WO2008029594A1 - Near-infrared-ray-absorbable material, near-infrared-ray-absorbable composition comprising the material, and their use - Google Patents

Abstract

A near-infrared-ray-absorbable material having a repeating unit represented by the general formula (1); and a near-infrared-ray-absorbable composition comprising the material. [General formula (1)] wherein M represents a metal atom; one of R1 to R20 represents a direct bond and another one of R1 to R20 represents a bivalent group represented by the general formula (2), and the others independently represent a hydrogen atom or a substituent; [General formula (2)] wherein X1 to X4 independently represent a direct bond or a bivalent group such as –O-, -S-, -COO-, -OCO-, -SO2- and -CO-; Ar1 and Ar2 independently represent an arylene group or a heteroarylene group; n represents a natural number; and Y represents a direct bond or a bivalent group such as an alkylene group, –O-, -S-, -NH-, -COO-, -SO2- and -CO-.

Description

 Specification

 Near-infrared absorbing material, near-infrared absorbing composition containing the same, and use thereof

 The present invention relates to a near-infrared absorbing material comprising a novel dithiol-based polymer, a near-infrared absorbing composition containing the near-infrared absorbing material, a laminate having a layer containing the near-infrared absorbing material, and the near-infrared material. The present invention relates to a near-infrared absorbing film including an infrared absorbing material and a near-infrared absorbing filter including the near-infrared absorbing material. More specifically, there are optical filters for semiconductor light receiving elements, plasma displays, liquid crystal displays, and various other near infrared absorption! /, Near infrared cut filters, near infrared absorption or near infrared cut films, Is an optical recording dye, a near-infrared absorbing material for laser marking, a near-infrared absorbing material in laser welding, and the near-infrared absorbing material useful in various applications, a laminate having a layer containing these near-infrared absorbing materials, The present invention relates to a near-infrared absorbing film containing the near-infrared absorbing material and a near-infrared absorbing filter containing the near-infrared absorbing material.

 Background art

 [0002] Various near-infrared absorbing materials having absorption in the near-infrared part are known.

 Among these near-infrared absorbing materials, the organic nickel complex generally has an absorption property in the near-infrared part of 950 nm to 1200 ηm, and has excellent properties as a near-infrared absorbing material. The main applications include optical filters for semiconductor light-receiving elements that have the function of absorbing and cutting near infrared rays, near-infrared absorbing films and near-infrared ray absorbing plates that block heat rays for energy conservation, and selective use of sunlight. Near-infrared absorbing film for agricultural purposes, recording medium using near-infrared absorption heat, near-infrared cut filter for electronic equipment, near-infrared filter for photography, protective glasses, sunglasses, heat ray-blocking film, optical recording It is used for applications such as dyes, optical character reading and recording, copy protection of confidential documents, electrophotographic photoreceptors, and laser welding. It is also used for noise cut filters for CCD cameras and filters for CMOS image sensors.

On the other hand, in a plasma display (PDP), a neon gas having a light emitting element of 800 to 1050 nm is used. As a result, there is a problem that malfunction of equipment using a near-infrared remote control occurs. To solve this problem, PDP uses a filter that absorbs near-infrared rays. This filter requires excellent visible transmission. In addition, the dyes used in this filter are required to have high thermal stability and high light resistance. However, changes in filter chromaticity and deterioration of near infrared absorption ability due to material deterioration are problems.

 [0004] In addition, in an optical device such as a camera or a video camera, a silicon diode element, a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), or the like is used to convert an optical signal into an electric signal. The These photoelectric conversion elements (hereinafter referred to as “optical elements”) have a wide light-sensitive region of 300-00; UOOnm, so in the near-infrared region compared to the human eye's visual sensitivity of 400-700 nm. It will be very sensitive. In general, optical devices such as cameras and video cameras need to be sensitive to wavelength light in the human visibility range, and wavelength light outside this range will interfere with unfavorable photometry and color reproducibility. It will be. Therefore, in this case, an optical filter that transmits visible light and efficiently absorbs and cuts near-infrared light is required.

 [0005] As a filter for the above-mentioned CCD and CMOS, a phosphoric acid ester copper compound dispersed in a resin (for example, see Patent Documents !! to 5), a composite optical filter having a low-pass function and a visibility correction function (for example, a patent) There is a filter made of a resin obtained by polymerizing phosphine oxide as a component of the monomer (see, for example, Patent Document 7), etc., but it is not always satisfactory in terms of durability and transparency. Nare ,.

[0006] Dithiol-based complexes are also known as near-infrared absorbing materials. Known dithiol-based complex near-infrared absorbing materials include bis (dithiobenzyl) nickel complex compounds (see, for example, Patent Documents 8 and 9), bis (1,2 acenaphthylene dithiolato) nickel complex compounds (for example, Patent Document 10), 4 tertbutyl-1,2 benzenedithiol nickel complex (for example, see Patent Document 11), and bis (dithiobenzil) nickel complex compound having an alkoxy group (for example, see Patent Document 12). As the polymer dithiol complex, a dithiolate nickel polymer complex (for example, see Patent Document 13), a bisdithiolene complex polymer (for example, see Patent Document 14), and the like are known. Bisdithiolene complex polymers have an absorption wavelength region at a relatively short wavelength of ~ 800 nm, It is unsuitable for use as a near-infrared absorbing material. In addition, since V does not have a substituent at the complex skeleton, it has poor solubility! /, And! /. In addition, polynuclear thiol complexes (for example, see Patent Document 15), quaternary phosphonium bis (cis 1,2-ethylenedithiolato) nickelate derivatives (for example, see Patent Document 16), dithiolate metal complexes having secondary alkyl groups. (See, for example, Patent Document 17) is also known as a long-wavelength absorption material, but it has low solubility in solvents, poor compatibility with resins, is low! It was not practical, such as lack of heat.

 Similarly, phthalocyanine-based materials are known as near-infrared absorbing compounds. Examples of such phthalocyanine-based materials include phthalocyanine compounds or naphthalocyanine compounds having a substituent (see, for example, Patent Document 18), phthalocyanine compounds having an amino group (see, for example, Patent Documents 19 to 23), fluorine-containing phthalocyanine compounds ( For example, Patent Documents 24 and 25) are known.

