JP2009191213A - Cyanine compound having cyclic amide group and near infrared absorbing composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new cyanine compound and a practical near infrared absorbing composition excellent in heat-resistant durability. <P>SOLUTION: Disclosed are a compound represented by general formula (1) and a near infrared absorbing composition containing the compound. In the formula, Z<SP>1</SP>and Z<SP>2</SP>each independently represents a non-metal atom group which forms a 5 or 6 membered-ring containing an -NHCO- group; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, and R<SP>6</SP>each independently represents an aliphatic group which may have a substituent; R<SP>3</SP>and R<SP>4</SP>, and R<SP>5</SP>and R<SP>6</SP>each may independently combine with each other to form a 5 or 6 membered-ring; L<SP>1</SP>represents a methine chain composed of 5 or 7 methines which may have a substituent; X<SP>-</SP>represents an anion; and c is 0 or 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel cyanine compound and a near-infrared absorbing composition containing the same.

  Various indolenine cyanine compounds are known (Patent Documents 1 and 2). However, a condensed indolenine cyanine compound containing a —NHCO— group is not known. In addition, aggregates of cyanine compounds are known as near-infrared absorbing compositions (Patent Documents 1 and 2).

Near-infrared absorbing dyes are filter dyes such as heat ray absorption filters, bandpass filters, and optical filters, invisible printing inks, infrared absorbing paints for preventing laser light reflection, flash toners, electrophotographic photoreceptors, light It is useful for applications such as a sensitizer for polymerization or photocrosslinking, an optical recording material such as an optical disk, and an optical sensor.
As a usage form of the near-infrared absorbing dye in the heat ray absorption filter, there are means such as inclusion in a transparent plastic, coating on the surface of a transparent plastic or transparent glass, and the like. Thereby, a transparent heat ray blocking filter is obtained. Applications include eyeglasses, automobiles, or heat ray shading agents for building materials.

It is also possible to use a near-infrared absorption filter as an optical filter for an image sensor such as a CCD. By using a near-infrared absorbing optical filter for these image pickup elements and blocking the incident near-infrared light, the spectral sensitivity of the image pickup element can be brought close to the visual sensitivity. A near infrared absorbing dye can be used as the near infrared absorbing filter.
A near-infrared absorbing dye can be used as a near-infrared absorbing filter on the surface of an image display device of a plasma display (PDP) to prevent malfunction.
When the near-infrared absorbing dye is used as an ink for invisible printing, it is possible to prevent copying of confidential documents.

  Conventionally, cyanine dyes, oxime or thiol metal complexes, naphthoquinone compounds, phthalocyanine compounds, and naphthalocyanine compounds are known as near-infrared absorbing dyes, but they have a problem of low heat fastness.

  As described above, near-infrared absorbing dyes are required for various applications, but conventionally known near-infrared absorbing dyes have not yet been satisfactory in terms of heat fastness.

JP 2002-90521 A Japanese Patent Laid-Open No. 10-231435

  An object of the present invention is to provide a novel cyanine compound (cyanine dye) and a near-infrared absorbing composition excellent in heat fastness containing the same. An object of this invention is to provide the near-infrared absorption filter using this near-infrared absorption composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cyanine compound having a specific chemical structure has an absorption maximum in the near infrared region and is excellent in heat fastness. It came to be completed. The specific means is as follows.

<1> A near-infrared absorbing composition comprising a compound represented by the general formula (1).

[Wherein, Z ¹ and Z ² each independently represent a nonmetallic atom group forming a 5- or 6-membered ring containing a —NHCO— group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , And R ⁶ each independently represents an aliphatic group which may have a substituent, and R ³ and R ⁴ , and R ⁵ and R ⁶ are each independently connected to each other to form 5 or A 6-membered ring may be formed. L ¹ represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]
<2> The near-infrared absorbing composition according to <1>, comprising a compound represented by the general formula (2).

[Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent an aliphatic group that may have a substituent, and R ⁹ , R ¹⁰ , and R 12 ¹¹ and R ¹² may be independently bonded to each other to form a ring. L ² represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]
<3> The near-infrared absorbing composition according to the general formula <2>, comprising a compound represented by the general formula (3).

[Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represents an aliphatic group that may have a substituent, and R ¹⁵ , R ¹⁶ , and R ¹⁷ and R ¹⁸ may be independently bonded to each other to form a ring. R ¹⁹ and R ²⁰ represent a hydrogen atom or may be bonded to each other to form a 5-, 6-, or 7-membered ring. R ²¹ represents a monovalent group, X ⁻ represents an anion, and c is 0 or 1. ]
<4> The near-infrared absorbing composition according to any one of <1> to <3>, wherein the compound is a dye forming an aggregate.
<5> The near infrared absorption composition according to any one of <1> to <4>, wherein the near infrared absorption region is a region having an absorption wavelength of 700 nm to 1000 nm.
<6> The near-infrared absorbing composition according to any one of <1> to <5>, comprising a solid fine particle dispersion of a cyanine compound.
<7> The near-infrared absorbing composition according to any one of <1> to <6>, which is a near-infrared absorbing filter.
<8> A compound represented by the general formula (2).

[Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent an aliphatic group that may have a substituent, and R ⁹ , R ¹⁰ , and R 12 ¹¹ and R ¹² may be independently bonded to each other to form a ring. L ² represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]
<9> A compound represented by the general formula (3).

[Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represents an aliphatic group that may have a substituent, and R ¹⁵ , R ¹⁶ , and R ¹⁷ and R ¹⁸ may be independently bonded to each other to form a ring. R ¹⁹ and R ²⁰ represent a hydrogen atom or may be bonded to each other to form a 5-, 6-, or 7-membered ring. R ²¹ represents a monovalent group, X ⁻ represents an anion, and c is 0 or 1. ]
<10> A compound represented by the general formula (4).

[Wherein R ²² represents an aliphatic group which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]

  The near-infrared absorbing composition containing the novel cyanine compound of the present invention exhibits absorption in the near-infrared region, has high heat fastness properties, and can exhibit good characteristics as a practical optical material.

The present invention is described in detail below.
First, the compound represented by the general formula (1) will be described.

[Wherein, Z ¹ and Z ² each independently represent a nonmetallic atom group forming a 5- or 6-membered ring containing a —NHCO— group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , And R ⁶ each independently represents an aliphatic group which may have a substituent, and R ³ and R ⁴ , and R ⁵ and R ⁶ are each independently connected to each other to form 5 or A 6-membered ring may be formed. L ¹ represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]

Examples of the indolenine ring formed by a nonmetallic atom group containing a —NHCO— group represented by Z ¹ and Z ² include the following compounds (in the compound represented by the general formula (1), L ¹ Only the cation part on the left of (methine chain) is shown).

In the compound, R ¹ , R ² , and R ³ each independently represents an aliphatic group that may have a substituent, and R ³ and R ⁴ are independently of each other from R ⁵ and R ^6. It may be linked to form a 5- or 6-membered ring. Of these, the compound (a) is particularly preferable.

  In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, or a substituted alkynyl group. The alkyl group may be cyclic. The chain alkyl group may have a branch. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and most preferably 1 to 8. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclopentyl, cyclohexyl, and 2-ethylhexyl groups. The alkyl group is preferably a methyl, ethyl, propyl or butyl group, particularly preferably a methyl or ethyl group.

The alkyl part of the substituted alkyl group is the same as the above alkyl group. Examples of substituents for substituted alkyl groups include halogen atoms (F, Cl, Br, I), cyano groups, hydroxyl groups, carboxyl groups, amino groups, carbamoyl groups, ureido groups, urethane groups, mercapto groups, sulfo groups, sulfamoyl groups. Group, aromatic group, heterocyclic group, —O—R, —CO—R, —CO—O—R, —O—CO—R, —NH—R, —N (R) ₂ , —NH—CO -R, -CO-NH-R, -CO-N (R) ₂ , -NH-CO-NH-R, -NH-CO-N (R) ₂ , -NH-CO-O-R, -S —R, —SO ₂ —R, —SO ₂ —O—R, —NH—SO ₂ —R, —SO ₂ —NH—R, —SO ₂ —N (R) ₂ are included. Examples of R include an aliphatic group, an aromatic group, or a heterocyclic group. Preferred examples of the substituent include a halogen atom, a carboxyl group, and a sulfo group, and particularly preferred is a sulfo group. The carboxyl group and the sulfo group may be in a salt state even when the hydrogen atom is dissociated. Examples of substituted alkyl groups include 2-hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 3-sulfopropyl, 4-sulfobutyl, benzyl, and phenethyl groups.

