resistance” of a filter for display. The light resistance of the electronic display filter is required to be practically 50% or more. Preferably it is 60% or more, More preferably, it is 70% or more, More preferably, it is 80% or more.

  Although it does not specifically limit as a wavelength which calculates | requires absorption intensity, 750 nm-1200 nm which can exhibit a performance as a near-infrared absorption of the filter for electronic displays to the maximum is mentioned. More preferably, since it is practically required that the electronic display filter has no color change, a change in the visible light region of 350 to 800 nm is small. When a visible light absorbing dye is also included in the pressure-sensitive adhesive of the present invention and has a visible light region control function, the change at the maximum absorption wavelength that exhibits the function is particularly small, and the remaining ratio is large. Is effective as a filter for electronic displays.

[Heat-resistant]
Those having heat resistance in addition to light resistance are effective in reducing deterioration during storage and transportation. Furthermore, it is also effective for direct attachment to an electronic display panel. For example, in the plasma display panel (PDP) which has been attracting attention as one of the electronic displays, a filter with the function of a front glass filter is pasted directly on the panel and the image is improved by eliminating reflection image reflection. A direct pasting method has been proposed which simplifies the process by reducing the number of members and reduces the weight by eliminating glass. In this method, since heat from the panel is directly transmitted to the electronic display filter itself, heat resistance is required more than the conventional method in which a gap is provided between the front glass filter and the electronic display panel.

The ratio calculated by “absorption intensity after exposure ÷ absorption intensity before exposure × 100”, which is obtained by comparing the absorption intensity before and after exposure at the maximum absorption wavelength before exposure for 250 hours in an environment at a temperature of 80 ° C., is 50 % Or more is practically necessary. More preferably, it is 80% or more.
More preferably, it is practically necessary for the ratio to be 50% or more after exposure for 500 hours. More preferably, it is 80% or more.

The wavelength for obtaining the absorption intensity is the same as the light resistance.
The particularly preferred heat resistance is calculated by “absorption intensity after exposure ÷ absorption intensity before exposure × 100”, which is obtained by comparing the absorption intensity before and after exposure at the maximum absorption wavelength before exposure for 250 hours in an environment of 90 ° C. The ratio is 50% or more, more preferably 80% or more.
Also, those having heat and moisture resistance are very effective in reducing deterioration during transportation and storage as well as in practical resistance and reliability. Export products that are heavy are transported by sea, but in a storage location near the bottom of the ship, the environment is very humid.

[Moisture and heat resistance]
The indicators of the performance physical properties of the heat and humidity resistance are as follows.
It is calculated by “absorption intensity after exposure ÷ absorption intensity before exposure × 100”, which is obtained by comparing the absorption intensity before and after exposure at the maximum absorption wavelength before exposure for 250 hours in an environment with a temperature of 60 ° C. and a relative humidity of 90%. It is practically necessary that the ratio is 50% or more. More preferably, it is 80% or more.
More preferably, it is practically necessary for the ratio to be 50% or more after exposure for 500 hours. More preferably, it is 80% or more.

The wavelength for obtaining the absorption intensity is the same as the light resistance.
In addition to these durability and reliability, it acts as a filter for electronic displays, particularly in the wavelength region of 750 nm to 1200 nm, and causes malfunctions in the surrounding electronic devices such as cordless phones and video decks using near infrared remote controls. Therefore, the function of shielding near infrared rays of 750 nm to 1200 nm is necessary.

As the shielding performance therefor, the sheet-like near-infrared absorbing dye-containing pressure-sensitive adhesive preferably has a spectral transmittance of 40% or less at the maximum absorption wavelength. More preferably, it is 20% or less, More preferably, it is 10% or less.
In order to shield the wavelength region of 750 nm to 1200 nm, it is preferable to contain a plurality of near infrared absorbing dyes as described above. If a single pigment can achieve a spectral transmittance of 40% or less, it is possible to achieve a more preferable spectral transmittance of 10% or less by containing a plurality of pigments.