 [0008] Furthermore, dimonium dyes are materials that absorb a wide range of long wavelengths (950 nm to UOOnm) and have very good transparency to visible light, and various types are known (for example, , See patent documents 26-29). And this pigment | dye also has high solubility and resin compatibility. However, heat resistance and light resistance are not always satisfactory.

 [0009] Further, as a special example, a dithiol nickel complex having an olefin copolymer as a substituent (for example, Patent Document 30) is also known, but the synthesis process is long and the difficulty of synthesis is high. It is difficult to adjust the concentration of the dye after synthesis because it is linked to the resin. It is clearly not practical considering that the molar extinction coefficient varies from synthesis to synthesis.

 [0010] The near-infrared absorbing dye used for the near-infrared absorbing material is generally dissolved in a solvent, then mixed with a resin and coated on a substrate such as plastic, or heated and kneaded with a resin. It is used after being formed into a film, sheet, plate or other shape. For this reason, the near-infrared absorbing dye is required to have excellent solubility in a solvent and compatibility with a resin. Furthermore, since the near-infrared absorbing material may be used outdoors, the near-infrared absorbing dye itself is required to have high durability, thermal stability, and the like.

[0011] Patent Document 1: W099 / 26951 Patent Document 2: W099 / 26952 Patent Document 3: Japanese Patent Laid-Open No. 2000-7871 Patent Document 4: W098 / 55885 Patent Document 5: Japanese Patent Laid-Open No. 2000-38396 Patent Document 6: Japanese Patent Laid-Open No. 8-146216 Patent Document 7: Japanese Patent Laid-Open No. 2000-98130 Patent Document 8: Japanese Patent Laid-Open No. 63-227597 Patent Document 9: Japanese Patent Laid-Open No. 64-61492 Patent Document 10: Japanese Patent No. 2923084 Patent Document 11: Special Japanese Patent Laid-Open No. 63-307853 Patent Document 12: Japanese Patent Laid-Open No. 2-264788 Patent Document 13: Japanese Patent Laid-Open No. 4 198304 Patent Document 14: US Patent No. 5089585 Patent Document 15: Japanese Patent Laid-Open No. 2005-181966 Patent Document 16: Japanese Patent Publication No. 6-72147 Patent Document 17: Japanese Patent Application Laid-Open No. 2005-232185 Patent Document 18: Japanese Patent Application Laid-Open No. 10-78509 Patent Document 19: Japanese Patent Application Laid-Open No. 2004-18561 Patent Document 20: Japanese Patent Application Laid-Open No. 2004-18561 Japanese Patent No. 2001-106689 Patent Document 21: Japanese Patent Laid-Open No. 2000-63691 Patent Document 22: Japanese Patent No. 2746293, Patent Document 23: Japan Special Patent No. 3226504 Patent Literature 24: Japanese Patent No. 2907624, Patent Literature 25: Japanese Patent No. 3014221 Patent Literature 26: Japanese Patent Laid-Open No. 05-247437 Patent Literature 27: Japanese Patent Laid-Open No. 2005-325292 Patent Literature 28 : Japanese Patent No. 3699464 Patent Document 29: Japanese Patent Laid-Open No. 2003-096040 Patent Document 30: US Patent No. 6489399

 Disclosure of the invention

 Problems to be solved by the invention

 [0012] Substituted benzenedithiolnickenole complexes, phthalocyanines, anthraquinones, bisdithiobenzylnickel complexes and the like, which are conventionally used as near-infrared absorbing dyes, are used as a near-infrared absorbing material. The results are not necessarily satisfactory. For example, phthalocyanines are substituted with various substituents to improve solubility in solvents, but as a result, light resistance, thermal stability, etc. are inferior. In addition, since the absorption spectrum is sharp, the wavelength range that can absorb near infrared rays is small. On the other hand, substituted benzenedithiol-nickel complexes are superior in that they are relatively easy to manufacture and have good durability. Solubility in solvents Force S is small and compatibility with resins There is a problem of being inferior.

 [0013] That is, when the near-infrared absorbing material is dissolved in a solvent and has a low solubility in a solvent! /, It is used to block near-infrared rays on the surface of glass, paper or resin used as a substrate. It becomes difficult to contain a sufficient amount of the dye. When the film thickness is increased to include a sufficient amount of dye, a new absorption band appears in the visible light region due to the stacking of the dye molecules, causing a reduction in visible light transmittance. In addition, the intermolecular interaction is increased, resulting in a decrease in near-infrared absorption characteristics. Also, when a near-infrared absorbing material is mixed with a monomer and this monomer is polymerized and cured to form a near-infrared absorbing member, if the solubility in the monomer is low, it becomes difficult to contain a sufficient amount of dye, When a dye having a sufficient solubility is contained, a problem arises that the near-infrared absorption layer becomes partially opaque due to the undissolved dye. In addition, the compatibility between the near-infrared absorbing material and the resin is poor, and there is a problem that it is difficult to obtain a layer having uniform near-infrared absorbing characteristics.

 [0014] Furthermore, the solubility of the dye in the solvent and the compatibility with the resin are low! / And it becomes difficult to contain a sufficient amount of the dye to block near infrared rays, and the transparency of visible light , Long wavelength (800 ~; UOOnm) absorption is also low and resistance is low.

[0015] On the other hand, the Hansen solubility parameter is used as a standard for evaluating the solubility between substances, that is, the compatibility. A parameter (SP value) is used, and the unit is represented by (cal / cm ³ ) ¹⁷² . Hereinafter, the Hansen solubility parameter (SP value) is simply abbreviated as “solubility parameter” or “SP value”. In recent years, theories and calculation methods for solubility parameters have advanced rapidly, and the frequency of use is increasing as an effective method for predicting the physical properties of solutions when selecting solvents in the chemical industry. The first solubility parameter is the dispersion force (δ), which occurs between the permanent dipoles of the molecule d

 Force (δ), molecular hydrogen bonding force (δ)

P h

 Those that are close to each other are easily soluble (Hideki Yamamoto, “SP Value Fundamentals-Applications and Calculations”, Information Technology Co., Ltd., April 3, 2006, 4th edition). In the conventional near-infrared absorbing composition and near-infrared absorbing filter, when the near-infrared absorbing material is mixed with the resin, the near-infrared absorbing material is difficult to dissolve uniformly due to the difference in SP value. There was a problem such as becoming a certain filter. In addition, compounds of any structure are excellent in light resistance and heat resistance, and have excellent strength, compatibility with resins, and solubility in solvents. This makes near infrared rays excellent in transparency and durability. It is difficult to predict whether an absorbent film or composition will be obtained!