  The alkenyl group may be cyclic. The chain alkenyl group may have a branch. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and most preferably 2 to 8. Examples of alkenyl groups include vinyl, allyl, 1-propenyl, 2-butenyl, 2-pentenyl, and 2-hexenyl groups. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The substituent of the substituted alkenyl group is the same as the substituent of the alkyl group.

  The alkynyl group may have a branch. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and most preferably 2 to 8. Examples of alkynyl groups include ethynyl and 2-propynyl groups. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The substituent of the substituted alkynyl group is the same as the substituent of the alkyl group.

  In the present specification, the aromatic group means an aryl group or a substituted aryl group. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. Examples of the aryl group include phenyl and naphthyl groups. The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent for the substituted aryl group include the same substituents as those for the alkyl group described above. Examples of substituted aryl groups include 4-carboxyphenyl, 4-acetamidophenyl, 3-methanesulfonamidophenyl, 4-methoxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, And 4-butanesulfonamidophenyl group.

  In the present specification, the heterocyclic ring is preferably a 5-membered ring or a 6-membered ring, and may be substituted with a substituent. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring. Examples of heterocyclic rings (including fused rings) include pyridine ring, piperidine ring, furan ring, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine Rings, phenoxazine rings, indoline rings, thiazole rings, pyrazine rings, thiadiazine rings, benzoquinoline rings, and thiadiazole rings are included. The substituent of the substituted heterocyclic group is the same as the substituent of the alkyl group.

Examples of the 5- or 6-membered ring independently formed by R ³ and R ⁴ , and R ⁵ and R ⁶ include cyclopentane and cyclohexane rings.

In the formula (1), L ¹ is a methine chain composed of 5 or 7 methines, and may have a substituent. The substituent is the same as the substituent for the alkyl group. Further, methine chains may be bonded to each other to form a 5-, 6-, or 7-membered ring (for example, cyclopentene, cyclohexene, cycloheptene).

X ⁻ represents an anion, and examples thereof include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ , and ClO ₄ ^−. It is done. c is 0 or 1; When the dye has an anionic substituent such as a sulfo group or a carboxyl group to form an inner salt, c is 0.

  Among the compounds represented by the general formula (1), the compound represented by the general formula (2) is preferable. The compound represented by the general formula (2) will be described.

[Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent an aliphatic group that may have a substituent, and R ⁹ , R ¹⁰ , and R 12 ¹¹ and R ¹² may be independently bonded to each other to form a ring. L ² represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]

In the general formula (2), the aliphatic groups represented by R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are R ¹ , R ² , R ^{3 in the} general formula (1). , R ⁴ , R ⁵ , and R ⁶ . R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² each independently form a ring by combining R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² to form a cyclopentane or cyclohexane ring. May be. The methine chain represented by L ² and the substituent are synonymous with L ¹ in the general formula (1). The anion represented by X ⁻ and c have the same meanings as described above in the general formula (1).

  Furthermore, the compound represented by General formula (3) is preferable.

[Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represents an aliphatic group that may have a substituent, and R ¹⁵ , R ¹⁶ , and R ¹⁷ and R ¹⁸ may be independently bonded to each other to form a ring. R ¹⁹ and R ²⁰ represent a hydrogen atom or may be bonded to each other to form a 5-, 6-, or 7-membered ring. R ²¹ represents a monovalent group. X ⁻ represents an anion, and c is 0 or 1. ]

The aliphatic groups for R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are as defined above. R ¹⁵ and R ¹⁶ , and R ¹⁷ and R ¹⁸ may be independently bonded to each other, and R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may be bonded to each other to form a cyclohexane ring or a cyclopentane ring. R ¹⁹ and R ²⁰ represent a hydrogen atom or may be bonded to each other to form a 5-, 6-, or 7-membered ring. Examples of the monovalent group represented by R ²¹ include the substituents described for the alkyl group. Furthermore, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —O—R, and —S—R are preferable. As R, an aliphatic group, an aromatic group, or a heterocyclic group is mentioned each independently. The aliphatic group, aromatic group and heterocyclic group are as defined above. X ^- anion, for For c, the same meanings as described above.