  From the above, the light resistance is required for the durability required as a filter for electronic displays. More preferably, heat resistance and moist heat resistance are also required, which leads to expansion of the use method of the electronic display filter and expansion of the practical range in addition to being practically effective.

  Further, the near-infrared absorbing dye-containing mixture, the near-infrared absorbing dye-containing adhesive, and the near-infrared absorbing filter of the present invention have a transmittance at a wavelength of 850 nm of 15% or less and a transmittance at a wavelength of 950 nm of 10% or less. By having such characteristics, even when used for a plasma display front filter, it is possible to prevent malfunction of other electronic devices in the vicinity.

  Embodiments of the present invention will be described below by way of examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Synthesis example 1
[Synthesis Example 1-1]

The above compound 1 (10 g, 40.0 mmol) obtained by a known method was dissolved in methylene chloride (80 mL) at room temperature and cooled to 0 ° C. Then, aluminum chloride (5.87 g) was added, and commercially available compound 2 (5.4 mL, 44 mmol) was added dropwise. The reaction solution was stirred at 0 ° C. for 3 hours and then poured into a 1 mol / L hydrochloric acid aqueous solution. Thereafter, the mixture was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 11.3 g of the target compound 3 (yield 76%).
Mass spectrometry result (EI-MS method): 374

[Synthesis Example 1-2]

(Condition 1)
Compound 3 (1.5 g, 4.07 mmol) was dissolved in acetic acid (10 mL), and a solution of bromine (0.65 g, 4.07 mmol) in acetic acid (10 mL) was added dropwise at room temperature. After dropping, the mixture was stirred for 1 hour at room temperature and then poured into ice water. Thereafter, the mixture was extracted with ethyl acetate, and the organic layer was neutralized with sodium bicarbonate. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography, but target compound 4 was not obtained.

(Condition 2)
Compound 3 (2.55 g, 6.82 mmol) was dissolved in THF (50 mL) at room temperature. After cooling to 0 ° C., phenyltrimethylammonium tribromide (2.69 g, 7.16 mmol) was added and stirred at 0 ° C. for 1 hour, and then the reaction solution was poured into ice water. Thereafter, the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and concentrated under reduced pressure to obtain the target compound 4. The obtained compound 4 was directly used in the next reaction (Synthesis Example 1-3).
Mass spectrometry result (EI-MS method): 452

[Synthesis Example 1-3]

Compound 4 (6.82 mmol) obtained in Synthesis Example 1-2 (Condition 2) is dissolved in acetone (35 mL) at room temperature, Compound 5 (1.09 g, 6.82 mmol) is added, and 30 minutes at room temperature. Stir. The inorganic salt produced was removed by filtration, and the filtrate was concentrated under reduced pressure. The obtained crude oily product was extracted with methylene chloride, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the target compound 6. The obtained compound 6 was directly used in the next reaction (Synthesis Example 1-4).
Mass spectrometry result (EI-MS method): 494

[Synthesis Example 1-4]

Compound 6 (6.82 mmol) obtained in Synthesis Example 1-3 was mixed with acetic acid (10 mL) and hydrobromic acid solution (hereinafter referred to as HBr-AcOH) (10 mL), and overnight at room temperature. Stir. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was neutralized with sodium hydrogen carbonate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 2.1 g of the intended compound 7 (Precursor 1) (yield 69%, three steps of Synthesis Examples 1-2 to 1-3).
Mass spectrometry result (EI-MS method): 448
In the present specification, a compound that reacts with a metal atom to obtain a near-infrared absorbing dye, such as the compound 7, may be simply expressed as “precursor”.

