JP2009092784A - Near-infrared absorbing thiazole compound and near-infrared absorbing filter using the same - Google Patents

Abstract

［式中、Ｒ_１およびＲ_２は、それぞれ独立に、脂肪族基または芳香族基であり；Ｒ_３およびＲ_４は水素原子または一価の基であり；Ｌ_１は、５または７個のメチンからなり、少なくとも１個はフェニル置換したメチンを有するメチン鎖である。但し、分子内に酸性基を少なくとも一つ以上含む］。
【選択図】なしA near-infrared absorption filter containing a thiazole cyanine compound is provided, and more specifically, a practical near-infrared absorption filter containing a thiazole cyanine compound and excellent in invisibility and light fastness is provided.
A near-infrared absorption filter comprising a cyanine compound represented by the following general formula (1).

Wherein R ₁ and R ₂ are each independently an aliphatic group or an aromatic group; R ₃ and R ₄ are a hydrogen atom or a monovalent group; L ₁ is 5 or 7 It consists of methine and at least one is a methine chain with phenyl-substituted methine. However, the molecule contains at least one acidic group].
[Selection figure] None

Description

  The present invention relates to a near-infrared absorption filter, and more particularly to a near-infrared absorption filter containing a thiazole compound.

Thiazole dyes are known for filters (Patent Document 1).
Thiazole dyes having a phenyl group on the methine chain are known as photographic dyes (Patent Documents 2 and 3). It is also widely used for photoelectric conversion elements and laser recording materials (Patent Documents 4 and 5). Furthermore, a thiazole cyanine dye substituted with phenyl on a 5-membered ring (Document 6) is known.

On the other hand, near-infrared absorbing dyes are filter dyes such as heat ray absorption filters, bandpass filters, optical filters, invisible printing inks, infrared absorbing paints for preventing laser light reflection, flash toners, electrophotographic photoreceptors, photopolymerization. Alternatively, it is useful for applications such as sensitizers for photocrosslinking, optical recording materials such as optical disks, and optical sensors.
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 for the near infrared absorbing filter.
A near-infrared absorbing dye can be used for the 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 the absorption in the visible region is large, and the IR region (700-1100 nm) is sufficient. There are drawbacks such as lack of proper absorption and low light fastness.

  As described above, near-infrared absorbing dyes are required for various applications, but conventionally known near-infrared absorbing dyes are not yet satisfactory in terms of practicality in terms of absorption and light fastness. There wasn't.

JP-A-2002-90521 JP-A-4-362932 JP 2002-90521 A JP 2005-093307 A JP-A-6-191153 Journal of Information Recording Materials, (1988), 16 (1), 23-31.

  An object of the present invention is to provide a near-infrared absorption filter, and more specifically, to provide a practical near-infrared absorption filter containing a thiazole compound and excellent in absorption and light fastness. Furthermore, this invention relates to the near-red absorption thiazole compound used for said near-infrared absorption filter.

As a result of intensive studies in order to solve the above problems, the present inventor has a thiazole compound having a specific chemical structure with little absorption in the visible part, an absorption maximum in the near infrared region, and excellent light fastness. As a result, the present invention has been completed.
The above problem has been achieved by the following specific means.
<1> A near-infrared absorption filter comprising a cyanine compound represented by the following general formula (1).

［式中、Ｒ_１およびＲ_２は、それぞれ独立に、脂肪族基または芳香族基であり；Ｒ_３およびＲ_４はそれぞれ独立に水素原子または一価の基であり；ｐおよびｑはそれぞれ独立に１から４の整数であり；Ｌ_１は、５または７個のメチンからなり、少なくとも１個はフェニル置換したメチンを有するメチン鎖である。但し、分子内に酸性基を少なくとも一つ以上含む］。
＜２＞前記一般式（１）で表されるシアニン化合物が、下記一般式（２）で表わされるシアニン化合物であることを特徴とする＜１＞記載の近赤外吸収フィルター。

[Wherein, R ₁ and R ₂ are each independently an aliphatic group or an aromatic group; R ₃ and R ₄ are each independently a hydrogen atom or a monovalent group; and p and q are each independently L ₁ is an integer from 1 to 4; L ₁ consists of 5 or 7 methines, at least one of which is a methine chain having a phenyl-substituted methine. However, the molecule contains at least one acidic group].
<2> The near-infrared absorption filter according to <1>, wherein the cyanine compound represented by the general formula (1) is a cyanine compound represented by the following general formula (2).

