JP4839056B2 - Infrared absorption filter and infrared absorption panel - Google Patents

Description

  The present invention relates to an infrared absorbing filter (or an infrared absorbing film, particularly a near infrared absorbing filter) containing a dye having an infrared absorbing ability (an infrared absorbing dye, particularly a near infrared absorbing dye), and an infrared absorbing panel including the infrared absorbing filter ( Near infrared absorption panel).

  As infrared absorption filters (near infrared absorption filters), vapor-deposited glass and phosphate glass containing metal ions are known. However, these glass infrared absorption filters are heavy and easy to break, and there is a problem that processing such as bending is difficult.

  In recent years, in order to solve these problems, plasticization of infrared absorption filters has been studied, and many materials have been proposed. Examples of such near infrared absorption filter materials include polyester resins, acrylic resins, polycarbonate resins, styrene resins, amorphous polyolefin resins, polyisocyanate resins, polyarylate resins, and cellulose resins, and infrared absorbing dyes. And a film obtained by coating a transparent film such as polyester with a coating solution obtained by dissolving or uniformly dispersing a visible light absorbing dye for color tone correction in a solvent, and drying and removing the solvent.

  These plastic infrared absorptive filters are required to exhibit infrared absorptivity with a thinner film thickness. For this reason, they are unevenly distributed, agglomerated, and applied to the surface of the pigment in the thin film formed after removing the solvent. In order to prevent precipitation or the like, it is necessary that the dye is in a high concentration and uniformly dispersed state in the binder resin. Furthermore, the dye dispersed in the binder resin is required to have long-term durability, and it is necessary that there is no deterioration due to the environment such as reaction between the dyes, heat, light, and moisture.

  Originally, most dyes used as infrared absorbers are very unstable to light, heat, and moisture, and the binder resin functions as a protective layer that prevents the deterioration of these dyes. Is required. However, the above-mentioned transparent resin, which is well known as a binder resin, does not have sufficient performance, and various resins have been proposed as countermeasures.

  For example, JP-A-11-116826 (Patent Document 1) discloses a film in which a plurality of pigments are dispersed in a transparent polymer resin. Further, it is described that a polyester copolymerized with a diol having a fluorene skeleton may be used.

  JP 2000-227515 A (Patent Document 2) is a near-infrared filter formed by laminating a coating layer made of a composition in which a near-infrared absorbing dye is dispersed in a binder resin on a substrate. A near-infrared absorption filter is disclosed in which the binder resin is selected from a polyester resin, an acrylic resin, a polyamide resin, a polyurethane resin, a polyolefin resin, or a polycarbonate resin.

  Japanese Patent No. 3308545 (Patent Document 3) discloses a multilayer near-infrared absorption including a near-infrared absorbing film in which a pigment having a near-infrared absorbing ability such as a phthalocyanine-based metal complex is dispersed in a transparent polymer resin. A multilayer infrared absorption film having a film and at least one of an electromagnetic wave absorption layer, an antireflection layer, and an ultraviolet absorption layer is disclosed. In this document, as the polymer resin, in addition to copolymer polyester, polymethyl methacrylate, polystyrene, amorphous polyolefin, polyisocyanate, polyarylate, triacetyl cellulose, etc. The polyester resin which copolymerized diol is illustrated.

  However, these resins do not have sufficient performance to uniformly disperse the infrared absorbing dye at a high concentration, and the durability of the obtained near infrared absorbing filter is insufficient, and a binder resin having higher performance is not available. It has been demanded.

JP-A-11-116826 (Claims) JP 2000-227515 A (Claims) Japanese Patent No. 3308545 (Claims and Examples)

  Accordingly, an object of the present invention is to provide an infrared absorption filter (near infrared absorption filter) that can contain or disperse a dye having infrared absorption ability (particularly, a near infrared absorption dye) uniformly and at a high concentration and has excellent durability. ) And an infrared absorption panel (near infrared absorption panel) including the infrared absorption filter.

  As a result of intensive studies to achieve the above problems, the present inventors have found that the combination of the polycarbonate resin of the present invention and an infrared absorbing dye (particularly a near infrared absorbing dye) causes aggregation of the dye and a reaction between the dyes. In addition, the dye can be contained or dispersed in a high concentration and uniformly in the polycarbonate resin, and the infrared absorbing filter excellent in durability that can stably hold the infrared absorbing dye without causing deterioration over a long period of time (or It was found that an infrared absorbing film) was obtained, and the present invention was completed.

  That is, the infrared absorption filter (near infrared absorption filter) of the present invention is composed of a polycarbonate resin containing a repeating unit represented by the following formula (1) and a dye having infrared absorption ability.

（式中、Zはそれが結合している炭素原子と一緒になって、炭素原子数１〜１０のアルキル基を有してもよい炭素原子数５〜７のシクロアルキリデン基を示す。R^1aおよびR^1bは同一又は異なり、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜１０のアリール基、炭素原子数７〜１４のアラルキル基、炭素原子数２〜６のアルケニル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜１０のアシル基、炭素原子数１〜４のアルコキシカルボニル基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選ばれた基を表わす。m1及びm2は同一又は異なる０〜４の整数を示す。）

(In the formula, Z represents a cycloalkylidene group having 5 to 7 carbon atoms which may have an alkyl group having 1 to 10 carbon atoms, together with the carbon atom to which it is bonded. R ^1a And R ^1b are the same or different and are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, carbon It consists of an alkenyl group having 2 to 6 atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group. Represents a group selected from the group, m1 and m2 represent the same or different integers of 0 to 4)

Preferably, a polycarbonate resin composed of a repeating unit represented by the following formula (2) is included.

The dye having infrared absorbing ability (particularly, the dye having near infrared absorbing ability) is a mixture of a phthalocyanine dye, a dithiol dye, and a diimmonium dye. For example, the following formulas (3) to (7) are used. The compounds shown are preferred.

（式中、複数のＲ^pは同一又は異なっていてもよく、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜１０のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜１４のアラルキル基、アミノ基、アミド基、イミド基、及び炭素原子数６〜１０のアリールチオ基からなる群から選ばれる基を表し、複数のａは同一又は異なり、０又は１〜４の整数を示す。ａが２以上の場合六員環上で隣接するＲ^pは互いに結合して環を形成していてもよい。Ｍ_pは、水素原子、２〜６価の金属原子又はその酸化物であり、カウンターアニオンで原子価が補われていてもよい。）

(In the formula, a plurality of R ^p may be the same or different, and are a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, Represents a group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, an amino group, an amide group, an imide group, and an arylthio group having 6 to 10 carbon atoms; multiple a same or different, R ^p good .M _p be bonded to each other to form a ring of .a represents an integer of 0 or 1 to 4 are adjacent on the six-membered ring and if more is , A hydrogen atom, a divalent to hexavalent metal atom or an oxide thereof, and the valence may be supplemented with a counter anion.)

（式中、Ｒ^t1、Ｒ^t2、Ｒ^t3およびＲ^t4は、同一又は異なって、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、炭素原子数７〜１４のアラルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜１０のアリールオキシ基、又はアミノ基であり。Ｍ_t1は４配位の遷移金属原子である。）

(Wherein R ^t1 , R ^t2 , R ^t3 and R ^t4 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. An aralkyl group having 7 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an amino group, and M _t1 is a tetracoordinate transition metal atom.)

（式中、Ｒ^t5、Ｒ^t6、Ｒ^t7およびＲ^t8は、同一又は異なって、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、炭素原子数７〜１４のアラルキル基、炭素原子数１〜１０のアルコキシ基、又はアミノ基であり、置換基を有していてもよい。Ｍ_t2は４配位の遷移金属原子であり、Ｑ⁺は１価のカチオンである。）

(In the formula, R ^t5 , R ^t6 , R ^t7 and R ^t8 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. An aralkyl group having 7 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an amino group, which may have a substituent, M _t2 is a tetracoordinate transition metal atom, and Q ⁺ is It is a monovalent cation.)

（式中、Ｒⁱ¹、Ｒⁱ²、Ｒⁱ³、Ｒⁱ⁴、Ｒⁱ⁵、Ｒⁱ⁶、Ｒⁱ⁷およびＲⁱ⁸は、同一又は異なって、炭素原子数１〜１０のアルキル基であり、Ｒ^j1、Ｒ^j2、Ｒ^j3およびＲ^j4は、同一又は異なって、水素原子又はフッ素原子であり、Ｘ^2-は二価のアニオンである。）

(Wherein R ⁱ¹ , R ⁱ² , R ⁱ³ , R ⁱ⁴ , R ⁱ⁵ , R ⁱ⁶ , R ⁱ⁷ and R ⁱ⁸ are the same or different and are alkyl groups having 1 to 10 carbon atoms, R ^j1 , R ^{i j2,} R ^j3 and R ^j4 is the same or different, a hydrogen atom or a fluorine atom, X ^2-is a divalent anion.)