 [0016] Therefore, the object of the present invention is easy to manufacture, good solubility in a solvent and good compatibility with a resin, and has a wide near-infrared absorption region and excellent heat resistance and durability. It is to provide an infrared absorbing material.

 Another object of the present invention is to provide a near-infrared absorbing composition containing a near-infrared absorbing material having the above excellent characteristics.

 [0017] Another object of the present invention is to provide a near-infrared-absorbing laminate containing at least one near-infrared absorbing material having the above-mentioned excellent characteristics, and to provide near-infrared absorption having the above-mentioned excellent characteristics. It is providing the resin film containing material.

 Another object of the present invention is to provide an optical filter containing a near-infrared absorbing material having the above excellent characteristics.

 Means for solving the problem

[0018] The present invention relates to the following near-infrared absorbing material, near-infrared absorbing composition, laminate, resin film, and optical filter.

[0019] [1] A near-infrared absorbing material having a repeating unit represented by the following general formula (1). [0020] General formula

 [Chemical 1]

[In the formula, M represents a metal atom, one of 1 ^ to 1 ^ ° represents a direct bond, and the other represents a divalent group represented by the following general formula (2). And the rest each independently represents a hydrogen atom or a substituent.)

 [0022] General formula (2):

 [Chemical 2]

X ¹ H- CH ₂ -X ^2- ■ Ar ¹ —— Y—— A--x ^3- ■ CH ₂ --X ⁴ —

[0023] (wherein ^1-4 represents a direct bond or single NHCO CONH NHCOO O CONH OS COO OCO SO CO C = CN = NS- S-, substituted or unsubstituted imino groups,

Ar ¹ and Ar ² represent a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group,

 n represents a natural number,

 Y is a direct bond or unsubstituted alkylene group, NHCO—, —CONH—, —NHC OO OCONH OS NH COO OCO SO CO C = CN = NS—S, substituted imino group or the following divalent organic residue A Represents )

 [0024] Divalent organic residue A:

[Chemical 3]

CH ₂ CH (CH ₃ ) ₂ C ₂ H ₅ — CH— C ₄ H ₉ CF ₃

 H, C, CH

 H2C ヽ zCH2

CH ₃ CH-,

CF ₃

H ₂

 Ten

 [0025] [2] In the near-infrared absorbing material according to [1] above, I ^ to R, one of the deviations is a direct bond, and R "to R ', one of the deviations is represented by the general formula (2) A near-infrared absorbing material, which is a group represented by

[0026] [3] in the near infrared absorbing material according to [1] is any one of the direct binding of I ^ to R ^5, any one of R ⁶ to R ^1Q general formula (2) A near-infrared absorbing material characterized by being a divalent group represented by:

[0027] [4] in the near infrared absorbing material according to [1] is any one of the direct binding of I ^ to R ^5, another of I ^ to R ⁵ have the general formula (2) A near-infrared absorbing material characterized by being a divalent group represented by

[0028] [5] In the near-infrared absorbing material according to [1], at least Hitotsugae one ether bond and / or Ar ¹ and Ar ² are substituted or unsubstituted phenylene group Xi～X ⁴ A near-infrared absorbing material characterized by

[0029] [6] In the near-infrared absorbing material according to [1], at least Hitotsugae one ether bond and Ar ¹ and Ar ² are substituted or unsubstituted phenylene group Xi～X ^4, and Y Is a near-infrared absorbing material, characterized in that is any one of the above divalent organic residues A.

 [7] In the near-infrared absorbing material described in [1] above, the near-infrared absorbing material has the general formula (

 1. A near-infrared absorbing material, which is a homopolymer having a repeating unit represented by 1).

[0031] [8] In the near-infrared absorbing material as described in [1] above, the near-infrared absorbing material contains at least two types of repeating units represented by the general formula (1) as repeating units. A near-infrared absorbing material, characterized by being a copolymer. [0032] [9] In the near-infrared absorbing material described in [2] above, the divalent group represented by the general formula (2) is bonded to! /, NA! /, And the benzene ring is substituted at the ortho position. A near infrared ray absorbing material characterized by comprising:

 [0033] A near-infrared absorbing composition comprising a non-resin resin and the near-infrared absorbing material according to any one of [1] to [9] above.

 [11] In the near-infrared absorbing composition according to [10] above, the dispersive force (δ) which is a Hansen solubility parameter of each of the binder resin and the near-infrared absorbing material, between the permanent dipoles of the molecule The force (δ) generated in the molecule and the hydrogen bonding force (δ) of the molecule are 7 · 0 <δ <dphd

9. Near-infrared absorbing composition, characterized in that 0, 0.1 <δ <5.5, 0.1 <δ <5.0

 P h

 object.

 [0035] [12] In the near-infrared absorbing composition described in [10] or [11] above, 0.0 to 20 parts by weight of the near-infrared absorbing material is blended with 100 parts by weight of the binder resin. A near infrared ray absorbing composition characterized by comprising:

[11] The near-infrared absorbing composition according to any one of [10] to [; 12] above, wherein the binder resin has a glass transition temperature of 80 ° C. or higher. Composition.

 [0037] [14] The near-infrared absorbing composition according to any one of [10] to [; 12] above, wherein the binder resin has a glass transition temperature of 0 ° C or lower. Composition.

 [0038] [15] The near-infrared absorbing composition as described in any one of [10] to [; 14] above, wherein the near-infrared absorbing composition further comprises a solvent.

 [16] In the near-infrared absorbing composition according to any one of [10] to [; 15], the near-infrared absorbing material has a near-infrared absorption wavelength represented by the general formula (1). A near-infrared absorbing composition comprising two or more different near-infrared absorbing materials.