Example 1

Compound 7 (2.1 g, 4.69 mmol) obtained in Synthesis Example 1 was dissolved in THF (25 mL), and 1 mol / L sodium methoxide (NaOMe) methanol solution (9.7 mL, 9. 85 mmol) was added and stirred for 30 minutes. To this reaction solution, a methanol solution (1 mL) of nickel chloride hexahydrate (0.56 g, 2.35 mmol) was added, and the mixture was further stirred for 30 minutes. The obtained reaction solution of the intermediate complex was poured into a mixed solution of toluene (50 mL) and acetic acid (7 mL), and stirred at 40 ° C. for 6 hours while bubbling air. The reaction solution was concentrated under reduced pressure, extracted with methylene chloride, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, then washed with methanol, and 1.7 g (yield 82%) of the target near-infrared absorbing dye 1 as “Exemplary Compound 23-1” described above. Obtained.
Mass spectrometry result (EI-MS method): 898
λmax (in chloroform): 935 nm

Example 2

The precursor 2 was obtained in the same manner as in Synthesis Examples 1-1 to 1-4. Then, according to the method of Example 1, the above-described “Exemplary Compound 21-1” of the near-infrared absorbing dye 2 was obtained in a yield of 87%.
Mass spectrometry result (EI-MS method): 898
λmax (in chloroform): 951 nm

Example 3

The precursor 3 was obtained in the same manner as in Synthesis Examples 1-1 to 1-4. Subsequently, according to the method of Example 1, the near-infrared absorbing dye 3 which is the “Exemplary Compound 21-2” was obtained in a yield of 85%.
Mass spectrometry result (EI-MS method): 786
λmax (in chloroform): 936 nm

Example 4

The precursor 4 was obtained in the same manner as in Synthesis Examples 1-1 to 1-4. Next, according to the method of Example 1, the near-infrared absorbing dye 4 which is the “Exemplary Compound 24-1” was obtained in a yield of 79%.
Mass spectrometry result (EI-MS method): 838
λmax (in chloroform): 934 nm

Example 5

The precursor 5 was obtained in the same manner as in Synthesis Examples 1-1 to 1-4. Subsequently, according to the method of Example 1, the near-infrared absorbing dye 5 which is the “Exemplary Compound 24-2” was obtained in a yield of 79%.
Mass spectrometry result (EI-MS method): 866
λmax (in chloroform): 934 nm

Example 6

The precursor 6 was obtained in the same manner as in Synthesis Examples 1-1 to 1-4. Subsequently, according to the method of Example 1, the near-infrared absorbing dye 6 as “Exemplary Compound 24-3” was obtained in a yield of 74%.
Mass spectrometry result (EI-MS method): 950
λmax (in chloroform): 950 nm

Synthesis example 2
[Synthesis Example 2-1]

Commercially available compound 8 (15 g, 91 mmol) and commercially available isoamyl iodide (20 g, 100 mmol) were dissolved in N, N-dimethylformamide (80 mL), potassium carbonate (20 g, 140 mmol) was added, and the mixture was stirred at room temperature for 12 hours. Stir. The obtained reaction solution was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 18 g of the target compound 10 (yield 84%).
Mass spectrometry result (EI-MS method): 234

[Synthesis Example 2-2]

Compound 10 (8.8 g, 38 mmol) obtained in Synthesis Example 2-1 was dissolved in carbon tetrachloride (100 mL), and N-bromosuccinimide (6.7 g, 38 mmol) and benzoyl peroxide (0.36 g, 1 0.1 mmol) was added, and the mixture was stirred with heating at 80 ° C. for 12 hours under nitrogen. The reaction solution was cooled to room temperature and washed with water, and then the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 11 g (yield 93%) of the target compound 11.
Mass spectrometry result (EI-MS method): 312

[Synthesis Example 2-3]