（式中、Ｒⁱ⁹、Ｒⁱ¹⁰、Ｒⁱ¹¹、Ｒⁱ¹²、Ｒⁱ¹³、Ｒⁱ¹⁴、Ｒⁱ¹⁵およびＲⁱ¹⁶は、同一又は異なって、炭素原子数１〜１０のアルキル基であり、Ｒ^j5、Ｒ^j6、Ｒ^j7およびＲ^j8は、同一又は異なって、水素原子又はフッ素原子であり、Ｚ^-は一価のアニオンである。）

^{(Wherein, R i9, R i10, R} i11, R i12, R i13, R i14, R i15 and R ⁱ¹⁶ is same or different, an alkyl group having 1 to 10 carbon atoms, R ^j5, R ^j6 , R ^j7 and R ^j8 are the same or different and are a hydrogen atom or a fluorine atom, and Z ⁻ is a monovalent anion.)

The infrared absorption filter may further contain a color correction pigment.
The ratio of the pigment having infrared absorbing ability may be, for example, about 0.01 to 30 parts by weight with respect to 100 parts by weight of the polycarbonate resin of the present invention. It is preferable that the infrared absorption filter selectively absorbs light in the infrared (particularly near infrared) region. Therefore, the average (average light transmittance) of light transmittance at 450 to 700 nm of the infrared absorption filter may be about 55% or more, and the average (average light transmittance) of light transmittance at 850 to 1100 nm is 30. % Or less.
The infrared absorption filter may be in the form of a film or may be formed by a casting method or a coating method.
The present invention also includes an infrared absorption panel provided with an infrared absorption filter.

  As used herein, “dispersion” does not only mean a state in which other substances are dispersed as fine particles of a plurality of molecules in a substance forming one phase, but also a single phase. It includes a state where other substances are scattered as single molecules in the substance to be formed, that is, a dissolved state.

  In the present invention, since a polycarbonate resin having a specific structure and an infrared absorbing dye (particularly a near infrared absorbing dye) are combined, a dye having an infrared absorbing ability (particularly, a near infrared absorbing dye) is uniformly contained or dispersed in a high concentration. And an infrared absorption filter (near infrared absorption filter) excellent in durability and an infrared absorption panel (near infrared absorption panel) provided with this infrared absorption filter.

  The infrared absorption filter (near infrared absorption filter) of the present invention is composed of a polycarbonate resin having a specific structure and a dye having an infrared (particularly near infrared) absorption ability (sometimes referred to as an infrared absorption dye). This infrared absorbing dye (near infrared absorbing dye) is contained in an infrared absorbing filter and is usually dispersed in the polycarbonate resin.

（式中、Zはそれが結合している炭素原子と一緒になって、置換基を有してもよい炭素原子数５〜７のシクロアルキリデン基を示す。R^1aおよびR^1bは同一又は異なり、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜１０のアリール基、炭素原子数７〜１４のアラルキル基、炭素原子数２〜６のアルケニル基、炭素原子数１〜１０のアルコキシ基、炭素原子数１〜１０のアシル基、炭素原子数１〜４のアルコキシカルボニル基、ハロゲン原子、ニトロ基、シアノ基を示す。m1、m2は同一又は異なる０〜４の整数を示す。） (Polycarbonate resin)
The polycarbonate resin usually contains a unit (repeating unit) represented by the following formula (1).

(In the formula, Z represents a cycloalkylidene group having 5 to 7 carbon atoms which may have a substituent together with the carbon atom to which it is bonded. R ^1a and R ^1b are the same or different. , An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and an alkenyl having 2 to 6 carbon atoms Group, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group, m1 and m2 are the same or Different integers from 0 to 4 are shown.)

In the formula (1), examples of Z include a cycloalkylidene group which may have a substituent having 5 to 7 carbon atoms, preferably a cyclohexylidene group.
In the above formula (1), the substituents R ^1a and R ^1b include alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, isobutyl group, t-butyl group and the like). _1-20 alkyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group etc.), cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C _5-10 cycloalkyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc.), etc. C _6-10 aryl group, preferably a C _6-8 aryl group, especially a phenyl group, an aralkyl group (benzyl group, C _6-10 aryl -C _1-4 alkyl, such as phenethyl group Etc.), an alkenyl group (vinyl group, C _2-6 alkenyl group such as propenyl group, preferably a C _2-4 alkenyl group), a hydrocarbon group (e.g., C _1-10 hydrocarbon group), an alkoxy group (C _1-4 alkoxy group such as methoxy group), acyl group (C _1-6 acyl group such as acetyl group), alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as methoxycarbonyl group), halogen An atom (a fluorine atom, a chlorine atom, etc.), a nitro group, a cyano group, etc. are mentioned.

Preferred substituents R ^1a (or R ^1b ) are an alkyl group (C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group), an aryl group (C _6-10 aryl group), an aralkyl group ( C _6-8 aryl-C _1-2 alkyl group), alkenyl group, halogen atom and the like, and particularly an alkyl group (for example, C _1-4 alkyl group such as methyl group) is preferable. The substituent R ^1a (or R ^1b ) may be substituted on the benzene ring alone or in combination of two or more. The substituents R ^1a and R ^1b may be the same or different from each other but are usually the same. The substituents R ^2a (or R ^2b ) may be different or the same in the same benzene ring.

In addition, the substitution position of the substituent R ^1a (or R ^1b ) is not particularly limited, and depends on the number of substitutions m1 (or m2) and the like, and the phenyl group has 2 to 6 positions (for example, 2 position, 3 position, 5 Position, 6-position, 3,5-position, etc.).
The preferred substitution numbers m1 and m2 are 0 or 1-3, more preferably 0 or 1-2. The substitution numbers m1 and m2 may be different but are usually the same in many cases.

In the formula (1), as a preferable combination, for example, Z is a cyclohexylidene group, m1 and m2 are 0 or 1, and substituents R ^1a and R ^1b are C _1-10 hydrocarbon groups (particularly, And a combination of an alkyl group such as a C _1-4 alkyl group).

Particularly preferred repeating units represented by the formula (1) include repeating units represented by the following formula (2).

  The polycarbonate resin of the present invention comprises a unit (repeating unit) represented by the formula (1) and a unit (repeating unit) represented by the following formula (8), and the repeating unit represented by the formula (1) 50 mol% or more, more preferably 75 mol% or more, and most preferably 100 mol%. At this time, it is particularly preferable that the repeating unit represented by the formula (1) is a repeating unit represented by the formula (2).

（式中、R^2aおよびR^2bはそれぞれ独立してハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基及び炭素数７〜２０のアラルキルオキシ基からなる群から選ばれる基を表し、ｎ１およびｎ２はそれぞれ独立に０〜４の整数であり、Wは、下記

で表される基であり、ここにR^３ａ及びR^３ｂは同一または異なり、水素原子または炭素数１〜１０の炭化水素基を表し、R^４ａ及びR^４ｂはそれぞれ独立して水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表す。）

(In the formula, R ^2a and R ^2b each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. A group selected from the group consisting of an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms. N1 and n2 are each independently an integer of 0 to 4, and W is

Wherein R ^3a and R ^3b are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ^4a and R ^4b each independently represent a hydrogen atom or a halogen atom. Or represents a C1-C3 alkyl group. )

  The polycarbonate resin of this development can be obtained by reaction of a dihydroxy compound and a carbonate-forming compound.

（式中、Ｚ、Ｒ^1a、Ｒ^1b、ｍ１及びｍ２は前記と同じ。） (Dihydroxy compound)
Although it does not specifically limit as a dihydroxy compound, When obtaining the polycarbonate resin which has a unit of the said Formula (1), the compound represented by following formula (1A) can be used.

(In the formula, Z, R ^1a , R ^1b , m1 and m2 are the same as described above.)

In the above formula (1A), preferred embodiments of the substituents (R ^1a , R ^1b ) and the number of substitutions (m1, m2) are the same as described above.
Examples of typical compounds represented by the formula (1A) are shown below.