 [0040] [17] The near-infrared absorbing composition according to any one of [10] to [; 16] above, wherein the near-infrared absorbing composition is further represented by the following general formula (11): A near infrared ray absorbing composition comprising a material.

[0041] General formula (11): [Chemical 4]

(Wherein M ² represents a metal atom, R ⁵ ° to R ⁵³ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, Or a substituted or unsubstituted silyl group or a substituted or unsubstituted acyl group, and two Rs in the same ligand may be bonded to each other to form a ring, which is also a monovalent salt. Also good.)

[18] In the near-infrared absorbing composition according to [17], R ⁵ ° to R ⁵³ in the general formula (11) are monovalent organic residues represented by the following general formula (12). A near-infrared ray absorbing composition characterized by being.

 [0044] General formula (12):

 [Chemical 5]

[In the formula, X ⁵ represents a direct bond or 0- ■ S − —CO—, a substituted or unsubstituted imino group, n ¹ represents a natural number, n ² represents 0 or a natural number, R ⁵⁴ ˜R ⁵⁸ represents a hydrogen atom or a substituent.

[19] The near-infrared absorbing composition as described in [18] above, wherein X ⁵ is a direct bond or —O ² and n ² is 1.

[0047] [20] above [18] or in the near infrared absorption composition according to [19], the near-infrared-absorbing composition characterized in that R ⁵⁴ and / or R ⁵⁸ is a substituent.

[0048] [21] The near-infrared absorbing composition according to any one of [10] to [20] above, wherein the noinder resin is a pressure-sensitive adhesive or an adhesive. Yes

 [0049] [22] The near-infrared absorbing composition according to any one of [10] to [20], wherein the near-infrared absorbing composition is a coating agent.

 [0050] [23] The near-infrared absorbing composition according to any one of [10] to [20] above, wherein the near-infrared absorbing composition is for a plasma display. .

 [0051] [24] The near infrared ray absorbing composition according to any one of [10] to [20], wherein the near infrared ray absorbing composition is laser welding.

 [0052] [25] The near-infrared absorbing composition according to any one of [10] to [20] above, wherein the near-infrared absorbing composition is for laser marking. .

 [0053] [26] The near-infrared absorbing composition according to any one of [10] to [20], wherein the near-infrared absorbing composition is for a heat ray shielding material. .

[27] The near-infrared absorbing composition as described in any one of [10] to [20] above, wherein the near-infrared absorbing composition is for LEDs.

[0055] [28] The near-infrared absorbing material according to any one of [1] to [9] above or [10

] To [20], a laminate comprising a layer containing the near-infrared absorbing composition according to any one of the above.

 [0056] [29] The laminate according to [28] above, wherein the laminate is an adhesive sheet.

 [0057] [30] A laminate according to the above [28] or [29], wherein the substrate is a transparent substrate.

 [0058] [31] A resin film comprising the near-infrared absorbing material according to any one of [1] to [9] or the near-infrared absorbing composition according to any one of [10] to [20].

 [0059] [32] An optical filter comprising the laminate according to any one of [28] to [30] above or the resin fine film according to [31].

[0060] [33] The optical filter according to the above [32], wherein the optical filter is for plasma display. [0061] [34] The optical filter as set forth in [32], wherein the optical filter is for a liquid crystal display.

[0062] [35] The optical filter according to [32], wherein the optical filter is for a CCD camera.

[0063] [36] The optical filter according to the above [32], wherein the optical filter is for a CMOS image sensor.

 The invention's effect

 [0064] The near-infrared absorbing material having a repeating unit represented by the general formula (1) of the present invention is easy to manufacture, has excellent light resistance and heat resistance, and has a wide absorption in the near-infrared region of 800 nm to 1100 nm. It is a polymer useful as a near-infrared absorbing material. In addition, the SP value of the near-infrared absorbing material of the present invention is close to the SP value of the binder resin and solvent used in the near-infrared absorbing composition! Compared with the resin and solvent, the content of the near-infrared absorbing material in the near-infrared absorbing composition can be increased as compared with the conventional one. Therefore, the near-infrared absorbing composition containing the near-infrared absorbing material of the present invention is thin! /, Forming a highly durable film with good near-infrared absorption even in a film and high light transmittance in the visible light region. can do.

 [0065] In addition, the near-infrared absorbing composition of the present invention can form a resin film with a force S that can form a film by applying the composition to a substrate, itself. The obtained near-infrared absorbing film, the laminate having this film, and the near-infrared absorbing resin film are used as an optical filter for plasma displays, liquid crystal displays, CCD cameras, CMOS image sensors, etc., and energy saving. Near-infrared absorbing films and near-infrared absorbing plates that block heat rays used for applications, agricultural near-infrared absorbing films for selective use of sunlight, recording media and laser welding that use near-infrared absorbing heat Near-infrared cut filter for electronic equipment, near-infrared filter for photography, protective glasses, sunglass, heat ray blocking film, dye for optical recording, optical character reading recording, confidential document copy prevention, electrophotographic photoreceptor, etc. It can be preferably used.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0066] The present invention provides a novel near-infrared absorption having a repeating unit represented by the general formula (1). Material, a near-infrared absorbing composition containing the novel near-infrared absorbing material, a laminate having the near-infrared absorbing material or a layer containing the near-infrared absorbing composition, and a near-infrared absorbing resin containing the near-infrared absorbing material The present invention relates to a near-infrared absorbing filter including a film, a near-infrared absorbing laminate, and a near-infrared absorbing resin film.

 [0067] The novel near-infrared absorbing material of the present invention will be specifically described below. General formula (1) which is the near infrared absorption material of the present invention:

 [0068] [Chemical 6]

In the polymer having a repeating unit represented by [0069], M represents a metal atom, one of 1 ^ to 1 ^ ° represents a direct bond, and the other represents a general formula (2):

[0070] [Chemical 7]

_{^{X 1 H- CH 2 ■ X 2}} - ■ Ar 1 - Y-- Ar 2 - -X 3 - -CH 2 "-X 4 -

[0071] (wherein, ~ ^4, Ar ¹ and Ar ^2, n, and Y represents. Things as previously defined) represents a divalent group represented by the rest each independently represent a hydrogen atom Or represents a substituent.