［式中、Ｒ_５およびＲ_６は水素原子、アルキル基、フェニル基、ハロゲン原子またはアルコキシ基であり；ｐおよびｑはそれぞれ独立に１から４の整数であり；Ｒ_７はフェニル基であり；Ｒ_８およびＲ_９は水素原子あるいはお互いに連結して５，６または７員環を形成する基であり；Ａは２価の連結基であり；Ｘは酸性基であり；Ｍ^ｎ＋はカチオンであり；ｎは１，２または３である］。
＜３＞前記一般式（１）または（２）で表されるシアニン化合物が会合体を形成していることを特徴とする＜１＞および＜２＞に記載の近赤外吸収フィルター。
＜４＞近赤外吸収領域が、吸収波長７００ｎｍ〜１１００ｎｍの領域であることを特徴とする＜１＞〜＜３＞のいずれか１項に記載の近赤外吸収フィルター。
＜５＞４００ｎｍの吸光度が最大吸収波長の吸光度の１／２０以下であることを特徴とする＜１＞〜＜４＞のいずれか１項に記載の近赤外吸収フィルター。
＜６＞前記一般式（１）で表されるシアニン化合物の固体微粒子分散体を含むことを特徴とする＜１＞〜＜５＞のいずれか１項に記載の近赤外吸収フィルター。
＜７＞下記一般式（２）で表わされる会合性近赤外吸収シアニン化合物。

[Wherein, R ₅ and R ₆ are a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group; p and q are each independently an integer of 1 to 4; R ₇ is a phenyl group; R ₈ and R ₉ are a hydrogen atom or a group linked to each other to form a 5, 6 or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation. Yes; n is 1, 2 or 3].
<3> The near-infrared absorption filter according to <1> and <2>, wherein the cyanine compound represented by the general formula (1) or (2) forms an aggregate.
<4> The near-infrared absorption filter according to any one of <1> to <3>, wherein the near-infrared absorption region is a region having an absorption wavelength of 700 nm to 1100 nm.
<5> The near-infrared absorption filter according to any one of <1> to <4>, wherein the absorbance at 400 nm is 1/20 or less of the absorbance at the maximum absorption wavelength.
<6> The near-infrared absorption filter according to any one of <1> to <5>, comprising a solid fine particle dispersion of a cyanine compound represented by the general formula (1).
<7> An associative near-infrared absorbing cyanine compound represented by the following general formula (2).

［式中、Ｒ_５およびＲ_６は水素原子、アルキル基、フェニル基、ハロゲン原子またはアルコキシ基であり；ｐおよびｑはそれぞれ独立に１から４の整数であり；Ｒ_７はフェニル基であり；Ｒ_８およびＲ_９は水素原子あるいはお互いに連結して５，６または７員環を形成する基であり；Ａは２価の連結基であり；Ｘは酸性基であり；Ｍ^ｎ＋はカチオンであり；ｎは１，２または３である］。
＜８＞下記一般式（３）で表わされる会合性近赤外吸収シアニン化合物。

[Wherein, R ₅ and R ₆ are a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group; p and q are each independently an integer of 1 to 4; R ₇ is a phenyl group; R ₈ and R ₉ are a hydrogen atom or a group linked to each other to form a 5, 6 or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation. Yes; n is 1, 2 or 3].
<8> An associative near-infrared absorbing cyanine compound represented by the following general formula (3).

［式中、Ｒ_１０はフェニル基であり；Ｒ_１１およびＲ_１２は水素原子あるいはお互いに連結して５，６または７員環を形成する基であり；Ａは２価の連結基であり；Ｘは酸性基であり；Ｍ^ｎ＋はカチオンであり；ｎは１，２または３である］。

[Wherein R ₁₀ is a phenyl group; R ₁₁ and R ₁₂ are a hydrogen atom or a group linked to each other to form a 5-, 6-, or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation; n is 1, 2 or 3].