Representative compounds include 1,1-bis (hydroxyphenyl) cycloalkanes such as 1,1-bis (hydroxyphenyl) cyclopentane {for example, 1,1-bis (4-hydroxyphenyl) cyclopentane. }; 1,1-bis (hydroxy-alkylphenyl) cyclopentane {eg, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (2-hydroxy-5-methylphenyl) ) Cyclopentane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-propylphenyl) cyclopentane, 1,1-bis (4-hydroxy-) 3-Isopropylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-n-butylphenyl) cycl 1,1-bis (1,2-bis (4-hydroxy-3-isobutylphenyl) cyclopentane, 1,1-bis [4-hydroxy-3- (1-methylpropyl) phenyl] cyclopentane, etc. Hydroxy-mono C _1-6 alkylphenyl) cyclopentane; 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-2,5-dimethylphenyl) Cyclopentane, 1,1-bis (4-hydroxy-3,5-diethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3,5-dipropylphenyl) cyclopentane, 1,1-bis ( 4-hydroxy-3,5-diisopropylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3,5-di-n-butylphenyl) 1 such as clopentane, 1,1-bis (4-hydroxy-3,5-diisobutylphenyl) cyclopentane, 1,1-bis [4-hydroxy-3,5-bis (1-methylpropyl) phenyl] cyclopentane 1,1-bis (hydroxy-diC _1-6 alkylphenyl) cyclopentane}, 1,1-bis (hydroxy-cycloalkylphenyl) cyclohexane {eg, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) 1,1-bis (hydroxy-mono C _5-8 cycloalkylphenyl) cyclopentane, etc., such as cyclopentane}, 1,1-bis (hydroxy-arylphenyl) cyclopentane {eg, 1,1-bis (4- hydroxy-3-phenyl-phenyl) cyclopentane 1,1-bis (hydroxy - mono C _6-8 ants Butylphenyl) cyclopentane; 1,1-bis (4-hydroxy-3,5-diphenyl phenyl) cyclopentane 1,1-bis (hydroxy - di C _6-8 aryl phenyl) cyclopentane, etc.}, 1,1 -Bis (hydroxy-aralkylphenyl) cyclopentane {for example, 1,1-bis [hydroxy-mono (C _6-8 arylC _1-, such as 1,1-bis (4-hydroxy-3-benzylphenyl) cyclopentane ₄ alkyl) phenyl] cyclopentane; 1,1-bis [hydroxy-di (C _6-8 arylC _1-4 alkyl) such as 1,1-bis (4-hydroxy-3,5-dibenzylphenyl) cyclopentane ) Phenyl] cyclopentane and the like}, 1,1-bis (hydroxy-alkenylphenyl) cyclopentane {eg, 1,1-bis (4-hydride) Carboxymethyl-3-propenylphenyl) cyclopentane 1,1-bis (hydroxy - mono C _2-4 alkenyl phenyl) cyclopentane, etc.}, 1,1-bis (hydroxymethyl - halophenyl) cyclopentane {e.g., 1,1 -1,1-bis (hydroxy-monohalophenyl) cyclopentane} such as bis (4-hydroxy-3-fluorophenyl) cyclopentane} and the like. 1,1-bis (hydroxyphenyl) cyclohexane {eg, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, etc.}; , 1-bis (hydroxy-alkylphenyl) cyclohexane {eg, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (2-hydroxy-5-methylphenyl) cyclohexane, 1, 1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-propylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-isopropylphenyl) cyclohexane, 1 , 1-Bis (4-hydroxy-3-n-butylphenyl) cyclohex 1,1-bis (hydroxy-) such as 1,1-bis (4-hydroxy-3-isobutylphenyl) cyclohexane, 1,1-bis [4-hydroxy-3- (1-methylpropyl) phenyl] cyclohexane Mono C _1-6 alkylphenyl) cyclohexane; 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-2,5-dimethylphenyl) cyclohexane, 1, 1-bis (4-hydroxy-3,5-diethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dipropylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5) -Diisopropylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-di-n-butylphenyl) cyclo 1,1 such as xane, 1,1-bis (4-hydroxy-3,5-diisobutylphenyl) cyclohexane, 1,1-bis [4-hydroxy-3,5-bis (1-methylpropyl) phenyl] cyclohexane -Bis (hydroxy-diC _1-6 alkylphenyl) cyclohexane}, 1,1-bis (hydroxy-cycloalkylphenyl) cyclohexane {eg 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane 1,1-bis (hydroxy-mono C _5-8 cycloalkylphenyl) cyclohexane etc.}, 1,1-bis (hydroxy-arylphenyl) cyclohexane {eg 1,1-bis (4-hydroxy-3-phenylphenyl) ) cyclohexane of 1,1-bis (hydroxy - mono C _6-8 Arirufu Yl) cyclohexane; 1,1-bis (4-hydroxy-3,5-diphenyl phenyl) cyclohexane 1,1-bis (hydroxymethyl - and di C _6-8 aryl) cyclohexane}, 1,1-bis ( Hydroxy-aralkylphenyl) cyclohexane {eg, 1,1-bis [hydroxy-mono (C _6-8 arylC _1-4 alkyl) phenyl] such as 1,1-bis (4-hydroxy-3-benzylphenyl) cyclohexane] Cyclohexane; 1,1-bis [hydroxy-di (C _6-8 arylC _1-4 alkyl) phenyl] cyclohexane etc. such as 1,1-bis (4-hydroxy-3,5-dibenzylphenyl) cyclohexane}, 1,1-bis (hydroxy-alkenylphenyl) cyclohexane {eg, 1,1-bis (4-hydroxy 1,1-bis such as 3-propenyl) cyclohexane (hydroxy - mono C _2-4 alkenyl phenyl) cyclohexane}, 1,1-bis (hydroxymethyl - halophenyl) cyclohexane {e.g., 1,1-bis (4- 1,1-bis (hydroxy-monohalophenyl) cyclohexane} such as hydroxy-3-fluorophenyl) cyclohexane. 1,1-bis (hydroxyphenyl) cycloheptane {eg, 1,1-bis (4-hydroxyphenyl) cycloheptane, etc.}; 1,1-bis (hydroxy-alkylphenyl) cycloheptane {eg, 1,1-bis Bis (4-hydroxy-3-methylphenyl) cycloheptane, 1,1-bis (2-hydroxy-5-methylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3-ethylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3-propylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3-isopropylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3-n- Butylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3-isobutylphenyl) cycloheptane, 1,1-bis [4-hydroxy-3- (1-methylpropyl) phenyl] cycloheptane such as 1,1-bis (hydroxy - mono C _1-6 alkyl phenyl) cycloheptane; 1,1-bis (4-hydroxy -3,5-dimethylphenyl) cycloheptane, 1,1-bis (4-hydroxy-2,5-dimethylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3,5-diethylphenyl) cycloheptane 1,1-bis (4-hydroxy-3,5-dipropylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3,5-diisopropylphenyl) cycloheptane, 1,1-bis (4- Hydroxy-3,5-di-n-butylphenyl) cycloheptane, 1,1-bis (4-hydroxy-3,5-diisobutylphenyl) cyclohexane Tan, 1,1-bis [4-hydroxy-3,5-bis (1-methylpropyl) phenyl] 1,1-bis such cycloheptane (hydroxy - di-C _1-6 alkyl phenyl) cycloheptane}, 1 1,1-bis (hydroxy-cycloalkylphenyl) cycloheptane {eg, 1,1-bis (hydroxy-mono C _5-8 cycloalkyl such as 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cycloheptane Phenyl) cycloheptane}, 1,1-bis (hydroxy-arylphenyl) cycloheptane {eg, 1,1-bis (hydroxy-) such as 1,1-bis (4-hydroxy-3-phenylphenyl) cycloheptane mono C _6-8 aryl phenyl) cycloheptane; 1,1-bis (4-hydroxy-3,5-diphenyl-phenylene ) 1,1-bis such cycloheptane (hydroxy - di C _6-8 aryl phenyl) cycloheptane, etc.}, 1,1-bis (hydroxy - aralkyl phenyl) cycloheptane {e.g., 1,1-bis (4- 1,1-bis [hydroxy-mono (C _6-8 arylC _1-4 alkyl) phenyl] cycloheptane such as hydroxy-3-benzylphenyl) cycloheptane; 1,1-bis (4-hydroxy-3,5 1,1-bis [hydroxy-di (C _6-8 arylC _1-4 alkyl) phenyl] cycloheptane etc.}, 1,1-bis (hydroxy-alkenylphenyl) cycloheptane such as -dibenzylphenyl) cycloheptane {For example, 1,1-bis (hydroxy-mono-C) such as 1,1-bis (4-hydroxy-3-propenylphenyl) cycloheptane _{2-4alkenylphenyl} ) cycloheptane}, 1,1-bis (hydroxy-halophenyl) cycloheptane {eg, 1,1-bis such as 1,1-bis (4-hydroxy-3-fluorophenyl) cycloheptane (Hydroxy-monohalophenyl) cycloheptane} and the like. Examples include 1,1-bis (hydroxyphenyl) cycloalkane having the above substituents.