  Moreover, in this invention, the compound represented by General formula (4) becomes an important intermediate body of various pigment | dyes.

[Wherein R ²² represents an aliphatic group which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]

In the general formula (4), the aliphatic group of R ²² has the same meaning as the aliphatic group of R ¹³ and R ^{14 in} the general formula (3), and the anion of X ⁻ and c are represented by the general formula (3). The anion and c are the same. More preferably, R ²² is an aliphatic group having 1 to 12 carbon atoms, and may be further substituted with a sulfo group or a carboxyl group.

Specific examples of the compound represented by the general formula (1), (2), or (3) are shown below, but the present invention is not limited thereto. Incidentally, in the following examples, PTS ^- represents a p- toluenesulfonate anion.

  In the synthesis of the dyes of the general formulas (1), (2), and (3), in addition to the description in the present specification, “Heterocyclic Compounds-Cyanine Soybeans” by FM Harmer "Heterocyclic Compounds Cyanine Dyes and Related Compounds", John Wiley & Sons-New York, London, 1964, and "DMSturmer" Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry ", Chapter 18, Section 14, 482-515, John Willy and Sons ( John Wiley & Sons)-New York, London, 1977, "Rods Chemistry・ Rodds Chemistry of Carbon Compounds ”2nd. Ed. Vol. IV, part B, 1977, Chapter 15, pp. 369-422, Elsevier Science Public Company, Inc. Inc.), New York, and JP-A-4-362932 and the references thereof can be appropriately synthesized.

The near-infrared absorbing composition of the present invention includes compounds (pigments) represented by the general formulas (1), (2), and (3). Furthermore, the pigment | dyes represented by General formula (2) and (3) are preferable, and the pigment | dye represented by General formula (3) is the most preferable. The wavelength preferably exhibits an absorption maximum in the range of 700 to 900 nm. The wavelength showing the absorption maximum (absorption maximum wavelength) may be that when the dye forms an aggregate.
In order to obtain a preferable absorption waveform, the near-infrared composition of the present invention may be a composition in which the dye is dissolved in water, a solvent, or the like, but the dye is brought into an associated state in order to improve absorption and light resistance. It is preferable (hereinafter, the dye in this state is also referred to as “aggregate dye”), and it is more preferable to use a dye in an aggregate state including a J aggregate. In addition, since the aggregate dye forms a so-called J band, it shows a sharp absorption spectrum peak. The dye association and the J band are described in detail in, for example, Photographic Science and Engineering, Vol. 18, No. 323-335 (1974)). The absorption maximum of the dye in the J-association state moves to the longer wave side than the absorption maximum of the dye in the solution state. Therefore, it can be determined by measuring the absorption maximum whether the dye contained in the near-infrared absorbing composition is in an associated state or a non-associated state.

  In the present invention, after the association (for example, a film) measured by the same apparatus with respect to the absorption maximum wavelength (λma) of the dye in the solvent measured by Shimadzu Corporation UV-3100Pc (trade name) When the absorption maximum wavelength (λmb) is 30 nm or longer, the dye after the association is referred to as an associated dye (aggregate dye). Here, as a better association state, it is preferably an association dye in which the difference between the absorption maximum wavelength in the solution state and the absorption maximum wavelength after association (λmb−λma) is 50 nm or more, and 70 nm or more. It is more preferable that the aggregated dye is used.

  In the formation of the aggregate dye of the present invention, the compound represented by the general formula (1), (2), or (3) is dissolved in water, and gelatin or a salt (for example, barium chloride, calcium chloride, etc.) is added. Thus, it can be used as an aggregate dye in water. Alternatively, it can be dispersed as solid fine particles (average particle diameter is preferably 0.001 to 100 μm, more preferably 0.005 to 50 μm) to form an aggregate dye. Dispersion can be carried out with a potassium salt or a sodium salt of a dye, and can also be carried out with a lake pigment by adding an aqueous solution of a metal salt (for example, magnesium chloride, zinc chloride, or barium chloride) to an aqueous solution of the dye. Conversely, an aqueous solution of a dye represented by the general formula (1), (2), or (3) may be added to the aqueous solution of the metal salt.