  The near-infrared absorption filter of the present invention has a small visible absorption, a large molar absorption coefficient and a maximum absorption in the near-infrared region, high light fastness, and good characteristics as a practical optical material. Excellent effect is exhibited.

The near infrared absorption filter of the present invention is shown in detail below.
First, the compound represented by the general formula (1) will be described.

In which R ₁ and R ₂ are each independently an aliphatic group or an aromatic group; R ₃ and R ₄ are each independently a hydrogen atom or a monovalent group; and p and q are each independently L is an integer from 1 to 4; L ₁ is a phenyl-substituted methine chain consisting of 5 or 7 methines. However, it contains at least one acidic group in the molecule.

The “aliphatic group” used in the present invention represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. These groups may have a substituent.
The alkyl group may be cyclic or linear. The chain alkyl group may have a branch. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and most preferably 1 to 8 carbon atoms. Examples of this alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclopropyl, cyclohexyl and 2-ethylhexyl.

The alkyl part of the substituted alkyl group is the same as the above alkyl group. Examples of the substituent of the substituted alkyl group include a halogen atom (F, Cl, Br, I atom), an aliphatic group, an aromatic group, a heterocyclic group, -OR ²⁰ , -COR ²¹ , -COOR ²² , -OCOR ²³ , ^{-NR 24 R 25, -NHCOR 26,} -CONR 27 R 28, -NHCONR 29 R 30, -NHCOOR 31, -SR 32, -SO 2 R 33, -SO 2 oR 34, -NHSO 2 R 35 or -SO ₂ NR ³⁶ R ³⁷ . R ^{20 to} R ³⁷ are each independently a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. In the case ^{R 22} in -COOR ²² is hydrogen (i.e., carboxyl) When ^{R 34} of Oyobi _SO 2 ^{OR 34} is a hydrogen atom (i.e., sulfo) also dissociate a hydrogen atom, of a salt It may be.
Examples of the substituted alkyl group include 2-hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl. 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl are particularly preferred.

The alkenyl group may be cyclic or chain-like. 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 the alkenyl group include vinyl, allyl, 1-propenyl, 2-butenyl, 2-pentenyl and 2-hexenyl.
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 be cyclic or chain-like. The chain 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.
The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. Examples of the substituent of the substituted alkynyl group include the same substituents as the alkyl group.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the aryl group described later. Examples of aralkyl groups include benzyl and phenethyl.
The aralkyl part of the substituted aralkyl group is the same as the above aralkyl group. The aryl part of the substituted aralkyl group is the same as the aryl group described later.

The “aromatic group” used in the present invention means an aryl group or a substituted aryl group.
The aryl group or substituted 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. Phenyl is preferred.
Examples of the substituent of the substituted aryl group include a nitro group and a cyano group in addition to the substituents described for the substituted alkyl group. Examples of substituted aryl groups include 4-carboxyphenyl, 4-acetamidophenyl, 3-methanesulfonamidophenyl, 4-methoxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl and 4-butanesulfonamidophenyl is included.

In the present invention, the heterocyclic group may have a substituent. The heterocyclic ring of the heterocyclic group is preferably a 5- or 6-membered ring. 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 Ring, phenoxazine ring, indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiadiazole ring.
The substituent of the heterocyclic ring is the same as the substituent of the substituted aryl group.

R ₁ and R ₂ are preferably alkyl groups having an acidic group (described later). 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl are particularly preferred.

Examples of the monovalent group of R ₃ and R ₄ include the substituents described for the aryl group. Furthermore, an alkyl group (as defined above), a phenyl group (as defined above), a halogen atom (as defined above) or an alkoxy group (as defined above) is preferable. Most preferred is the chloro atom.

L ₁ is a methine chain composed of an odd number of methines, and preferably 5 or 7. Seven is most preferred. At least one of the methine groups has a phenyl group, and the phenyl group may have a substituent (synonymous with a substituted aryl group). The phenyl group is preferably substituted with a central (meso-position) methine group. Further, methine chains may be bonded to each other to form a 5-, 6- or 7-membered ring (for example, cyclopentene, cyclohexene, cycloheptene ring).