  The compound represented by the formula (1A) can be obtained by a reaction between a cycloalkanone (such as cyclohexanone) and a corresponding phenol. For example, 1,1-bis (4-hydroxyphenyl) cyclohexane may be obtained, for example, by reaction of phenol and cyclohexanone.

(Carbonate-forming compound)
The carbonate-forming compound (carbonate-forming derivative, carbonate precursor) which is a raw material of the polycarbonate resin means a compound capable of forming a carbonate bond. Examples of such carbonate-forming compounds include phosgenes (phosgene, diphosgene, triphosgene, etc.), carbonates [eg, dialkyl carbonates (dimethyl carbonate, diethyl carbonate, etc.), diaryl carbonates (diphenyl carbonate, dinaphthyl carbonate, etc.). Carbonic acid diesters such as phosgene and the like. Among them, phosgene and diphenyl carbonate are preferably used. The carbonate-forming compounds may be used alone or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin may be, for example, about 5,000 to 100,000, preferably about 8,000 to 50,000, and more preferably about 10,000 to 30,000. The viscosity average molecular weight (M) here is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving the polycarbonate resin in methylene chloride at a concentration of 0.7 g / dl at 20 ° C. into the following equation. It is a thing.
η _sp /C=[η]+0.45×[η] ² C
[Η] = 1.23 × 10 ⁻⁴ M ^0.83 (C is a resin concentration of 0.7)

  When the viscosity average molecular weight is too small (for example, smaller than 5,000), the heat resistance of the polycarbonate resin may be lowered. In addition, when the viscosity average molecular weight is too large (for example, greater than 100,000), not only is the synthesis of the polycarbonate resin difficult, but also melting occurs when the infrared absorption filter of the present invention is produced by melt kneading. Kneading may be difficult, and when an infrared absorption filter is produced by a casting method or a coating method, the solubility in a solvent may be reduced.

  The glass transition point (Tg) of the polycarbonate resin may be, for example, about 80 to 250 ° C., preferably about 100 to 200 ° C. If the Tg is too low (for example, lower than 80 ° C.), the heat resistance of the infrared absorption filter of the present invention may be reduced. If the Tg is too high (greater than 250 ° C.), When manufacturing an infrared absorption filter, melt kneading may be difficult.

  The polycarbonate resin can be produced by a reaction means known per se for producing an ordinary polycarbonate resin. For example, in a reaction using phosgene as a carbonate-forming compound, a reaction of a dihydroxy compound and phosgene is usually performed in the presence of an alkali compound such as sodium hydroxide or potassium hydroxide, and a solvent such as methylene chloride or chlorobenzene. Good. At this time, in order to promote the reaction, for example, a tertiary amine such as triethylamine or a quaternary ammonium salt such as tetra-n-butylammonium bromide or a phosphonium salt such as tetra-n-butylphosphonium bromide is used. You can also.

  When a carbonic acid diester such as diphenyl carbonate is used as the carbonate-forming compound, the dihydroxy compound and the carbonic acid diester may be heated and reacted in an inert gas atmosphere to distill off the resulting alcohol or phenol. . At this time, in order to promote the reaction, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal salts of alkaline metals such as boron and aluminum, alkaline earth metal salts, quaternary Normal esterification reaction of ammonium salts, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, silicon compounds, germanium compounds, tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. The catalyst used for the transesterification reaction can also be used.

  Moreover, the said polycarbonate resin can use the monofunctional phenols normally used as a terminal stopper in the polymerization reaction. When a monofunctional phenol is used as a terminal terminator, the terminal can be sealed with a group derived from a monofunctional phenol, and a polycarbonate resin excellent in thermal stability can be obtained.

The pigment | dye which has an infrared absorptivity should just be a pigment | dye which has an absorption or absorption area | region in an infrared region at least, especially a near infrared region (for example, about 850-1100 nm). Therefore, it is preferable that the maximum absorption wavelength of the pigment having infrared absorbing ability is in the range of 800 to 1000 nm. Examples of such dyes, full Taroshianin dyes, dithiol-based dye (or dithiolene dyes), preferably diimmonium dyes, in the present invention, phthalocyanine dye, mixtures of dithiol dyes and diimmonium dye is used.

（式中、複数のＲ^pは同一又は異なっていてもよく、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜１０のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜１４のアラルキル基、アミノ基、アミド基、イミド基、及び炭素原子数６〜１０のアリールチオ基からなる群から選ばれる基を表し、置換基を有していてもよく、複数のａは同一又は異なり、０又は１〜４の整数を示す。ａが２以上の場合六員環上で隣接するＲ^pは互いに結合して環を形成していてもよい。Ｍ_pは、水素原子、２〜６価の金属原子又はその酸化物であり、カウンターアニオンで原子価が補われていてもよい。） (Phthalocyanine dye)
Examples of the phthalocyanine dye include a compound represented by the following formula (3).

(In the formula, a plurality of R ^p may be the same or different, and are a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, Represents a group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, an amino group, an amide group, an imide group, and an arylthio group having 6 to 10 carbon atoms; A plurality of a may be the same or different and each represents 0 or an integer of 1 to 4. When a is 2 or more, adjacent R ^p on the 6-membered ring are bonded to each other to form a ring. M _p is a hydrogen atom, a divalent to hexavalent metal atom or an oxide thereof, and the valence may be supplemented with a counter anion.)

In the group represented by R ^p (for example, an alkyl group, an amino group, and the like), the substituent includes a hydrocarbon group (for example, an alkyl group (for example, a C _1-6 alkyl group such as a methyl or ethyl group), a cycloalkyl group, etc. Group (C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (C _6-10 aryl group such as phenyl group, preferably C _6-8 aryl group), aralkyl group (benzyl group etc.) C _6-10 aryl-C _1-4 alkyl group etc.)], alkoxy groups (C _1-4 alkoxy groups such as methoxy group, ethoxy group, butoxy group etc.), acyl groups (C _1-6 such as acetyl group). Acyl group), halogen atom (fluorine atom, chlorine atom, etc.), hydroxyl group, nitro group, cyano group, amino group [amino group, substituted amino group (mono- or dialkylamino group such as dimethylamino group (C _1-4) Alkylamino group and the like))] and the like. The substituents may be substituted singly or in combination of two or more.

In R ^p of the formula (3), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom (preferably a fluorine atom, a chlorine atom, and particularly a fluorine atom). Examples of the alkyl group include C _1-20 alkyl groups (preferably C _3-10 alkyl groups) such as a methyl group, a t-butyl group, a t-amyl group (1,1-dimethylpropyl group), and a trifluoromethyl group. Examples of the alkoxy group include an alkoxy group corresponding to the alkyl group such as a butoxy group [for example, a C _1-20 alkoxy group (preferably a C _3-10 alkoxy group)] and the like. Examples of the aryl group include a C _6-10 aryl group such as a phenyl group (preferably a C _6-8 aryl group). The aryloxy group includes an aryloxy group corresponding to the aryl group such as a phenoxy group [ For example, C _6-10 aryloxy group (preferably C _6-8 aryloxy group)] and the like can be mentioned. Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group (preferably a C _6-8 aryl-C _1-2 alkyl group).

Examples of the amino group include mono- or di-C _1-10 alkylamino groups (preferably mono- or di-C _1-4 alkylamino groups) such as amino group and dimethylamino group, alkylideneamino groups (for example, octadecanideneamino group). (—NH═CH—C ₁₇ H ₃₅ ) and the like. Examples of the amide group include an acylamide group (such as an acetamide group), and examples of the imide group include a methylphthalimide group. Examples of the arylthio group include C _6-10 arylthio groups (preferably C _6-8 arylthio group) such as phenylthio group and p-methylphenylthio group. Further, adjacent R ^p may form a ring, for example, a hydrocarbon ring such as an arene ring (such as a benzene ring) or a cycloalkane ring (such as a cycloalkane ring). You may have the same substituent (an alkyl group etc.).
The substitution position of the group R ^p is not particularly limited, and may be any of positions 3 to 6 of the benzene ring.

  In the formula (3), examples of the metal atom represented by Mp include alkaline earth metals (Mg, etc.), periodic table group 13 metals (Al, etc.), periodic table group 14 metals (Si, Ge, Sn, Pb, etc.), transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Rh, etc.) and the like.

The counter anion (or valence a supplement group), for example, a hydroxyl group, a halide ion (chloride ion, bromide ion, etc. iodide ion), tri C ₁ such as trialkyl silyl group (trihexyl silyloxy _-10 alkylsilyloxy groups), metal acid ions (such as hexafluoroantimonate ions (SbF ₆ ⁻ )), inorganic acid ions (halogen ions such as perchlorate ions, hexafluorophosphate ions (PF ₆₎ ^-) ions containing phosphorus, such as tetrafluoroborate ion (BF ₄ ^- ion containing boron, etc.)) and the like.