 [0072] The metal atom of に お け る in the general formula (1) is not particularly limited as long as it is a metal atom, but nickel, cobalt, platinum, palladium or copper is more preferable.

[0073] Further, the "substituent" of 1 ^ to ° is a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted thioalkoxy group, cyano group, amino group, mono or disubstituted amino group, hydroxyl group, mercapto group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylothio group, substituted or unsubstituted aryl group , Replaced or not It represents a substituted heteroaryl group, and the “substituent” may form a conjugated or non-conjugated ring with or without substitution between adjacent substituents. Preferred examples of the “substituent” include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, and a mono- or di-substituted amino group. In addition, examples of the conjugated or non-conjugated ring that is substituted or unsubstituted between adjacent substituents include 5- or 7-membered oxygen, nitrogen, and sulfur atoms between adjacent substituents. Aliphatic, carbocyclic aromatic, heterocyclic aromatic, and heterocyclic ring may be mentioned, and these rings may further have a substituent at any position. Hereinafter, these groups will be described in more detail.

 [0074] The substituted or unsubstituted alkyl group constituting the "substituent" of 1 ^ to 1 ^ ° is not particularly limited as long as it is a substituted or unsubstituted alkyl group. The alkynole group may be linear, branched, or cyclized cycloalkyl group. Specific examples of substituted or unsubstituted alkyl groups include, for example, methyl, ethyl, propyl, butyl, sec butyl, tert butyl, pentyl, hexyl, 2-ethylhexyl. Group, heptyl group, octyl group, isooctyl group, stearyl group, trichloromethine group, trifluoromethylol group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexaenyl group, 2 cyclopentene-1-yl group, 2, 4 cyclopentagen 1 iridur group and the like.

 [0075] Further, the substituted or unsubstituted alkoxy group constituting the "substituent" of 1 ^ to ° is not particularly limited as long as it is a substituted or unsubstituted alkoxy group. Group, ethoxy group, propoxy group, n butoxy group, sec butoxy group, tert butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, stearyloxy group, trifluoromethoxy group and the like.

 [0076] Further, the substituted or unsubstituted thioalkoxy group constituting the "substituent" of 1 ^ to ° is not particularly limited as long as it is a substituted or unsubstituted thioalkoxy group. Examples thereof include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec-butylthio group, a tert butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

[0077] The mono- or di-substituted amino group constituting the "substituent" of 1 ^ to ° is mono- or di- It is not particularly limited as long as it is a di-substituted amino group. For example, methylamino group, dimethylamino group, ethylamino group, jetylamino group, dipropylamino group, dibutylamino group, diphenylamino group, bis (acetoxymethyl) Amino group, bis (acetoxochet

And dibenzylamino groups.

[0078] Further, examples of the substituted or unsubstituted aryloxy group constituting the "substituent" of 1 ^ to ° include a phenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group and the like. .

 [0079] Further, examples of the substituted or unsubstituted arylothio group constituting the "substituent" of 1 ^ to o include a phenylthio group and a 3-fluorophenylthio group.

 [0080] The substituted or unsubstituted aryl group constituting the "substituent" of 1 ^ to ° is, for example, a phenyl group, a biphenylenyl group, a triphenylenyl group, a tetraphenylenyl group, 3-nitrophenyl. Group, 4-methylthiophenenyl group, 3,5-dicyanophenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-tamenyl group, mesityl group, pentarenyl group, Indul, naphthyl, anthracenyl, azulenyl, heptarelinole, acenaphthylenyl, phenenyl, fluorenyl, antholinol, anthraquinolyl, 3-methinoleanthrinole, phenanthrinol, pyrenyl, Chrysinole group, 2-ethinole 1-chrysinole group, piceninole group, perileninole group, 6-clonal perireninole group, pen Examples include a taphenyl group, a pentacenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an ovalenyl group.

[0081] In addition, examples of the substituted or unsubstituted heteroaryl group constituting the "substituent" of 1 ^ to ° are, for example, thionyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyradyl group. Group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, phthalajuryl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acrylidinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, flazanyl group Phenoxazinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, 2-methylpyridyl group, 3-cyanopyridyl group and the like. [0082] Further, as a conjugated or non-conjugated ring having a substituted or unsubstituted group formed by the bonding of adjacent substituents constituting the "substituent" of 1 ^ to °, for example, substituted cyclohexyl Group, naphthyl group and the like.

On the other hand, in the above general formula (2), Xi X ⁴ is a direct bond or NHCO—, —CON H, 1 NHCOO, 1 NHCONO, 1 OCONH, 1 O, 1 S, 1 COO, 1 OCO, 1 SO 1, 1 CO, C = C, N = N—, S—S—, a substituted or unsubstituted imino group, preferably an ether bond group, an ester bond group, a substituted or unsubstituted imino group.

 [0084] Examples of the substituted imino group include the following.

[Chemical 8]

In addition, Ar ¹ and A in the general formula (2) represent a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, preferably a substituted or unsubstituted phenylylene group. is there.

 [0086] The substituted or unsubstituted arylene group is preferably a monocyclic or condensed ring arylene group having 6 to 60 carbon atoms, more preferably 6 to 40 carbon atoms, still more preferably 6 to 30 carbon atoms. Is an arylene group. Specific examples include phenylene, biphenylene, naphthalenezyl, anthracenezyl, phenanthrene lindyl, pyrenezyl, triphenylinole, benzophenanthin lindinore, perylene diole, pentaphenylene ginole, pentasensyl, etc. These groups may have a substituent. Examples of these substituents include those similar to the above-described 1 ^-° C substituents.

[0087] The substituted or unsubstituted heteroarylene group is preferably a monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms, more preferably a nitrogen atom, A monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms containing at least one of an oxygen atom or a sulfur atom, more preferably a 5 or 6 membered carbon group having 4 to 30 carbon atoms. An aromatic heterocyclic group. Specific examples of aromatic heterocyclic groups include pyrrole ', Huena

And these groups may have a substituent. Examples of these substituents include the same ones as the above-mentioned 1 ^-° C substituents.