Magnesium (2.4 g, 100 mmol) was dispersed in THF (15 mL) and a small piece of iodine was added. After stirring this at room temperature for 10 minutes, a THF solution (60 mL) of compound 11 (10 g, 32 mmol) obtained in Synthesis Example 2-2 was added dropwise. After the dropwise addition, the reaction solution was stirred at room temperature for 1 hour and then cooled to 0 ° C. To this reaction solution, a THF solution (60 mL) of commercially available compound 12 (4.6 g, 36 mmol) was added dropwise. After dropping, the mixture was stirred at room temperature for 1 hour, poured into a 1 mol / L hydrochloric acid aqueous solution, and extracted with ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 7.5 g of the target compound 13 (yield 65%).
Mass spectrometry result (EI-MS method): 360

[Synthesis Example 2-4]

A solution of dimethylsulfoxide (1.1 g, 14 mmol) in methylene chloride (20 mL) was added dropwise at −78 ° C. to a solution of ogisaryl chloride (2.0 g, 16 mmol) in methylene chloride (20 mL). To this reaction solution, a solution obtained by dissolving Compound 13 (4.7 g, 13 mmol) obtained in Synthesis Example 2-3 in methylene chloride (20 mL) was added, stirred for 15 minutes, and then triethylamine (9.4 mL, 66 mmol). Was added. The reaction solution was warmed to room temperature, extracted with methylene chloride, and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 3.2 g of the target compound 14 (yield 68%).
Mass spectrometry result (EI-MS method): 359

[Synthesis Example 2-5]

According to the method of Synthesis Example 1-2 (Condition 2), Synthesis Example 1-3, and Synthesis Example 1-4, 2.2 g of the target Compound 15 (Precursor 7) was obtained from Compound 14 obtained in Synthesis Example 2-4. Obtained (yield 85%).
Mass spectrometry result (EI-MS method): 432

Example 7

According to the method of Example 1, from the precursor 7 obtained in Synthesis Example 2-5, the near-infrared absorbing dye 7 as “Exemplary Compound 5-16” was obtained in a yield of 73%.
Mass spectrometry result (EI-MS method): 866
λmax (in chloroform): 970 nm

Example 8

Precursor 8 was obtained in the same manner as in Synthesis Examples 2-1 to 2-5. Then, according to the method of Example 1, the above-described “Exemplary Compound 5-15” of the near-infrared absorbing dye 8 was obtained in a yield of 74%.
Mass spectrometry result (EI-MS method): 866
λmax (in chloroform): 975 nm

Precursor 8 was obtained in the same manner as in Synthesis Examples 2-1 to 2-5. Then, according to the method of Example 1, near-infrared absorbing dye 8 was obtained in a yield of 74%.
Mass spectrometry result (EI-MS method): 866
λmax (in chloroform): 975 nm

Comparative Example 1
9.4 mL of a 1 mol / L sodium methoxydethanol solution (1.05 g) is added to 1.0 g (3.75 mmol) of 4,5-bis (sec-propylthio) -1,3-dithiol-2-one obtained by a known method. 5 equivalents) was added and stirred at 25 ° C. for 30 minutes. To this was added 0.5 equivalent of nickel chloride hexahydrate dissolved in 1 mL of methanol, and the mixture was further stirred at 25 ° C. for 30 minutes. To this mixed solution, 50 mL of toluene and 2.0 g of acid type ion exchange resin (DIAION-PK212; H type) were added, and the reaction was carried out by stirring for 3 hours while bubbling air. The resulting green reaction solution was filtered, and the ion exchange resin was filtered off. The filtrate was washed with water and concentrated. Methanol (25 mL) was added thereto, and after hanging, the solid was collected by filtration to obtain a near-infrared absorbing dye represented by the following formula in a yield of 81%.
Mass spectrometry result (EI-MS method): 536
λmax (in chloroform): 1007 nm

Evaluation Example FIGS. 1 to 9 show the results of spectral transmission spectrum measurement of the near-infrared absorbing dyes obtained in Examples 1 to 8 and Comparative Example 1.
Moreover, the test piece was manufactured using these near-infrared absorption pigment | dyes, and the following aging test, a heat-and-humidity test, and the heat-resistance test were done. The results are shown in Tables 1 and 2. Absorption intensity was obtained by spectral transmission spectrum measurement (measured by a spectrophotometer UV-3600 manufactured by Shimadzu Corporation), and the absorption intensity at the maximum absorption wavelength of each test piece was calculated from the transmittance.