Below, shows typical phthalocyanine dye represented by the formula (3), Mp, using a combination of R ^p, a, and the counter anion in the table below. In the table, “H” represents a hydrogen atom, “F” represents a fluorine atom, and “Cl” represents a chlorine atom.

In addition, a commercial item can also be utilized for such a phthalocyanine dye (phthalocyanine metal complex). Examples of such commercially available products include the following products from Nippon Shokubai Co., Ltd .; eXcolor “814K”, “810K”, “812K”, “905B”, “IR-1”, “IR-3” Can be used suitably.
The phthalocyanine dyes may be used alone or in combination of two or more.

（式中、ＸおよびＹは、同一又は異なって、酸素原子、硫黄原子、ＮＨ又はＮＨ₂を示し、Ｒ^tは、同一又は異なってシアノ基又は置換基を有していてもよいフェニル基を示し、隣接する炭素原子に置換するＲ^tは、ベンゼン環又はナフタレン環を形成していてもよい。Ｍｔは、４配位の遷移金属原子を示し、カウンターアニオンで原子価が補われていてもい。） (Dithiol dye)
Examples of the dithiol dye (or dithiolene dye) include a compound represented by the following formula.

Wherein X and Y are the same or different and each represents an oxygen atom, a sulfur atom, NH or NH ₂ , and R ^t is the same or different and represents a phenyl group which may have a cyano group or a substituent. shown, R ^t that substituting adjacent carbon atoms may be combined to form a benzene ring or a naphthalene ring .Mt is a transition metal atom tetracoordinate, Some have valence is compensated by a counter anion .)

  In the above formula, examples of the tetracoordinate transition metal atom Mt include Ti, V, Cr, Co, Ni, Zr, Mo, Fe, Ru, Pd, Os, and Pt. A preferred Mt is Ni. Examples of the substituent include the same substituents as those exemplified above (for example, a substituted amino group such as an alkyl group, an aryl group, an alkoxy group, a halogen atom, and a dimethylamino group).

（式中、Ｒ^t1、Ｒ^t2、Ｒ^t3およびＲ^t4は、同一又は異なって、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、炭素原子数７〜１４のアラルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜１０のアリールオキシ基、又はアミノ基であり。Ｍ_t1は４配位の遷移金属原子である。）

（式中、Ｒ^t5、Ｒ^t6、Ｒ^t7およびＲ^t8は、同一又は異なって、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、炭素原子数７〜１４のアラルキル基、炭素原子数１〜１０のアルコキシ基、又はアミノ基であり、置換基を有していてもよい。Ｍ_t2は４配位の遷移金属原子であり、Ｑ⁺は１価のカチオンである。）
上記式（４）および（５）において、Ｍ_t1およびＭ_t2で表される４配位の遷移金属原子としては、前記と同様の金属原子が挙げられ、特に、Ｎｉが好ましい。 Preferred examples of the dithiol dye include aromatic dithiol metal complexes represented by the following formula (4) or (5).

(Wherein R ^t1 , R ^t2 , R ^t3 and R ^t4 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. An aralkyl group having 7 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an amino group, and M _t1 is a tetracoordinate transition metal atom.)

(In the formula, R ^t5 , R ^t6 , R ^t7 and R ^t8 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. An aralkyl group having 7 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an amino group, which may have a substituent, M _t2 is a tetracoordinate transition metal atom, and Q ⁺ is It is a monovalent cation.)
In the above formulas (4) and (5), examples of the tetracoordinate transition metal atom represented by M _t1 and M _t2 include the same metal atoms as described above, and Ni is particularly preferable.

In the above formulas (4) and (5), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include a C _1-10 alkyl group such as a methyl group (preferably a C _1-4 alkyl group).
Examples of the aryl group include a C _6-10 aryl group (preferably a C _6-8 aryl group) such as a phenyl group, a dimethylaminophenyl group, and a methoxyphenyl group.
Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group (preferably a C _6-8 aryl-C _1-2 alkyl group).
Examples of the alkoxy group include an alkoxy group corresponding to the alkyl group such as a methoxy group and a butoxy group [for example, a C _1-10 alkoxy group (preferably a C _1-4 alkoxy group)]. Examples thereof include mono- or di-C _1-10 alkylamino groups (preferably mono- or di-C _1-4 alkylamino groups) such as dimethylamino group and diethylamino group.

In the formula (5), the monovalent cation represented by Q ⁺ is a tetraalkylammonium ion (tetraC _1-10 alkylammonium ion such as tetrabutylammonium ion, preferably tetraC _1-6 alkyl). Ammonium ions, etc.), cations containing phosphorus atoms [eg (CH ₃ O) ₃ P ⁺ etc.], etc., and tetra C _1-4 alkylammonium ions are preferred.

Hereinafter, representative dithiol dyes represented by the above formula (4) are represented by the above formula (5) using a combination of M _t1 , R ^t1 , R ^t2 , R ^t3 and R ^t4. Representative dithiol dyes are shown in the table below using combinations of M _t2 , R ^t5 , R ^t6 , R ^t7 , R ^t8 and Q ⁺ . In the table, “Bu ₄ N ⁺ ” represents “tetrabutylammonium ion”.

As the aromatic dithiol metal complex represented by the formula (4) or (5), a commercially available product may be used, and a 4-coordinate transition metal atom represented by M _t1 or M _t2 and 1, 2 It can also be synthesized utilizing a reaction with -diphenyl-1,2-ethenedithiols. Examples of 1,2-diphenyl-1,2-ethenedithiols include, for example, 1,2-diphenyl-1,2-ethenedithiol, 1,2-di (alkoxyphenyl) -1,2-ethenedithiol (for example, 1,2-di (C _1-4 alkoxyphenyl) -1,2-ethenedithiol, etc.) such as 1,2-di (4-methoxyphenyl) -1,2-ethenedithiol.

  The dithiol dyes (the aromatic dithiol metal complexes) may be used alone or in combination of two or more. In particular, the aromatic dithiol-based metal complex represented by the formula (4) or (5) has strong absorption at 850 to 900 nm, and blocks the near-infrared wavelength used for a remote control or the like. A near-infrared absorption filter using a metal complex is effective in preventing malfunction of the remote control.

（式中、Ｒⁱ¹、Ｒⁱ²、Ｒⁱ³、Ｒⁱ⁴、Ｒⁱ⁵、Ｒⁱ⁶、Ｒⁱ⁷およびＲⁱ⁸は、同一又は異なって、炭素原子数１〜１０のアルキル基であり、Ｒ^j1、Ｒ^j2、Ｒ^j3およびＲ^j4は、同一又は異なって、水素原子又はフッ素原子であり、Ｘ^2-は二価のアニオンである。）

（中、Ｒⁱ⁹、Ｒⁱ¹⁰、Ｒⁱ¹¹、Ｒⁱ¹²、Ｒⁱ¹³、Ｒⁱ¹⁴、Ｒⁱ¹⁵およびＲⁱ¹⁶は、同一又は異なって、炭素原子数１〜１０のアルキル基であり、Ｒ^j5、Ｒ^j6、Ｒ^j7およびＲ^j8は、同一又は異なって、水素原子又はフッ素原子であり、Ｚ^-は一価のアニオンである。） (Diimonium dye)
Examples of the diimmonium dye include a compound (aromatic diimmonium compound) represented by the following formula (6) or (7).

(Wherein R ⁱ¹ , R ⁱ² , R ⁱ³ , R ⁱ⁴ , R ⁱ⁵ , R ⁱ⁶ , R ⁱ⁷ and R ⁱ⁸ are the same or different and are alkyl groups having 1 to 10 carbon atoms, R ^j1 , R ^{i j2,} R ^j3 and R ^j4 is the same or different, a hydrogen atom or a fluorine atom, X ^2-is a divalent anion.)

(In the ^formula , R ⁱ⁹ , R ⁱ¹⁰ , R ⁱ¹¹ , R ⁱ¹² , R ⁱ¹³ , R ⁱ¹⁴ , R ⁱ¹⁵ and R ⁱ¹⁶ are the same or different and are alkyl groups having 1 to 10 carbon atoms, R ^j5 , R ^j6 , R ^j7 and R ^j8 are the same or different and are a hydrogen atom or a fluorine atom, and Z ⁻ is a monovalent anion.)