  The content of the compound represented by the general formula (1), (2), or (3) in the near-infrared absorbing composition of the present invention can be adjusted as necessary. It is preferable to contain 1-30 mass%, and it is more preferable to contain 0.5-10 mass%.

  Examples of solid fine particle dispersions of dyes include, for example, “Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation” published by Technical Information Association, “Pigment Encyclopedia” published by Asakura Shoten Co., Ltd. It is described in detail in “Latest“ pigment dispersion ”practical know-how / examples” published by the Technical Information Association. In order to obtain a solid fine particle dispersion, an ordinary disperser can be used. Examples of the disperser include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill. The disperser is described in JP-A-52-92716 and International Publication No. 88/074794. A vertical or horizontal medium disperser is preferred.

  Dispersion may be carried out in the presence of a suitable medium (eg, water, alcohol, cyclohexanone, 2-methoxy-1-methylethyl acetate). It is preferable to use a surfactant for dispersion. As the surfactant for dispersion, an anionic surfactant (described in JP-A-52-92716 and International Publication No. 88/077944) is preferably used. If necessary, an anionic polymer, a nonionic surfactant, or a cationic surfactant may be used.

  After dissolving the coloring matter of the present invention in a suitable solvent, a poor solvent may be added to the solution to form fine particles, and the powder may be obtained as necessary. Also in this case, the above dispersing surfactant may be used. Alternatively, dissolution may be performed by adjusting the pH, and then the pH may be changed to precipitate pigment fine particles. These fine particles are also preferably the above-mentioned aggregate dyes. When the aggregate dye is fine particles (or microcrystals), the average particle size is preferably 1000 μm or less, more preferably 0.001 μm to 100 μm, and particularly preferably 0.005 μm to 50 μm. In the present invention, the average particle diameter means a volume average particle diameter unless otherwise specified, and is measured using a laser diffraction scattering method or a dynamic light scattering method.

For the purpose of improving the dispersibility of the coloring matter of the present invention, an ordinary pigment dispersant or surfactant can be added. As these dispersants, many types of compounds are used. For example, phthalocyanine derivatives (commercial product: EFKA-745 (trade name, manufactured by Efka)), Solsperse 5000 (trade name, manufactured by Generala);
Organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (trade name, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (trade name, manufactured by Yusho Co., Ltd.) and the like;
Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Emulgen A60 (product) Nonionic surfactants such as name, manufactured by Kao Corporation;
Anionic surfactants such as W004, W005, W017 (trade names, manufactured by Yusho Co., Ltd.), Na dodecylbenzenesulfonate, Demol SNB (trade names, manufactured by Kao Corporation);
EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above, trade name, manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8 , Disperse Aid 15, Disperse Aid 9100 (trade name, manufactured by San Nopco), etc .;
Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (trade names, manufactured by Zeneca Corporation);
Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (trade name, manufactured by Asahi Denka Co., Ltd.) ) And Isonet S-20 (trade name, manufactured by Sanyo Kasei Co., Ltd.).

  The said dispersing agent may be used independently and may be used in combination of 2 or more type. The amount of the dispersant added is preferably about 1 to 150 parts by mass with respect to 100 parts by mass of the dye.

  The composition of the present invention may contain an anti-fading agent, an antioxidant, or an ultraviolet ray inhibitor. Anti-fading agents include hydroquinone derivatives, hydroquinone diethers, phenol derivatives, spiroindane, methylenedioxybenzene, chroman, spirochroman, coumaran derivatives, hydroquinone monoethers, p-aminophenol derivatives, and bisphenol derivatives. The hydroquinone derivatives are described in US Pat. Nos. 3,935,016 and 3,982,944. Hydroquinone diether is described in U.S. Pat. No. 4,254,216 and JP-A-55-21004. The phenol derivative is described in JP-A No. 54-145530. Spiroindane and methylenedioxybenzene are described in British Patent Nos. 2062888 and 2077455. As for chroman, spirochroman, and coumaran derivatives, US Pat. Nos. 3,432,300, 3,573,050, 3,574,627, 3,764,337, JP-A-52-152225, 53-17729, 53-20327, There is description in each gazette of 61-90156. Hydroquinone monoether and p-aminophenol derivatives are described in British Patent Nos. 1347556 and 2066975, JP-B Nos. 54-12337, and JP-A Nos. 55-6321. The bisphenol derivative is described in US Pat. No. 3,700,455 and Japanese Patent Publication No. 48-31625.