(Manufacture of adhesives)
A near-infrared absorbing dye was added to 8.0 g of toluene and stirred, and then 16.0 g of an acrylic adhesive main agent (manufactured by Soken Chemical Co., Ltd., SK Dyne “registered trademark” 1811L) was added and thoroughly stirred to dissolve. . A specified amount of an isocyanate-based curing agent (manufactured by Soken Chemical Co., Ltd., L-45) was added therein and stirred well to produce a near-infrared absorbing dye-containing pressure-sensitive adhesive. Bubbles entrained at the time of stirring were subjected to ultrasonic waves or stopped to collect the bubbles upward and then removed. SK dyne 1811L has an acid value of 0 mgKOH / g and a hydroxyl value of 0.2 mgKOH / g.

(Manufacture of test pieces)
The near-infrared-absorbing dye-containing pressure-sensitive adhesive is coated on a 75 μm-thick polyethylene terephthalate film using a Baker-type applicator at a thickness of 200 μm, dried at 100 ° C. for 2 minutes, and absorbed at a near-infrared thickness of 20 μm. A dye-containing pressure-sensitive adhesive layer was formed. Next, a 75 μm thick polyethylene terephthalate film is pressure-bonded to the near-infrared absorbing dye-containing pressure-sensitive adhesive layer side with a roller to obtain a test piece of a laminate (near-infrared absorbing filter) sandwiching the near-infrared absorbing dye-containing pressure-sensitive adhesive layer. It was.

(Aging test)
The specimen was left for 3 days under conditions of a temperature of 24 ° C. and a relative humidity of 45%. The change in the absorption intensity after the test with respect to the absorption intensity before the test was determined, and the evaluation was performed according to the following criteria.
A: No substantial change Δ: Change of less than 10% ×: Change of 10% or more

(Moisture and heat resistance test)
The test piece was placed in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 90%, and left for 120 hours, 240 hours and 480 hours. The change in the absorption intensity after the test with respect to the absorption intensity before the test was determined, and the evaluation was performed according to the following criteria.
◎: Absorption strength after test with respect to absorption strength before test is 95% or more ○: Absorption strength after test with respect to absorption strength before test is 90% or more and less than 95% Δ: Absorption strength after test with respect to absorption strength before test 85% or more and less than 90% x: Absorption strength after test with respect to absorption strength before test is less than 85%

(Heat resistance test)
The test piece was placed in a thermostatic bath at a temperature of 80 ° C. and left for 120 hours, 240 hours and 480 hours. The change in the absorption intensity after the test with respect to the absorption intensity before the test was determined, and the evaluation was performed according to the following criteria.
◎: Absorption strength after test with respect to absorption strength before test is 95% or more ○: Absorption strength after test with respect to absorption strength before test is 90% or more and less than 95% Δ: Absorption strength after test with respect to absorption strength before test 85% or more and less than 90% x: Absorption strength after test with respect to absorption strength before test is less than 85%

  FIG. 10 shows the spectral transmission spectrum measurement results before and after the wet heat resistance test of the near infrared absorbing dye 1, and FIG. 11 shows the spectral transmission spectrum measurement results before and after the heat resistance test. Moreover, the spectral transmission spectrum measurement result before and after the wet heat resistance test of the near-infrared absorbing dye produced in Comparative Example 1 is shown in FIG. 12, and the spectral transmission spectrum measurement result before and after the heat resistance test is shown in FIG.