In the above formula (6) or (7), examples of the alkyl group include the above-exemplified alkyl groups, for example, C _1-10 alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, A C _1-8 alkyl group is preferable, and a C _1-6 alkyl group is more preferable. The alkyl group may be a perfluoroalkyl group, and examples thereof include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

In the formula (6), the divalent anion X ²⁻ is not particularly limited, and examples thereof include oxygen ions (O ²⁻ ), inorganic acid ions [carbonate ions (CO ₃ ²⁻ ), sulfate ions (SO ₄ ). ^2- ) etc.], organic acid ions [oxalate ion (C ₂ O ₄ ^2- ) etc.] and the like. In the formula (7), examples of the monovalent anion Z ⁻ include the same anions as the counter anion, and in particular, metal acid ions (such as hexafluoroantimonate ion (SbF ₆ ⁻ )), Inorganic acid ion (halogen ion such as perchlorate ion, ion containing phosphorus such as hexafluorophosphate ion (PF ₆ ⁻ ), ion containing boron such as tetrafluoroborate ion (BF ₄ ⁻ ), etc. Etc.) are preferred.

In the formula (6) or (7), preferred R ^{i1 to} R ⁱ⁸ (or R ^{i9 to} R ⁱ¹⁶ ) and R ^j1
Examples of combinations with ^{˜R j4} (or R ^{j5 ˜R j8} ) include the former / the latter = butyl group / hydrogen atom, pentyl group / hydrogen atom, butyl group / fluorine atom, and the like.
The following table shows typical diimmonium dyes represented by the formula (7) using combinations of R ^{i9 to} R ⁱ¹⁶ , R ^{j5 to} R ^j8 and Z ⁻ .

Infrared absorbing dye constituting the infrared absorption filter of the present invention, the infrared absorption wavelength region of the color-containing (in particular the absorption wavelength region of near-infrared) and the maximum absorption wavelength slightly different order, full Taroshianin dyes, dithiol dyes, and diimmonium combining all three of each dye of dye used.

  The ratio of the infrared absorbing dye is 0.01 to 30 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the polycarbonate resin (or resin component) of the present invention. About a part. Usually, it may be about 0.01 to 10 parts by weight. In particular, when using a phthalocyanine dye, a dithiol dye, and / or a diimmonium dye, the ratio of the phthalocyanine dye is 0.01 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin (or resin component) of the present invention. About 3.0 parts by weight (preferably 0.05 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight), and the ratio of the dithiol dye is 0.01 to 3.0 parts by weight (preferably Is about 0.05 to 2.5 parts by weight, more preferably 0.1 to 2.0 parts by weight, and the ratio of the diimmonium dye is 0.1 to 10 parts by weight (preferably 0.2 to 8.0 parts by weight). Part, more preferably about 0.5 to 6.0 parts by weight). In addition, the said polycarbonate resin as binder resin which comprises the near-infrared absorption filter of this invention can disperse | distribute various pigments uniformly, and can make the density | concentration of the said pigment | dye with respect to the said binder resin deep.

  The ratio of the infrared absorbing dye is determined based on whether the film thickness of the infrared absorbing filter and other films (such as an electromagnetic wave absorbing layer) that can be used in combination with the infrared absorbing filter of the present invention have near infrared absorbing ability. It is preferable to adjust according to the above. For example, when combined with an electromagnetic wave absorbing layer (heat ray reflective glass) having near infrared reflection characteristics, the phthalocyanine dye is added in an amount of 0.01-2.100 with respect to 100 parts by weight of the polycarbonate resin (or resin component) of the present invention. It is preferable to use about 0 parts by weight, about 0.5 to 2.5 parts by weight of the dithiol dye, and about 0.2 to 6.0 parts by weight of the diimmonium dye. When the near infrared absorbing film has a film thickness of about 10 μm and the electromagnetic wave absorbing layer has no near infrared absorbing ability, the phthalocyanine dye 0 is used with respect to 100 parts by weight of the polycarbonate resin (or resin component) of the present invention. It is preferable to use about 0.1 to 1.0 parts by weight, about 0.5 to 2.0 parts by weight of a dithiol dye, and about 1.0 to 6.0 parts by weight of a diimmonium dye. When the concentration of the dye is smaller than the above-described concentration range, the visible light transmittance is high, but the infrared (near infrared) absorption is small and may not function as an infrared absorption filter. Moreover, when the density | concentration of each pigment | dye is larger than the above-mentioned density range, although infrared absorption is large, since visible light transmittance | permeability becomes low, it is unpreferable.

  The infrared absorption filter may further contain a color correction pigment. That is, in the infrared absorption filter of the present invention (particularly, the near infrared absorption filter), in order to freely correct the color tone of the infrared absorption filter, a visible light absorbing dye for color tone correction is used together with a pigment having near infrared absorption ability. It may be used. Such color tone correction is particularly important when, for example, the infrared absorption filter is used as an infrared absorption filter for a display such as a plasma display.

  Such a visible light absorbing dye for color tone correction may be a dye capable of absorbing visible light (particularly, having a narrow visible light absorption band and high transmittance at other wavelengths). For example, conventional coloring Agents (for example, dyes such as black pigments, red pigments, green pigments, blue pigments) may be used. When the infrared absorbing dye has absorption in the visible light region, the infrared absorbing dye It can also be used as a correction dye. Examples of such color tone correction dyes include cyanine dyes, quinone dyes, azo dyes, indigo dyes, polyene dyes (polymethine dyes, etc.), spiro dyes, porphyrins, phthalocyanine dyes, and the like. It is done. The color tone correction dyes may be used alone or in combination of two or more.

In the infrared absorption filter of the present invention, for the purpose of selectively blocking infrared rays (especially near infrared rays), light transmittance in the infrared region (especially near infrared region) is low, and further, other regions (especially It is important that the light transmittance in the visible light region) is high. In the present invention, the light transmittance in the infrared region (particularly the near-infrared region) is low by combining a specific binder resin and a pigment having near-infrared absorption ability (and a color tone correction pigment as necessary), and An infrared absorption filter having high light transmittance in the visible light region can be obtained. Specifically, the average light transmittance at 450 to 700 nm is 55% or more [for example, 55 to 100%, preferably 60% or more (for example, 60 to 99%), more preferably 70% or more (for example, 70 to 70%). The average light transmittance at 850 to 1100 nm is 30% or less [for example, 0 to 30%, preferably 15% or less (for example, 0.5 to 15%), more preferably 10% or less (for example, about 1 to 10%)].
Moreover, antioxidant, a heat stabilizer, a flame retardant, etc. can be suitably added and used for the infrared rays absorption filter of this invention in the range which does not impair the effect of this invention as needed.

  Antioxidants that can be used in the near-infrared absorption filter of the present invention are usually known antioxidants, and examples thereof include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Among these, phenolic antioxidants, particularly alkyl-substituted phenolic antioxidants are preferred. Specifically, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert-butyl 4-hydroxybenzylphosphonate diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2- [β- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5.5) undecane and the like. These antioxidants may be used alone or in combination of two or more. The range of the preferable addition amount of these antioxidants may be about 0.0001 to 0.05% by weight with respect to the entire components of the near infrared absorption filter.

  The heat stabilizer that can be used in the near infrared absorption filter of the present invention is preferably a phosphorus stabilizer, and examples thereof include phosphite compounds, phosphate compounds, and phosphonite compounds. Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4 -Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Phosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and the like.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl Examples thereof include phosphate and diisopropyl phosphate.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Examples thereof include phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-biphenylene diphosphonite, and the like. It is done.
Among these, tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphate, and trimethyl phosphate are preferable.

  These heat stabilizers may be used alone or in combination of two or more. The heat stabilizer is preferably 0.001 to 0.5% by weight, more preferably 0.005 to 0.3% by weight, based on the entire components of the near infrared absorption filter.

  The near-infrared absorption filter of the present invention further includes additives such as flame retardants, ultraviolet absorbers, mold release agents, antistatic agents, antibacterial agents, lubricants, fillers, and other thermoplastic resins (other polycarbonate resins). , Polyester resin, etc.) may be added in a small proportion within a range not impairing the object of the present invention.

  The infrared absorption filter (near infrared absorption filter) of the present invention may have any shape or form depending on the application, but is preferably in the form of a film (or film). Such a film-like infrared absorption filter (infrared absorption film) may be a film (coating film) formed on a substrate or the like, or may be a single film without a substrate or the like.