[0088] In the general formula (2), n represents a natural number, Y represents a direct bond or an unsubstituted alkylene group, NHCO CONH NHCOO OCONH OS NH COO OCO SO CO C = CN = N-S-S- Represents a substituted imino group or the following divalent organic residue A. As the substituent of the substituted imino group, a linear, branched or cyclic alkyl group is preferable.

[0089] Divalent organic residue A:

 [Chemical 9]

[0090] The repeating unit represented by the general formula (1) is preferably (i) I ^ R

Shift or one is a direct bond, a repeating unit, one of (mouth) I ^ R ⁵ any one of R ^U R ² ° is a divalent radical I Table by formula (2) One is a direct bond, and any one of R ⁶ R ^1Q is a divalent group represented by the general formula (2), or (C) I ^ R ⁵ ! / One is a direct bond and the other one of I ^ R ⁵ is a divalent group represented by the general formula (2). More preferably, the following general formula (4) (7) The repeating unit represented by these is mentioned.

[0091] General formula (4): [Chemical 10]

[0093] General formula [Chemical 12]

[0094] General formula

 [Chemical 13]

Υ、 ηは、上記一 般式（1)および（2)で記載したものと同じものを表わす。 In the above general formulas (4) to (7), M, ¹ to! ^ ² . ,

Υ and η are the same as those described in the above general formulas (1) and (2).

[0096] The repeating unit of the general formula (1) has a substituted or unsubstituted aryl including the substituent constituting the divalent group of the general formula (2), so that the dispersion force (δ) is increased. Is done. Medium d

 However, the force (δ) generated between the permanent dipoles of the molecule is increased by using a group having a halogen atom or a carbonyl group as 1 ^ to 1 ^ ° of the phenyl group. One more

 Ρ

As ^ ~Χ ⁴ of general formula (2), sulfides bond group, ether bond, urethane bond group, an amino-de-binding group, a carbonyl group, an ester group, an amino group, a substituted or unsubstituted alkylene group It is possible to increase δ and δ ρ of near-infrared absorbing materials by using

 It is. Since the near-infrared absorbing material of the present invention has the basic skeleton of the general formula (1), SP straight is 7.0 <δ <9.0, 0.1 <δ <5.5, 0.1 < δ <5.0. Also, the above one d p h

 Including the repeating units represented by the general formulas (4) to (7), the repeating unit represented by the general formula (1) has a divalent group represented by the general formula (2). When combined,! /, NA! /, And at least one benzene ring is substituted at the ortho position of the benzene ring, the solubility in a solvent is improved. Preferred examples of the substituent at the ortho position of the benzene ring include a halogen atom and an alkyl group having 1 to 20 carbon atoms such as a chlorine atom and a methyl group. In addition, when the substituent of the benzene ring is an alkoxy group or a mono- or di-substituted amino group, the divalent group represented by the general formula (2) is bonded to! / It is preferable to replace it with the place.

[0097] The SP of the near-infrared spring absorbing material is 7 · 0 <δ <9.00, 0.1 <δ <5.5, 0.1 <δ <5.

 d p h

By setting the value to 0, the SP value of near-infrared absorbing materials, resins, and solvents will be close, the solubility in the solvent and the compatibility with the resin will increase, the Haze value will decrease, and the light transmittance in the visible region will be high. 800nm ~; UOOnm near-infrared region can be cut efficiently, and high-intensity near-infrared absorption film, near-infrared absorption filter, etc. can be made. In this case, the solubility index in the solvent is 1. Owt% or more with respect to toluene, 0.2 wt% or more with respect to ethyl acetate, and 1. Owt% or more with respect to methyl ethyl ketone. If it is so soluble, it is possible to create a low Haze with less turbidity when it is mixed with a resin to make a film. If the solubility is lower than this, the film is opaque and has a high Haze, which is inappropriate for use in an optical filter or the like.

[0098] In the present invention, the polymer having the repeating unit represented by the general formula (1) may be a homopolymer or a copolymer. The copolymer may be a copolymer composed of two or more kinds of repeating units represented by the general formula (1), or the repeating unit represented by the general formula (1) and the general formula (1). And a copolymer containing a repeating unit not corresponding to the repeating unit represented by The copolymer may be a random, block, or graph copolymer. The copolysynthetic component other than the repeating unit represented by the general formula (1) is a compound having a polymerizable reaction end, for example, a small number of OH groups in the same molecule. Compounds with at least two, compounds with halogen and OH groups in the same molecule, compounds with multiple halogen groups in the same molecule, compounds with multiple COOH groups in the same molecule, COC1 group in the same molecule Multiple compounds, compounds with OH and COOH groups in the same molecule, compounds with multiple NH groups in the same molecule

 2

 And compounds having NH and COOH groups in the same molecule.

 2

 [0099] The weight-average molecular weight of the near-infrared absorbing material of the present invention is not particularly limited from the viewpoint of heat resistance and light resistance. For example, it is 1,000 to 10 in terms of polystyrene by gel permeation chromatography measurement. The power is preferably about 000.

 [0100] The near-infrared absorbing material represented by the general formula (1) of the present invention has an absorption region at 800 nm to 1, lOOnm, and therefore can be preferably used as a near-infrared absorbing material. Since the general formula (4) and the general formula (5) are structural isomers and can be used without distinction, either one of them may be used as a near-infrared absorbing material, or the structure without separation. It may be used as a mixture of isomers. Further, units having different near infrared absorption regions may be copolymerized as necessary, or polymers having different near infrared absorption regions may be mixed.

 [0101] The near-infrared absorbing material represented by the general formula (1) may be used in any combination of homopolymers. Further, the near-infrared absorbing material having the structure represented by the general formula (11) is used at the same time. It's okay. When using a near-infrared absorbing material having the structure represented by the general formula (11), a single structure may be used! /, Or a combination of different structures may be used.

 [0102] Table 1 specifically shows typical structural examples of the repeating unit represented by the general formula (1) used in the polymer which is the near-infrared absorbing material of the present invention. The repeating unit constituting the polymer of the material is not limited to the repeating unit shown in the following specific examples. Table 1 shows only the structure of each unit monomer, and does not show its polymerization form. Further, the structural isomers of the general formula (4) and the general formula (5) are representatively described by the repeating unit of the general formula (5).