  The near-infrared absorption filter using the near-infrared-absorbing dye of the present invention and the pressure-sensitive adhesive containing the same is suitable for the near-infrared absorption wavelength region and is excellent in durability, so that it is a front surface for displays such as plasma displays. It is widely used in fields where near-infrared rays are to be shielded, such as filters, near-infrared shielding films, sunglasses, protective glasses, and remote control receivers.

Claims (18)

A near-infrared absorbing dye characterized by being represented by the following general formula (1).

[In general formula (1),
R ¹ and R ² each independently represents a heterocyclic group which may have a substituent.
X ¹ and X ^2, each independently represents a monovalent group having at least one atom for a total of 4 or more selected from the group consisting of carbon atom, oxygen atom, nitrogen atom and a silicon atom, X ¹ and X ² may be bonded to each other via a linking group.
M represents a metal atom.
The benzene ring A may have a substituent R ^f which may be different from each other in addition to X ¹ , and adjacent R ^f may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^f is bonded to each other to form a condensed ring, m is an integer of 0 to 4, and when R ^f is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent.
The benzene ring B may have a substituent R ^g which may be different from each other in addition to X ² , and adjacent R ^gs may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^g is bonded to form a condensed ring, n is an integer of 0 to 4. When R ^g is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ] In the general formula (1), X ¹ and X ² are each independently —OR ^a (R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms). The near infrared ray absorbing dye according to claim 1. In the general formula (1), R ¹ and R ² each independently represent at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may have a substituent. The near-infrared absorbing dye according to claim 1, wherein the near-infrared absorbing dye is a heterocyclic group having In the said General formula (1), R < ¹ > and R < ² > is respectively independently the thienyl group which may have a substituent, The near-infrared absorption pigment | dye of Claim 3 characterized by the above-mentioned. In the general formula (1), the substituent R ^f and the substituent R ^g are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group, or an alkyl group having 1 to 10 carbon atoms. The near-infrared absorbing dye according to any one of claims 1 to 4, which is a group or a linear or branched alkoxy group having 1 to 10 carbon atoms. 6. The near infrared absorbing dye represented by the general formula (1) is a near infrared absorbing dye represented by the following general formula (2a) or (2b). The near-infrared absorbing dye according to any one of the claims.

[In the general formulas (2a) and (2b),
R ³ represents a thienyl group which may have a substituent.
R ^a represents a linear or branched alkyl group having 3 to 10 carbon atoms.
R ^b represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms (provided that when R ^b is a branched alkoxy group, R ^b is the same group as OR ^a ).
M ¹ represents a metal atom. ]   The near-infrared absorbing dye according to any one of claims 1 to 6, wherein the maximum absorption wavelength is in the range of 850 nm to 1200 nm.   A near-infrared absorbing dye-containing pressure-sensitive adhesive comprising the near-infrared absorbing dye according to any one of claims 1 to 7.   Furthermore, the near-infrared absorption dye containing adhesive agent of Claim 8 containing the 2nd near-infrared absorption dye which has a maximum absorption wavelength in the range of 750 nm-1200 nm.   The maximum absorption wavelength is shorter than the near-infrared absorbing dye according to any one of claims 1 to 7 contained in the adhesive, and the maximum absorption wavelength is in the range of 750 nm to 950 nm. 10. The near-infrared absorbing dye-containing pressure-sensitive adhesive according to claim 9, further comprising a second near-infrared absorbing dye. The near-infrared absorbing dye-containing pressure-sensitive adhesive according to claim 10, wherein the second near-infrared absorbing dye is a near-infrared absorbing dye represented by the following general formula (3).