  As described above, the infrared absorption filter (near infrared absorption filter) of the present invention is usually obtained by dispersing a dye having infrared absorption ability in a polycarbonate resin having a specific repeating unit, and the shape or form thereof. Depending on the method, it can be produced or formed into a film using a conventional method such as a casting method, a coating method, a melt extrusion method (extrusion molding method or the like). Specifically, the infrared absorption filter is formed by casting (forming a film) from a coating solution obtained by uniformly dispersing a pigment having near infrared absorption ability in the polycarbonate resin solution, glass, styrene. -Based resin, acrylic resin, amorphous polyolefin resin, cellulosic resin, coating method of coating on transparent sheet or film such as polyester resin and polycarbonate resin, blending pigment with infrared absorbing ability and the above polycarbonate resin And it can obtain by methods, such as the method of forming into a film by the melt extrusion method. Among them, a method of forming a film by a casting method or a coating method (forming a film), that is, a casting method from a coating solution obtained by uniformly dispersing a pigment having a near infrared absorption ability in the polycarbonate resin solution A method of forming a film by the coating method or a coating method obtained by coating the coating liquid on a transparent film is preferable. That is, since the film is formed at a high temperature (for example, a temperature of 200 ° C. or more) in the normal melt extrusion method, there is a possibility that the dye is thermally decomposed, whereas in the casting method or the coating method, it is relatively low temperature (for example, 150 The film can be formed and dried at a temperature below (° C.), so that thermal decomposition of the dye having infrared absorption ability can be suppressed or prevented, and dyes with low heat resistance can be used as long as they can be dissolved or uniformly dispersed in a solvent. Because it can.

  In the casting method, the coating solution is poured onto a glass plate, mirror-finished metal plate or polyester film, etc., and the coating solution is spread on the surface of the plate with a stick with a certain gap and then dried. The film can be peeled from the surface by a simple method to obtain a film. In such a casting method, a film may be produced using a mechanized casting machine. In the coating method, a film layer can be formed by applying a coating solution on a film or panel by a bar coating method, a spray coating method, a dip coating method, a flow coating method, or the like and drying. In addition, when coating on a film continuously, various roll coaters can be used preferably. In such coating, for example, the coating solution is extruded at a constant speed from a T-die onto a film moving at a predetermined speed (for example, several meters to several tens of meters), and then dried. You may use the machine which removes a solvent in a zone and performs a series of processes which wind up a film.

  As a solvent for the coating liquid (specifically, a solvent for dissolving a polycarbonate resin used for preparing the near-infrared absorption filter of the present invention by a casting method or a coating method and dispersing a pigment), resin and pigment In addition to practical solubility, a solvent that is inert to the dye and has a practically preferable boiling point may be selected. Examples of such solvents include halogen-based organic solvents (for example, aliphatic halogen compounds such as chloroform, dichloromethane, dichloroethane), non-halogen-based organic solvents (for example, aromatic hydrocarbons such as toluene, xylene, methyl ethyl ketone, Ketones such as acetone, cyclohexanone, and cyclopentanone, and ethers such as tetrahydrofuran. The solvents may be used alone or in combination of two or more.

  Since the concentration of the coating solution needs to be adjusted depending on the type of solvent, the film thickness of the filter to be created, the creation method, and the like, for example, it may be in the range of 1 to 30% by weight, Preferably, it may be about 5 to 25% by weight.

  The film thickness of the near-infrared absorption filter of the present invention is not unconditional because it is necessary to appropriately adjust depending on the type and concentration of the dye used, but it may be in the range of 1 to 100 μm, preferably 1 to 50 μm, More preferably, it may be about 1 to 20 μm.

  The present invention also includes an infrared absorption panel (near infrared absorption panel) or an infrared absorption multilayer film provided with the infrared absorption filter. That is, the infrared absorption filter may be combined with another film or panel having near infrared absorption ability or a film or panel having a specific function to form an infrared absorption multilayer film or an infrared absorption multilayer panel. Specific functions include, for example, electromagnetic wave absorption ability, antireflection ability, and shape retention ability.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.
Evaluation of the binder resin (the resin obtained in the synthesis example, that is, the polycarbonate resin and the polyester resin) and the infrared absorption filter were performed by the following methods.

(1) Viscosity average molecular weight (M) measurement: The specific viscosity (η _sp ) obtained from a solution in which a binder resin was dissolved in methylene chloride at a concentration of 0.7 g / dl at 20 ° C. was determined by inserting it into the following equation.
η _sp /C=[η]+0.45×[η] ² C
[Η] = 1.23 × 10 ⁻⁴ M ^0.83 (C is a resin concentration of 0.7)
(2) Film thickness: The film thickness of the infrared absorption filter thin film obtained by applying and drying on a glass substrate was measured using a thin film measuring instrument (QuoreMSPA1000 manufactured by Mamiya Oppy).
(3) Presence / absence of dye aggregation: Observation was performed with an optical microscope at a magnification of 500 times, and the presence / absence of dye aggregation in the infrared absorption filter was visually examined.
(4) Average visible light transmittance: It was determined by measuring the light transmittance at 450 to 700 nm using a near infrared spectrophotometer (Nireco model 6500).
(5) Average infrared transmittance: It was determined by measuring the light transmittance at 850 to 1100 nm using a near infrared spectrophotometer (Nireco model 6500).
(6) Environmental resistance test: The light transmittance (average visible light transmittance and average infrared transmittance) after treating the infrared absorption filter in a constant temperature and humidity environment of 60 ° C. and 90% humidity for 600 hours, It compared with the light transmittance before a process.

[Synthesis Example 1]
To a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 14863 parts of ion-exchanged water and 5772 parts of 48% aqueous sodium hydroxide were added, and 2148 parts of 1,1-bis (4-hydroxyphenyl) cyclohexane and sodium hydrosal were added. After dissolving 4 parts of phyto and adding 8518 parts of methylene chloride, 1000 parts of phosgene was blown in over 60 minutes at 23-27 ° C. with stirring. After the completion of phosgene blowing, 38 parts of p-tert-butylphenol was added, and 2 parts of triethylamine was further added, followed by stirring at 20 to 27 ° C. for 40 minutes to complete the reaction. The methylene chloride layer containing the product was washed with dilute hydrochloric acid and pure water, and then methylene chloride was evaporated to obtain a polycarbonate resin. The average molecular weight of the obtained polycarbonate resin was 21,000.

[Synthesis Example 2]
In a reactor equipped with a thermometer, a stirrer, and a decompressor, 2235 parts of dimethyl terephthalate, 1000 parts of ethylene glycol, 4037 parts of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 0.92 of calcium acetate Part was added and gradually heated and melted while stirring, and a transesterification reaction was performed at 180 to 230 ° C. to distill off methanol. Subsequently, 3.51 parts of di-n-butyltin oxide was added, and the temperature was gradually raised to 290 ° C. and 100 Pa, and ethylene glycol was removed while reducing the pressure to obtain a polyester resin. The resulting polyester resin had a viscosity average molecular weight of 18,400.

Example 1
94 parts of the polycarbonate resin obtained in Synthesis Example 1, 1 part of nickel-bis-1,2-diphenyl-1,2-ethenedithiolato (MIR101, manufactured by Midori Chemical Co., Ltd.), phthalocyanine dye (manufactured by Nippon Shokubai, EEX Color) 810K) and 1 part of diimmonium dye (manufactured by Nippon Kayaku Co., Ltd., IRG022) were added to 341 parts of cyclopentanone and stirred at room temperature for 10 hours to obtain a coating solution. The dispersion state of each pigment in the obtained coating solution was good. This coating solution is formed into a glass plate shape by spin coating so that the thickness of the coating film after drying is 4.0 μm, and is dried at 80 ° C. for 30 minutes using an oven. A film (infrared absorbing filter) was obtained. The appearance of the coating film was in a good state with no unevenness. Further, when the aggregation of the dye was observed, no aggregates or the like were observed. The light transmittance at 400 nm to 1200 nm of this coating film was measured, an environmental resistance test was performed, and then the spectrum of light transmittance was measured again. The light transmittance spectrum before and after the environmental resistance test is shown in FIG. Table 4 shows the visible light transmittance and infrared transmittance before and after the environmental resistance test.

(Comparative Example 1)
Using the polyester resin obtained in Synthesis Example 2, a coating solution and a coating film were obtained in the same manner as in Example 1. The obtained coating liquid dispersed each pigment | dye satisfactorily, and the external appearance of the coating film was a favorable state with no unevenness. Table 4 shows the results of the same observations and tests as in Example 1.

(Comparative Example 2)
A coating solution and a coating film were obtained in the same manner as Example 1 using Panlite L-1250 (polycarbonate composed of 2,2-bis (4-hydroxyphenyl) propane) manufactured by Teijin Chemicals Limited. Although the obtained coating liquid dispersed each pigment | dye favorably, aggregation of the pigment | dye was seen in the coating film and the external appearance was not favorable.
The results are shown in Table 4.