  A metal complex (as described in US Pat. No. 4,245,018 and JP-A-60-97353) or a singlet oxygen quencher may be added to the composition. The singlet oxygen quencher includes a nitroso compound (as described in JP-A-2-300288), a diimmonium compound (as described in US Pat. No. 4,656,612), and a nickel complex (as described in JP-A-4-146189). , And antioxidants (described in European Patent 820057A1).

The composition of the present invention can be used for each application described in the background art.
When the composition containing the compound of the present invention is formed into a film by coating or the like, the thickness of the dry coating film is preferably 0.1 μm to 1 cm, more preferably 0.5 μm to 100 μm.

  The composition of the present invention preferably further contains a polymer binder. Polymer binders include natural polymers (eg, gelatin, cellulose derivatives, alginic acid) or synthetic polymers (eg, polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymers, polystyrene, polycarbonate, Water-soluble polyamides) can be used as the polymer binder. Particularly preferred are hydrophilic polymers (eg, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, water-soluble polyamide in the natural polymer and the synthetic polymer).

  The filter of the present invention may be prepared using a transparent support. The transparent support is preferably made of glass or a polymer film. Examples of polymers include cellulose esters (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose nitrate), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene) Naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polyarylate (eg, bisphenol A and Phthalic acid condensate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene) Poly (meth) acrylic acid ester (e.g., polymethyl methacrylate), polysulfone, polyether sulfone, polyether ketone, polyether imide, and polyoxyethylene. Cellulose triacetate, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and polyethylene naphthalate are preferred. The thickness of the transparent support is preferably 5 μm to 5 cm, more preferably 25 μm to 1 cm, and most preferably 80 μm to 1.2 mm. The thickness of the coating film made of the composition in this case is as described above.

  The transmittance of the transparent support with respect to light having a wavelength of 400 to 1100 nm is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

An ultraviolet absorber may be added to the transparent support. The addition amount of the ultraviolet absorber is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass with respect to the transparent support. As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc, and a kaolin. It is preferable to subject the transparent support to a surface treatment. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferred, and corona discharge treatment is more preferred.

Moreover, the near-infrared absorption composition of this invention contains the compound represented by General formula (1), (2), or (3) in a photocurable composition or a thermosetting composition. It may be made up of. As the photocurable composition or the thermosetting composition, a composition containing a compound having an ethylenically unsaturated group is preferable. Examples include monofunctional acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, methacrylate, polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Examples include functional acrylates and methacrylates. Furthermore, the Japan Adhesion Association magazine Vol. 20, no. The thing introduced as a photocurable monomer and oligomer on pages 7,300-308 is mentioned.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1: Synthesis of Compound (9) The synthesis route of Compound (9) is shown below.

Synthesis of Compound c 25 g of Compound a (manufactured by Wako Pure Chemical Industries), 30 g of Compound b (manufactured by Wako Pure Chemical Industries, Ltd.) and 140 mL of sulfolane were mixed and heated at 190 ° C. for 4 hours. After completion of the reaction, 280 mL of water was added, and the precipitated crystals were filtered. 27 g of compound c was obtained.

Synthesis of Compound d 57 g of reduced iron, 1 g of NH ₄ Cl, 20 mL of water and 300 mL of isopropanol were mixed, and 26 g of Compound a was added thereto. After refluxing for 5 hours, the mixture was filtered, and the filtrate was concentrated to obtain 21 g of compound d.

Synthesis of Compound e 21 g of Compound d, 100 mL of water and 34 mL of hydrochloric acid were mixed, and an aqueous solution of 9 g of sodium nitrite was added dropwise to this solution at 5 ° C. or lower. The solution was added to 73 g of SnCl ₂ .2H ₂ O, 40 mL of H ₂ O, and 70 mL of hydrochloric acid, and the precipitated crystals were separated by filtration to obtain 20 g of a compound e form.