Examples of the acidic group include a carboxyl group (may be a salt) or a sulfo group (may be a salt). It is particularly preferable to have a sulfo group. The molecule has one or more acidic groups, more preferably 2 or more, and more preferably 2 to 4 acidic groups. One of the acidic groups forms a salt in the molecule, and the other cation forming a salt of the acidic group includes a hydrogen atom, an alkali metal ion (Li ⁺ , Na ⁺ , K ⁺ ), an alkaline earth metal ion ( Examples, Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ ), transition metal ions (eg, Ag ⁺ , Fe ⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ ), other metal ions (eg, Al ³⁺ ) Ammonium ion, triethylammonium ion, tributylammonium ion, pyridinium ion and tetrabutylammonium ion are preferred.

  Of the compounds represented by the general formula (1), the compound represented by the general formula (2) is particularly preferred. The compound represented by the general formula (2) will be described.

Wherein R ₅ and R ₆ are a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group; p and q are each independently an integer of 1 to 4; R ₇ is a phenyl group; ₈ and R ₉ are a hydrogen atom or a group linked to each other to form a 5, 6 or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation N is 1, 2 or 3.

The alkyl group, phenyl group, halogen atom and alkoxy group represented by R ₅ , R ₆ and R ₇ have the same meanings as the respective groups described for the general formula (1). When R ₅ and R ₇ are halogen atoms, a chloro atom is most preferable. Examples of the divalent linking group represented by A include alkylene and phenylene, and alkylene is preferable. The alkylene linking group has 1 to 6 carbon atoms and may be branched. The 5, 6 or 7-membered ring formed by bonding R ₈ and R ₉ to each other has the same meaning as described above.

  Examples of the acidic group include a carboxyl group (may be a salt) or a sulfo group (may be a salt). It is particularly preferable to have a sulfo group. The cation forming the counter salt is as defined above.

  Furthermore, an associative cyanine compound represented by the general formula (3) is preferable.

Wherein R ₁₀ is a phenyl group; R ₁₁ and R ₁₂ are a hydrogen atom or a group linked to each other to form a 5, 6 or 7-membered ring; A is a divalent linking group; X Is an acidic group; M ^{n +} is a cation; n is 1, 2 or 3.
The phenyl group represented by R ₁₀ , the 5, 6 or 7-membered ring formed by R ₁₁ and R ₁₂ , the divalent linking group of A, the acidic group of X, and the cation of M ^{n +} are as defined above.
A plurality of compounds represented by the general formula (3), usually 4 or more molecules, preferably 10 to 30 molecules associate to form an aggregate. As will be described later, this aggregate is confirmed by measuring the difference between the absorption maximum in the solution state and the absorption maximum in the filter.

  Specific examples of the compounds represented by the general formulas (1) to (3) (hereinafter sometimes referred to as dyes) are shown below, but the present invention is not limited to these exemplary compounds.

  The compounds represented by the general formulas (1) and (2) are described by FM Harmer, “Heterocyclic Compounds Cyanine Dies and”, “Heterocyclic Compounds Cyanines Dies and” “Related Compounds” ”, John Wiley & Sons, New York, London, 1964, and“ Dam M. Stimmer ”,“ Heterocyclic Compounds-Special Topic in Heterocyclic Chemistry (Special Topics in Heterocyclic) c chemistry), Chapter 18, Section 14, pages 482-515, John Wiley & Sons, New York, London, 1977, "Rods Chemistry of Carbon Compounds". (Rodds Chemistry of Carbon Compounds) "2nd. Ed. vol. IV, part B, published in 1977, Chapter 15, pages 369-422, published by Elsevier Science Publishing Company Inc., New York, JP 4-362932 It can be synthesized by reference.

The near-infrared absorption filter of the present invention contains a compound represented by the general formula (1), (2) or (3) (hereinafter sometimes referred to as a dye), and its wavelength is in the range of 700 to 1100 nm. It is preferable that it exhibits an absorption maximum. The wavelength showing the absorption maximum (absorption maximum wavelength) may be that when the dye forms an aggregate. Furthermore, as an absorption spectrum of the near-infrared absorption filter of the present invention, it is preferable that the side absorption in the visible region (400 to 600 nm) is small. More specifically, the absorbance (Dv) at an absorption wavelength of 400 nm is preferably 1/10 or less of the absorbance (Dm) at the absorption maximum wavelength, more preferably 1/15 or less, and 1/20 or less. It is particularly preferred.
In order to obtain a preferable absorption waveform, the near-infrared filter 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. (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. Regarding dye association and J band, see, for example, Photographic Science and Engineering, Vol. 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 absorption filter is in an associated state or a non-associated state.