  As apparent from Table 4, the infrared absorption filter obtained in Example 1 had good infrared absorption performance with no pigment aggregation, high visible light transmittance, and low infrared transmittance. Furthermore, as is clear from FIG. 1, the infrared absorption performance was not deteriorated by the environmental resistance test. On the other hand, the infrared absorption filter shown in Comparative Example 1 showed the same infrared absorption performance as that of the example, but deterioration was observed by the environmental resistance test. In Comparative Example 2, the dyes aggregated and a uniform infrared absorption filter could not be obtained.

  In the infrared absorbing filter (near infrared absorbing filter) of the present invention, by using the specific polycarbonate resin of the present invention, the infrared absorbing dye (near infrared absorbing dye) can be uniformly dispersed in the resin. There is no aggregation of pigments or reaction between pigments. For this reason, it is possible to achieve both blocking of infrared rays (particularly, near infrared rays) and transmission of visible light with a thin film (for example, a thin film of about several tens of μm). In addition, the near-infrared absorption filter of the present invention is composed of the specific polycarbonate resin of the present invention, and the dye having infrared absorption ability (near infrared) is stabilized in the specific polycarbonate resin. Deterioration due to light, moisture, etc. is remarkably suppressed, and stable performance can be maintained over a long period of time.

  Therefore, the infrared absorption filter (and infrared absorption panel) of the present invention absorbs infrared rays (near infrared rays) generated from various applications that require high performance and durability, such as video output devices and lighting fixtures. Remote control that uses light in the infrared (particularly near infrared) region for communication, infrared absorption filter (near infrared filter) that prevents malfunction of the infrared communication port and prevents malfunction of devices controlled by these remote control devices, etc. Available as Further, it can be suitably used as a near-infrared absorption filter used for light-receiving sensitivity correction and color tone correction of a light-receiving element or an image sensor of an optical device. Specifically, the infrared absorption filter (and infrared absorption panel) of the present invention is, for example, an infrared absorption filter (infrared ray) such as a plasma display (or a front panel of a plasma display), a solid-state image sensor (CCD) camera, a photodiode or the like. It can be suitably used as an absorption panel) and is extremely useful.

FIG. 1 is a light transmittance spectrum of the coating film obtained in Example 1 before and after the environmental resistance test.

Claims (21)

An infrared absorption filter comprising a polycarbonate resin containing a repeating unit represented by the following formula (1) and a dye having an infrared absorbing ability which is a mixture of a phthalocyanine dye, a dithiol dye and a diimmonium dye .

(In the formula, Z, together with the carbon atom to which it is attached, represents a cycloalkylidene group having 5 to 7 atoms. R ^1a and R ^1b are the same or different and are alkyl having 1 to 20 carbon atoms. Groups, cycloalkyl groups having 6 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 14 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, and 1 to 10 carbon atoms. A group selected from the group consisting of an alkoxy group, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, and a cyano group, and m1 and m2 are the same or different. Represents an integer of ~ 4.) The infrared absorption filter according to claim 1, wherein the formula (1) is represented by the following formula (2).

  The infrared absorption filter according to claim 1, wherein the repeating unit represented by the formula (1) is 50 mol% or more in 100 mol% of all repeating units of the polycarbonate resin.   The infrared absorption filter according to claim 3, wherein formula (1) is represented by formula (2).   The infrared absorption filter according to claim 1, comprising a polycarbonate resin composed of 100 mol% of the repeating unit represented by the formula (1) and a dye having infrared absorption ability.   The infrared absorption filter according to claim 5, wherein formula (1) is represented by formula (2).   The infrared absorption filter according to claim 1, wherein the maximum absorption wavelength of the dye having infrared absorption ability is in the range of 800 to 1000 nm. The phthalocyanine dye is represented by the following formula (3)

Wherein (3), R ^p are the same or different, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an amino group, an amide group, an imide group or arylthio group, with R ^p The group represented may have a substituent, and adjacent R ^p may be combined with the carbon atom to which they are bonded to form a ring, and a is an integer of 0 to 4. And M _p is a hydrogen atom, a divalent to hexavalent metal atom or an oxide thereof, and the valence may be supplemented by a counter anion.
In infrared absorption filter according to claim 1, wherein the dye represented. In the formula (3), R ^p is a fluorine atom, a chlorine atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms. An oxy group, an aralkyl group having 7 to 14 carbon atoms, an amino group, an amide group, an imide group, or an arylthio group, and the group represented by R ^p is an alkyl group or alkylidene group having 1 to 10 carbon atoms as a substituent. May have an acyl group, a is an integer of 0 to 4, M _p is a hydrogen atom, a 2 to 6 valent metal atom or an oxide thereof, and the valence is supplemented by a counter anion. The infrared absorption filter according to claim 8 , which may be provided. The dithiol dye is represented by the following formula (4)

In formula (4), R ^t1 , R ^t2 , R ^t3 and R ^t4 are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group or an amino group, The groups represented by R ^t1 , R ^t2 , R ^t3 and R ^t4 may have a substituent, and M _t1 is a tetracoordinate transition metal atom.
A dye represented by

In formula (5), R ^t5 , R ^t6 , R ^t7 and R ^t8 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group or an amino group, and R ^t5 , The group represented by R ^t6 , R ^t7 and R ^t8 may have a substituent, M _t2 is a tetracoordinate transition metal atom, and Q ⁺ is a monovalent cation. at least one is a dye according to claim 1 infrared absorption filter according selected from the group consisting of that dye. In formula (4) and formula (5), R ^t1 , R ^t2 , R ^t3 , R ^t4 R ^t5 , R ^t6 , R ^t7 and R ^t8 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, an amide group, an imide group, or an arylthio group, The group represented by R ^t1 , R ^t2 , R ^t3 , R ^t4 , R ^t5 , R ^t6 , R ^t7 and R ^t8 may have a C 1-10 alkyl group as a substituent, The infrared absorption filter according to claim 10 , wherein M _t2 is a tetracoordinate transition metal atom, and Q ⁺ is a monovalent cation. The diimmonium dye is represented by the following formula (6)

In formula (6), R ⁱ¹ , R ⁱ² , R ⁱ³ , R ⁱ⁴ , R ⁱ⁵ , R ⁱ⁶ , R ⁱ⁷ and R ⁱ⁸ are the same or different and are alkyl groups, and R ^j1 , R ^j2 , R ^j3 and R ^j4 is the same or different, is a hydrogen atom or a fluorine atom, X ²⁻ is a divalent anion, and a dye represented by the following formula (7):

In formula (7), R ⁱ⁹ , R ⁱ¹⁰ , R ⁱ¹¹ , R ⁱ¹² , R ⁱ¹³ , R ⁱ¹⁴ , R ⁱ¹⁵ and R ⁱ¹⁶ are the same or different and are alkyl groups, and R ^j5 , R ^j6 , R ^j7 and R ^j8 is the same or different and is a hydrogen atom or a fluorine atom; Z ⁻ is a monovalent anion;
In at least one of an infrared absorption filter according to claim 1, wherein a dye selected from the group consisting of dyes represented. In formula (6) and formula (7), R ⁱ⁹ , R ⁱ¹⁰ , R ⁱ¹¹ , R ⁱ¹² , R ⁱ¹³ , R ⁱ¹⁴ , R ⁱ¹⁵ and R ⁱ¹⁶ are each an alkyl group having 1 to 10 carbon atoms, and R ^j1 , R ^{j2, R j3, R j4,} R j5, R j6, R j7 and ^{R j8} is the same or different and are hydrogen atom or a fluorine ^{atom, X 2-is} a bivalent anion, Z ^- is a monovalent The infrared absorption filter according to claim 12 , which is a dye represented by an anion.   The infrared absorption filter according to claim 1, comprising a color correction pigment.   The infrared absorption filter according to claim 1, wherein the ratio of the dye having infrared absorption ability is 0.01 to 30 parts by weight with respect to 100 parts by weight of the polycarbonate resin containing the repeating unit represented by the formula (1).   The infrared ray absorption filter according to claim 1, wherein an average light transmittance at 450 to 700 nm is 55% or more, and an average light transmittance at 850 to 1100 nm is 30% or less.   The infrared absorption filter according to claim 1, wherein the infrared absorption filter is formed by a casting method or a coating method.   The infrared absorption filter according to claim 1, which has a film shape.   The infrared absorption filter according to claim 1, which is an infrared absorption panel comprising one or more layers selected from an electromagnetic wave absorption layer, an antireflection layer, or a shape retention layer.   The infrared absorption filter according to claim 1, wherein the display has an infrared absorption panel including one or more layers selected from an electromagnetic wave absorption layer, an antireflection layer, or a shape maintaining layer.   A camera comprising an infrared absorption panel comprising the infrared absorption filter according to claim 1.

Images