[0103] [Table 1]

.9.S90/.00Zdf/X3d 83 t6S6蘭 OOZ OAV

P— 1 7

.9.S90 / .00Zdf / X3d 83 t6S6 orchid OOZ OAV

P— 1 7

P— 1 8

P— 1 9

P— 35 P—2 0

P— 35

P—3

P- 37

P- 38

P - 6 6

P-6 6

P-6

[0104] The near-infrared absorbing material having a repeating unit represented by the general formula (1) of the present invention can be produced, for example, according to the following synthesis scheme. In each formula, R ^{21 to} R ²⁴ are a phenyl group or a phenylene group which may be substituted with a substituent, Q is a part of the general formula (2),-[CH 2] -X ′ -Ar'-Y-Ar'-X ^3- [CH] Equivalent to one. The following synthesis

 2 n 2 n

Although there is no example of the polymer represented by the general formula (6) or the general formula (7) in the scheme, the polymer represented by the general formula (6) or the general formula (7) is also exemplified by, for example, a compound It can be produced in the same manner by using a compound in which one Br or one OH group of A or B is substituted with R ²¹ and R ²² or R ²¹ which is the same group. These synthesis schemes show only a part of the scheme for synthesizing the near-infrared absorbing material of the present invention, and the synthesis scheme of the near-infrared absorbing material of the present invention is limited to the following! Of course.

 [0105] The starting compounds A and B represented by the general formula in the synthesis scheme are, for example, Journal of

 American Chemical Society, 87: 7, April 5, 1965 or (by a method according to the synthesis method described in US Pat. No. 5,089,585).

 [0106] <Synthesis Scheme 1>

[Chemical 14]

 [0107] Synthesis Scheme 2>

[Chemical 15]

 [0108] <Synthesis Scheme 3>

 [Chemical 16]

 B

R ² V eo R ²³ —OOC- Q 卜 COO-

, 22, 24 to s

 R

[0109] <Synthesis Scheme 4>

[Chemical 17]

[0110] The synthesis in the above scheme is performed, for example, as follows.

 (Example of synthesis conditions)

 Under a nitrogen atmosphere, a base such as NaOH, KOH, KCO, NaCO, or triethylamine in a polar solvent such as dimethylformamide, dimethylsulfoxide, or methylethylketone, is equivalent to 2 to 50 equivalents, preferably 8 Equivalent to 20 equivalents containing Q with diol, diamine, diacid chloride, dibromide 40 ° C ~; 150 ° C, preferably 50 ° C ~; It is possible to synthesize compounds having repeating units of Remove the insoluble material by filtration and reprecipitation in alcohol such as methanol or ethanol.

 [0111] On the other hand, in the present invention, other near-infrared absorbing materials can be used as necessary together with the near-infrared absorbing material having the repeating unit represented by the general formula (1). As a near infrared ray absorbing material that can be particularly preferably used in the present invention, there is a near infrared ray absorbing material represented by the following general formula (11).

 [0112] General formula (11):

 [Chemical 18]

[In the formula, M ² represents a metal atom, R ⁵ ° to R ⁵ substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, Or a substituted or unsubstituted silyl group or a substituted or unsubstituted acyl group; The two Rs in the ligand may be bonded to each other to form a ring or may be a monovalent salt. )

[0114] In the near-infrared absorbing material represented by the general formula (11), the metal atom of M ² is not particularly limited as long as it is a metal atom, but nickel, cobalt, platinum, noradium or copper is preferable. More preferred is nickel.

[0115] For substituted or unsubstituted alkyl group of R ⁵ ° to R ⁵³ in the general formula (11), substituted or is not intended to be Yogu particularly limited as long as it is an alkyl group unsubstituted. The alkyl group may be linear, branched or cyclized cycloalkyl group. Specific examples of substituted or unsubstituted alkyl groups include methyl, ethyl, propyl, butyl, sec butyl, tert butyl, pentyl, hexyl, and 2-ethynole hexyl groups. , Heptyl group, octyl group, isooctyl group, stearyl group, trichloromethyl group, trifunoleolomethyleno group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexagenyl group, 2-cyclopentene-1-yl group 2, 4-cyclopentadiene 1 ylidyl group, benzyl group, phenethyl group, phenoxychtyl group, o methylbenzyl group, o chlorobenzyl group, etc., preferably butyl group, hexyl group, 2-ethynole group Linear and branched alkyl groups with about 3 to 20 carbon atoms such as hexyl groups, benzyl groups, phenethyl groups, o methylbenzyl groups, o Phenyl group-substituted alkyl group such as downy Njiru group, a phenoxy-substituted alkyl groups such as Fuenokishechiru group, more preferably those having a substituent at each phenyl group.

[0116] The substituted or unsubstituted aryl group of R ⁵ ° to R ⁵³ in the general formula (11) includes, for example, a phenyl group, a biphenylenyl group, a triphenylenyl group, a tetraphenylenyl group, and 3-nitrophenyl. Group, 4-methylthiophenenyl group, 3,5-disyanphenyl group, o-, m- and p trinole group, xylinole group, o-, m and p tamenyl group, mesityl group, pentalenyl group, indur group, Naphthyl, anthracenyl, azulenyl, heptaenyl, acenaphthylenyl, phenalenyl, fluorenyl, anthryl, anthraquinonyl, 3 methinoleanthrinol, phenanthrinole, pyrenyl, chrysinol, 2 -Chetinore 1-Chriseninole group, Piseninole group, Perireninole group, 6-clonal perireninole group, Pentafe Group, pentacenyl group, Tetorafue two Reniru group to, Kisafueniru group to, hexa Examples thereof include a senyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an ovalenyl group, and a substituted or unsubstituted phenyl group is preferable.

[0117] The substituted or unsubstituted heteroaryl group of R ⁵ ° to R ⁵³ in the general formula (11) includes, for example, thionyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyradyl group, pyrimidinyl Group, pyridazinyl group, indolyl group, quinolyl group, isoquinolinol group, phthalajur group, quinoxalinyl group, quinazolinyl group, carbazolyl group, attaridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, benzothiazyl group, phenothiazyl group Examples include a benzoxazolyl group, a benzimidazolyl group, a 2-methylpyridyl group, and a 3-cyanopyridyl group.