  In the present invention, after the association (for example, 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.

  The aggregate dye of the present invention is formed by dissolving the dye represented by the general formula (1), (2) or (3) in water and adding gelatin or a salt (for example, barium chloride, calcium chloride, etc.) in water. It can be an aggregate dye. Further, it can be dispersed as solid fine particles 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 absorption filter of the present invention can be adjusted as necessary. It is preferable to contain 30 mass%, and it is more preferable to contain 0.5-10 mass%.

The dye of the present invention can also be used as a solid fine particle dispersion. For such solid fine particle dispersions, for example, “Pigment Dispersion Technology-Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation” published by Technical Information Association, “Encyclopedia of Pigments” 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.

Further, as a fine particle forming method, the dye of the present invention is dissolved in a suitable solvent, and then a poor solvent is added to the solution to make fine particles, and if necessary, it may be powdered by a conventional method. 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, unless otherwise specified, the average particle diameter means a volume average particle diameter, which 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 kinds of compounds are used. For example, phthalocyanine derivatives (commercial product: EFKA-745 (trade name, manufactured by Efka)), Solsperse 5000 (trade name, manufactured by Zeneca); organo Siloxane 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, poly Nonionics such as oxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Emulgen A60 (trade name, manufactured by Kao Corporation) Surfactants: Anionic surfactants such as W004, W005, W017 (trade name, manufactured by Yusho Co., Ltd.), sodium dodecylbenzenesulfonate, Demol SNB (trade name, manufactured by Kao Corporation); EFKA -46, EFKA-47, EFKA- 7EA, 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 Co., Ltd.) and the like; various Solsperse dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 (trade name, GENECA ( Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (trade name, Asahi) (Manufactured by Denka) And Isonetto S-20 (trade name, manufactured by Sanyo Chemical Industries Co., Ltd.) and the like.

  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 in the composition of the present invention is preferably about 1 to 150 parts by mass with respect to 100 parts by mass of the dye.

  You may add a fading inhibitor, antioxidant, and a ultraviolet-ray inhibitor to the filter layer containing the pigment | dye of this invention. Antifading 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 (described in US Pat. No. 4,245,018 and JP-A-60-97353) or a singlet oxygen quencher may be added to the filter layer. The singlet oxygen quencher includes a nitroso compound (described in JP-A-2-300288), a diimmonium compound (described in US Pat. No. 4,656,612), a nickel complex (described in JP-A-4-146189) and an antioxidant (Europe). Patent 820057A1).

  The thickness of the filter layer is preferably 0.1 μm to 1 cm, and more preferably 0.5 μm to 100 μm.

  The filter layer further includes a polymer binder. Natural polymers (eg, gelatin, cellulose derivatives, alginic acid) or synthetic polymers (eg, polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, polycarbonate, water-soluble polyamide) It can be used as a polymer binder. A hydrophilic polymer (the above-mentioned natural polymer, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, water-soluble polyamide) is particularly preferred.

  The filter of the present invention has 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 or less, more preferably 25 μm to 1 cm, and most preferably 80 μm to 1.2 mm.

  The transmittance of the transparent support 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 of the transparent support, and more preferably 0.05 to 10% by mass. 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 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 filter of this invention comprises the compound represented by General formula (1) (2) or (3) in a photocurable composition and a thermosetting composition. Also good. A composition containing a compound having an ethylenically unsaturated group is preferred as the photocurable composition or the thermosetting composition. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolethanetri ( Multifunctional such as (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylates and methacrylates. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

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

Example 1
Compounds 5, 9, and 19 were synthesized by the following route.