Synthesis of Compound f and Compound g 16.4 g of Compound e, 13 g of isopropyl methyl ketone, and 50 mL of acetic acid were mixed, and this solution was refluxed for 3 hours. The mixture was heated and 6.4 g of compound g was obtained by column chromatography.
¹ HNMR (300 MHz, DMSO-D6): δ 11.15 (s, 1H), 11.21 (s, 1H), 7.6 (s, 1H), 7.32 (s, 1H), 4.65 ( t, 2H), 2.86 (s, 3H), 2.60 (t, 2H), 2.13 (m, 2H), 1.49 (s, 6H)

Synthesis of Compound h 25 g of Compound i (manufactured by Wako Pure Chemical Industries, Ltd.) and 54.6 g of Compound j (manufactured by Tokyo Chemical Industry) were stirred at 100 ° C. for 2 hours, 200 ml of acetone was added, the precipitated crystals were filtered, and 49 g of Compound h was filtered. Got.

Synthesis of Compound (9) 1.7 g of Compound g, 0.8 g of Compound h and 15 mL of methanol were mixed. To this solution, 1 mL of acetic anhydride and 1.4 mL of triethylamine were added and stirred for 2 hours. 0.5 g of potassium acetate was added to the reaction solution, and the precipitated crystals were filtered to obtain 0.7 g of Compound (9). λmax was 835 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.65 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was over 300 ° C.

Example 2: Synthesis of Compound (8) The synthesis route of Compound (8) is shown below.

Synthesis of Compound k 16.4 g of Compound e, 13 g of isopropyl methyl ketone, and 50 mL of acetic acid were mixed, and this solution was refluxed for 3 hours to obtain Compound f, and then 13 g of ethyl p-toluenesulfonate (PTS-Et) was added. In addition, the mixture was heated at 140 ° C. for 5 hours, and 8.4 g of compound k was obtained by column chromatography.
¹ HNMR (300 MHz, DMSO-D6): δ 11.58 (s, 1H), 11.22 (s, 1H), 7.6 (s, 1H), 7.45 (d, 2H), 7.32 ( s, 1H), 7.10 (d, 2H), 4.42 (q, 2H), 2.83 (s, 3H), 2.27 (s, 3H), 1.58 (s, 6H), 1.40 (t, 3H)

Compounds were synthesized Compound l in the same manner as in the synthesis of the compound h in l. However, 4-phenylpyridine was used in place of compound i.

Synthesis of Compound (8) 1.1 g of Compound k, 0.4 g of Compound 1 and 15 ml of methanol were mixed, and 0.5 mL of acetic anhydride and 0.7 mL of triethylamine were added to this solution and stirred for 2 hours. 0.5 g of potassium acetate was added to the reaction solution, and the precipitated crystals were filtered to obtain 0.3 g of Compound (8). λmax was 815 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.77 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was 278-280 ° C.

Example 3: Synthesis of compound (11) Compound (11) was prepared in the same manner as in Example 1 using compound k (synthesized with reference to Chem. Ber .; GE; 110; 1977; 1259-1268). Synthesized. λmax was 704 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.57 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was 230-235 ° C.

Example 4: Synthesis of Compound (5) Compound 1 (J. Org. Chem. USSR (Engl. Trans.); EN; 14; 1978; synthesized with reference to 2214-2221) was used as Example 1 Similarly, the compound (5) was synthesized. λmax was 875 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.88 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was over 300 ° C.

  Other compounds can be synthesized in the same manner as described above.

Example 5
A mixture of 0.5 g of the compound (dye) (9) of the present invention, 0.05 g of Emulgen A60 (manufactured by Kao Corporation), 10 g of zirconia beads (0.1 mm), and 4.5 g of distilled water was added to a planetary ball mill ( And a dispersion was obtained. The average particle size of the compound (9) was 0.30 μm.

  0.6 g of the dispersion obtained above was added to 2.0 g of a 4 mass% gelatin aqueous solution at 40 ° C. and mixed. This liquid was spin-coated on a glass substrate to prepare a near infrared absorption filter A having an infrared absorption layer having a dry thickness of 2 μm.

Example 6
Except for using the dye (compound) (5), (11), and (8) of the present invention instead of the dye (compound) (9) of the present invention used in Example 5, it is completely the same as Example 5. Similarly, dispersions and near-infrared absorption filters B, C, and D were prepared. The average particle diameters of the dyes (5), (11), and (8) were 0.25 μm, 0.40 μm, and 0.35 μm, respectively.