[In general formula (3),
X and Y each independently represent a sulfur atom, an oxygen atom, or a nitrogen atom that may have a substituent.
M ² represents a metal atom.
(A) when X is a nitrogen atom having a substituent;
The substituent of the nitrogen atom is a compound represented by the following general formula (4a),

(In the general formula (4a),
R represents a monovalent substituent having a total of 3 or more of at least one kind selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, and the terminal of R is represented by the general formula (3) It may be bonded to the benzene ring.
R ′ represents an arbitrary monovalent substituent, and R ′ may be bonded to each other to form a condensed ring.
When R ′ is not bonded to form a condensed ring, n ′ is an integer of 0 to 4, and when R ′ is bonded to form a condensed ring, the condensed ring is arbitrary. May have a monovalent substituent. )
R ^X and R ^Y each independently represent a monovalent substituent, and may be bonded via a linking group, or R ^X and R ^Y may be bonded to form a condensed ring. )
(B) when X is an oxygen atom or a sulfur atom;
R ^Y represents a monovalent substituent.
R ^X is a compound represented by the following general formula (4b).

(In the general formula (4b),
X ^h represents a monovalent group having a total of 3 or more of at least one kind of atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a silicon atom.
R ^h represents an arbitrary monovalent substituent, and R ^h may be bonded to each other to form a condensed ring.
When R ^h is bonded to form a condensed ring, p is an integer of 0 to 4, and when R ^h is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]] The near-infrared absorbing dye represented by the general formula (3) is a second near-infrared absorbing dye represented by the following general formula (5). Infrared absorbing dye-containing adhesive.

[In general formula (5),
R ⁴ represents a hydrogen atom; a linear or branched alkyl group having 1 to 5 carbon atoms; an alkyl group, an alkoxy group, a substituted amino group, or a phenyl group optionally having a halogen atom as a substituent; an alkyl group or an alkoxy group Represents a phenylthio group optionally having a substituted amino group or a halogen atom as a substituent.
R ⁶ represents a linear or branched alkyl group having 3 to 10 carbon atoms.
R ⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms (provided that when R ⁵ is a branched alkoxy group, R ⁵ is OR ⁶ and the same group).
M ⁴ represents a metal atom. ] The near-infrared absorbing dye-containing pressure-sensitive adhesive according to claim 9 or 10, wherein the second near-infrared absorbing dye is a near-infrared absorbing dye represented by the following general formula (6).

[In general formula (6),
R ⁷ and R ⁸ represent a hydrocarbon group which may have a substituent, a carbonyl group which may have a substituent, a cyano group, a halogen atom or a hydrogen atom.
R ⁹ and R ¹⁰ represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
M ⁵ represents a metal atom. ]   Furthermore, (meth) acrylic-type resin is contained, The near-infrared absorption dye containing adhesive agent of any one of Claim 8 thru | or 13 characterized by the above-mentioned.   A near-infrared absorbing filter comprising the near-infrared-absorbing dye-containing pressure-sensitive adhesive layer according to any one of claims 8 to 14.   A front filter for a plasma display, comprising the near-infrared absorption filter according to claim 15.   A plasma display comprising the front filter for plasma display according to claim 16. A near-infrared absorbing dye represented by the following general formula (1) and a second near-infrared absorbing dye having a maximum absorption wavelength in the range of 750 nm to 950 nm. Pigment mixture for absorption filters.

[In general formula (1),
R ¹ and R ² each independently represents a heterocyclic group which may have a substituent.
X ¹ and X ^2, each independently represents a monovalent group having at least one atom for a total of 4 or more selected from the group consisting of carbon atom, oxygen atom, nitrogen atom and a silicon atom, X ¹ and X ² may be bonded to each other via a linking group.
M represents a metal atom.
The benzene ring A may have a substituent R ^f which may be different from each other in addition to X ¹ , and adjacent R ^f may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^f is bonded to each other to form a condensed ring, m is an integer of 0 to 4, and when R ^f is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent.
The benzene ring B may have a substituent R ^g which may be different from each other in addition to X ² , and adjacent R ^gs may be bonded via a linking group, and bonded to form a condensed ring. May be formed.
When R ^g is bonded to form a condensed ring, n is an integer of 0 to 4. When R ^g is bonded to form a condensed ring, the condensed ring is an arbitrary ring. It may have a monovalent substituent. ]

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