＜化合物５の合成＞
ａ １．６ｇおよびｂ ０．８１ｇをメタノール１０ｍｌに溶解し、無水酢酸０．７ｍｌおよびトリエチルアミン２．１ｍｌを加え、５０℃で２時間反応させ、酢酸カリウム１．５ｇを加え、析出した結晶を濾過した。その後、ＭｅＯＨ／Ｈ２Ｏ＝１／１で精製を行い、化合物５を０．３ｇ得た。 λｍａｘはジメチルスルホキシド中で８０１ｎｍだった。モル吸収係数はジメチルスルホキシド中１．１１×１０^５ｄｍ^３／ｍｏｌ ｃｍであった。融点は２５２〜２５７℃だった。
＜化合物９の合成＞
ａ １．６ｇおよびｂ １ｇをメタノール１０ｍｌに溶解し、無水酢酸１ｍｌおよびトリエチルアミン２ｍｌを加え、５０℃で２時間反応させ、酢酸カリウム１．５ｇを加え、析出した結晶を濾過した。その後、ＭｅＯＨ／Ｈ２Ｏ＝１／１で精製を行い、化合物９を１．６ｇ得た。λｍａｘはジメチルスルホキシド中で８０８．５ｎｍだった。モル吸収係数はジメチルスルホキシド中１．８１×１０^５ｄｍ^３／ｍｏｌ ｃｍであった。融点は２５７〜２６１℃だった。
＜化合物１９＞
ａ ２．４ｇおよびｂ １．４７ｇをメタノール２５ｍｌに溶解し、無水酢酸２ｍｌおよびトリエチルアミン２ｍｌを加え、５０℃で２時間反応させ、酢酸カリウム１．５ｇを加え、析出した結晶を濾過した。その後、ＭｅＯＨ／Ｈ２Ｏ＝１／１で精製を行い、化合物１９を１ｇ得た。λｍａｘはジメチルスルホキシド中で８３７．５ｎｍだった。モル吸収係数はジメチルスルホキシド中１．７０×１０^５ｄｍ^３／ｍｏｌ ｃｍであった。融点は２３０〜２３５℃だった。
その他の化合物も上記の例と同様に合成できる。

<Synthesis of Compound 5>
a 1.6 g and b 0.81 g were dissolved in 10 ml of methanol, 0.7 ml of acetic anhydride and 2.1 ml of triethylamine were added, reacted at 50 ° C. for 2 hours, 1.5 g of potassium acetate was added, and the precipitated crystals were filtered. did. Thereafter, purification was performed with MeOH / H 2 O = 1/1 to obtain 0.3 g of Compound 5. λmax was 801 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.11 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was 252 to 257 ° C.
<Synthesis of Compound 9>
1.6 g of a and 1 g of b were dissolved in 10 ml of methanol, 1 ml of acetic anhydride and 2 ml of triethylamine were added, reacted at 50 ° C. for 2 hours, 1.5 g of potassium acetate was added, and the precipitated crystals were filtered. Thereafter, purification was performed with MeOH / H 2 O = 1/1 to obtain 1.6 g of Compound 9. λmax was 808.5 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.81 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was 257-261 ° C.
<Compound 19>
A 2.4 g and b 1.47 g were dissolved in 25 ml of methanol, 2 ml of acetic anhydride and 2 ml of triethylamine were added and reacted at 50 ° C. for 2 hours, 1.5 g of potassium acetate was added, and the precipitated crystals were filtered. Thereafter, purification was performed with MeOH / H 2 O = 1/1 to obtain 1 g of Compound 19. λmax was 837.5 nm in dimethyl sulfoxide. The molar absorption coefficient was 1.70 × 10 ⁵ dm ³ / mol cm in dimethyl sulfoxide. The melting point was 230-235 ° C.
Other compounds can be synthesized in the same manner as in the above example.

(Example 2)
A mixture of 0.5 g of the compound of the present invention (Exemplary Compound 18), 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 mixed with a planetary ball mill (Germany). To obtain a dispersion. The average particle radius of the obtained particles was 0.21 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 solution was spin-coated on a glass substrate and dried at 100 ° C. for 2 minutes to form a filter layer having a thickness of 2 μm, thereby producing an infrared absorption filter A.
(Example 3)
In the same manner as in Example 2 except that Exemplified Compounds 19, 20, 15, 9 and 5 of the present invention were used instead of Exemplified Compound 18 of the present invention used in Example 2, a dispersion and an infrared absorption filter B, C, D, E and F were prepared.