Comparative Example 1
A dispersion and a near-infrared absorption filter E were prepared in exactly the same manner as in Example 5 except that the comparative dye (Comparative Example a) was used instead of the dye (9) of the present invention used in Example 5. did. Comparative Example a is a dye described in JP-A-10-231435, represented by the following formula.

Test example [filter evaluation test]
The following evaluation was performed about each created filter. The results are shown in Table 1.
<Absorption>
The absorption maximum wavelength (λmb) of the filter was measured using UV-3100Pc (trade name, manufactured by Shimadzu Corporation). Further, the absorption maximum wavelength (λma) of each dye dissolved in the solvent was measured (measured by dissolving 1 mg of the dye in 100 mL of the solvent).
<Heat resistance>
A filter was placed on a hot plate (NP-6 type manufactured by Shibata Chemical Co., Ltd.) heated to 220 ° C. and left for 70 minutes. The image density before and after heating was measured using the above 3100PC,
(Concentration after heating / Concentration before heating) × 100 = Dye remaining ratio (%)
As evaluated.

1 and 2 show the absorption spectrum of the filter A (FIG. 1) and the absorption spectrum of the dye (9) dissolved in the solvent (DMSO) (FIG. 2).
As is clear from Table 1 and FIGS. 1-2, the filter of the present invention has a longer absorption maximum wavelength than solution absorption, and has excellent heat resistance.

2 is a graph showing an absorption spectrum of filter A in Table 1. It is a graph which shows the absorption spectrum of the pigment | dye (9) of Table 1. FIG.

Claims (10)

The near-infrared absorption composition characterized by including the compound represented by General formula (1).

[Wherein, Z ¹ and Z ² each independently represent a nonmetallic atom group forming a 5- or 6-membered ring containing a —NHCO— group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , And R ⁶ each independently represents an aliphatic group which may have a substituent, and R ³ and R ⁴ , and R ⁵ and R ⁶ are each independently connected to each other to form 5 or A 6-membered ring may be formed. L ¹ represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ] The near-infrared absorbing composition according to claim (1), comprising a compound represented by the general formula (2).

[Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent an aliphatic group that may have a substituent, and R ⁹ , R ¹⁰ , and R 12 ¹¹ and R ¹² may be independently bonded to each other to form a ring. L ² represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ] The near-infrared absorption composition of General formula (2) characterized by including the compound represented by General formula (3).

[Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represents an aliphatic group that may have a substituent, and R ¹⁵ , R ¹⁶ , and R ¹⁷ and R ¹⁸ may be independently bonded to each other to form a ring. R ¹⁹ and R ²⁰ represent a hydrogen atom or may be bonded to each other to form a 5-, 6-, or 7-membered ring. R ²¹ represents a monovalent group, X ⁻ represents an anion, and c is 0 or 1. ]   The near-infrared absorbing composition according to any one of claims 1 to 3, wherein the compound is a dye forming an aggregate.   The near-infrared absorbing composition according to any one of claims 1 to 4, wherein the near-infrared absorbing region is a region having an absorption wavelength of 700 nm to 1000 nm.   The near-infrared absorbing composition according to claim 1, comprising a solid fine particle dispersion of a cyanine compound.   It is a near-infrared absorption filter, The near-infrared absorption composition of any one of Claims 1-6 characterized by the above-mentioned. A compound represented by the general formula (2).

[Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent an aliphatic group that may have a substituent, and R ⁹ , R ¹⁰ , and R 12 ¹¹ and R ¹² may be independently bonded to each other to form a ring. L ² represents a methine chain composed of 5 or 7 methines which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ] A compound represented by the general formula (3).

[Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represents an aliphatic group that may have a substituent, and R ¹⁵ , R ¹⁶ , and R ¹⁷ and R ¹⁸ may be independently bonded to each other to form a ring. R ¹⁹ and R ²⁰ represent a hydrogen atom or may be bonded to each other to form a 5-, 6-, or 7-membered ring. R ²¹ represents a monovalent group, X ⁻ represents an anion, and c is 0 or 1. ] The compound represented by General formula (4).

[Wherein R ²² represents an aliphatic group which may have a substituent, X ⁻ represents an anion, and c is 0 or 1. ]

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