Example 4
Dispersions and infrared absorption filters G, H and I were used in the same manner as in Example 2 except that comparative dyes a, b and c were used in place of the exemplified compound 18 of the present invention used in Example 2. It was created. Comparative Example a is a dye described in JP-A-2002-90521, Comparative Example b is a dye described in JP-A-4-362932, and Comparative Example c is a journal described in Journal of Information Recording Materials, (1988), 16 (1), 23-31.

(Filter evaluation)
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 dimethyl sulfoxide or methyl alcohol was measured (measured by dissolving 1 mg of dye in 100 ml of DMSO).

<Invisibility>
About invisibility, the value (Dv / Dm) obtained by dividing the absorption density (Dv) of 400 nm of the filter by the density (Dm) of the absorption maximum wavelength using UV-3100Pc (trade name, manufactured by Shimadzu Corporation). Indicated.

<Light resistance>
Using a weather meter (Atlas C.I65, trade name, manufactured by Atlas Co., Ltd.), the filter was irradiated with xenon light (100,000 lx) for 20 hours, and the image density before and after the xenon irradiation was measured using the above 3100PC. Post-concentration / pre-irradiation concentration = dye residual rate was evaluated.

[Table 1]
---------------------------------------
Fill Dye λmb / film λma / solvent invisibility light-resistant tar (exemplary compound)
---------------------------------------
A 18 1080nm 837nm / DMSO 0.015 95%
B 19 1060 nm 837 nm / DMSO 0.030 85%
C 20 1045 nm 837 nm / DMSO 0.011 95%
D 15 900 nm 809 nm / DMSO 0.018 90%
E 9 975 nm 809 nm / DMSO 0.009 80%
F 5 1025 nm 801 nm / DMSO 0.011 97%
G a 940 nm 823 nm / DMSO 0.090 50%
H b 970 nm 781 nm / MeOH 0.174 0%
I c 640 nm 807 nm / MeOH 0.080 0%
---------------------------------------

  As is apparent from Table 1, the filter of the present invention has a longer wave than the solution absorption, and is excellent in invisibility and light resistance.

Claims (8)

A near-infrared absorption filter comprising a cyanine compound represented by the following general formula (1).

[Wherein, R ₁ and R ₂ are each independently an aliphatic group or an aromatic group; R ₃ and R ₄ are each independently a hydrogen atom or a monovalent group; and p and q are each independently L ₁ is an integer from 1 to 4; L ₁ consists of 5 or 7 methines, at least one of which is a methine chain having a phenyl-substituted methine. However, the molecule contains at least one acidic group]. The near-infrared absorption filter according to claim 1, wherein the cyanine compound represented by the general formula (1) is a cyanine compound represented by the following general formula (2).

[Wherein, R ₅ and R ₆ are a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group; p and q are each independently an integer of 1 to 4; R ₇ is a phenyl group; R ₈ and R ₉ are a hydrogen atom or a group linked to each other to form a 5, 6 or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation. Yes; n is 1, 2 or 3].   The near-infrared absorption filter according to claim 1 or 2, wherein the cyanine compound represented by the general formula (1) or (2) forms an aggregate.   The near-infrared absorption filter according to any one of claims 1 to 3, wherein the near-infrared absorption region is a region having an absorption wavelength of 700 nm to 1100 nm.   The near-infrared absorption filter according to any one of claims 1 to 4, wherein the absorbance at 400 nm is 1/20 or less of the absorbance at the maximum absorption wavelength.   The near-infrared absorption filter according to claim 1, comprising a solid fine particle dispersion of a cyanine compound represented by the general formula (1) or (2). An associative near-infrared absorbing cyanine compound represented by the following general formula (2).

[Wherein, R ₅ and R ₆ are a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group; p and q are each independently an integer of 1 to 4; R ₇ is a phenyl group; R ₈ and R ₉ are a hydrogen atom or a group linked to each other to form a 5, 6 or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation. Yes; n is 1, 2 or 3]. An associative near-infrared absorbing cyanine compound represented by the following general formula (3).

[Wherein R ₁₀ is a phenyl group; R ₁₁ and R ₁₂ are a hydrogen atom or a group linked to each other to form a 5-, 6-, or 7-membered ring; A is a divalent linking group; X is an acidic group; M ^{n +} is a cation; n is 1, 2 or 3].