[0118] Examples of the substituted or unsubstituted silyl group of R ⁵ ° to R ⁵³ in the general formula (11) include triisopropyl silyl group, trimethylsilyl group, dimethylphenylsilyl group, tert-butyldimethylsilyl group dodecyldimethylsilyl group, etc. Is mentioned.

[0119] Examples of the substituted or unsubstituted Ashiru group R ⁵ ° to R ⁵³ in the general formula (11), Benzoi group, etc. Asechiru group.

 [0120] The monovalent salt in the general formula (11) has a structure represented by the following general formula (13).

 [0121] General formula (13):

 [Chemical 19]

[0122] (In the formula, any cation is represented, and M ² and R ⁵ ° to R ⁵³ are the same as defined in the general formula (11).)

[0123] In the general formula (13), X ⁺ is preferably a quaternary ammonium cation, a pyridinium cation, and a quaternary phosphonium cation. Examples of the quaternary ammonium cation include tetraethyl ammonium ion, tetraptyl ammonium ion, benzyltrimethyl ammonium ion, and pyridinium cation includes hexadecyl pyridinium. Examples include ureum cations and N-butyl-4-methylpyridinium ions, and quaternary phosphonium cations include, but are not limited to, tetrabutinorephosphonium ion, tripheninorepheptinorephosphonium ion, and tetraphenylphosphonium ion.

 [0124] Further, when taking a monovalent ionic structure, R in the same ligand is preferably a ring structure bonded to each other. Particularly preferred is CH 2 —CH 1.

 Examples of the near infrared absorbing material represented by the general formula (11) are shown in Table 2, but the near infrared absorbing material represented by the general formula (11) is not limited to the following.

[0125] [Table 2]

P P—

C ₄ Hg — SS I C4H9

C4H9 — S s 1 C ₄ Hg

 P P— 2

〇6Hi3― S _{s ς} S― C ₆ H ₁₃

 \ /

/ ^N

 C6H13―S S C6H- | 3

 P P— 3

C ₄ Hg (2H5) HCn2C― S s-, S— CH2CH (C2H5) C4H9 4 (2H5) HCri2C "" -s ss ss 3-, _s -CH2CH (C2Hs) C4H9

P P-4

 P P— 5

 P P— 6

F ₃ C (H ₂ C) ₄ — S, S- (CH ₂ ) ₄ CF ₃ F ₃ C (H ₂ C) _4. — S s— (CH ₂ ) ₄ CF ₃

 P P— 7

P P-8 PP-9

P P— 1 0

PP

PP

P P- 1 5

P P- 1 6

P P

P P

P P- 1 9

0 one d d

6 ε—d d

8 ε—d d

ε-d d

9 ε-d d

9 ε -a d

.9.S90 / .00Zdf / X3d 617 t6S6 orchid OOZ OAV PP-4

 P P— 4 2

Ni

, S 8 s no (C ₄ H ₉ ) ₄ P

 P P-4 3

 P P-4 4

[0126] Near-infrared absorbing materials represented by general formula (1) and general formula (11) (general formula (11) includes a near-infrared absorbing material represented by general formula (13)). When included at the same time, these may be included in any ratio, but a preferred ratio is a near infrared absorbing material represented by the general formula (1): a compound power represented by the general formula (11): 1 by weight ratio : 0.5-1: 5 is preferable. In this case, the near-infrared absorbing material represented by the general formula (1) “one ^ — [CH ² ] -X ²

 2 n

—A —Y—Ar ² — X ³ — [CH] —X ⁴ — ”is a divalent group represented by the general formula (11)

 2 η

 A co-compatibility effect occurs, and the near-infrared absorbing material represented by the general formula (1) is uniformly dispersed or dissolved in the resin. As a result, heat resistance and light resistance are improved.

 [0127] A near-infrared absorbing material having a repeating unit of the general formula (1), and the general formula

The composition containing the near-infrared absorbing material having the repeating unit of (1) can be used in any application that requires near-infrared absorption, and its usage mode and usage mode. However, the structure of the near infrared ray absorbing material is not limited. sand That is, the near-infrared absorbing material of the present invention is a near-infrared absorbing material (near-infrared absorbing dye) other than the near-infrared absorbing material containing the repeating unit structure of the above general formula (1), for example, the general formula It can be used together with auxiliary materials such as a near-infrared absorbing material represented by (11), other near-infrared absorbing materials, stabilizers such as ultraviolet absorbers and antioxidants. The near-infrared absorbing material of the present invention is dissolved in a solvent together with these auxiliary components or dispersed in a solvent or water, or if necessary, dissolved in a solvent together with a binder resin or the like, or dispersed in a solvent or water. The near-infrared absorbing layer can be formed by forming an absorbing composition and using it as a coating agent and applying it to a substrate or the like. Furthermore, if the binder resin is capable of forming a self-supporting film, for example, the composition is applied onto a peelable substrate to form a film, and then the film is removed from the peelable substrate. It can be peeled off and used as a near-infrared absorbing film. The coating agent referred to in the present invention is a processing material having near infrared absorptivity composed of a liquid composition or a paste-like composition containing a resin and / or an organic solvent or water. The coating agent of the present invention can be prepared by dissolving or dispersing the near-infrared absorbing material of the present invention in an appropriate coating agent. The coating agent of the present invention may be an oily coating agent or an aqueous coating agent.

Further, instead of forming the near-infrared absorbing layer as described above, the near-infrared absorbing material of the present invention is applied to other functional layers such as an adhesive or an adhesive layer, an ultraviolet absorbing layer, a hard coat layer, and a substrate. You may make it contain and give a near-infrared absorption characteristic to these layers. For example, in order to contain the near-infrared absorbing material of the present invention in an adhesive layer or an adhesive layer, a conventional known adhesive is added to the adhesive composition. There is a near-infrared ray-absorbing adhesive! /, To obtain an adhesive. This near-infrared-absorbing adhesive layer uses an adhesive to form a near-infrared-absorbing adhesive layer or adhesive layer. This layer may be used as a near infrared absorption filter layer. At this time, if necessary, the other components may be included. Further, if necessary, it can be contained in a molding resin to form a molded product having a near-infrared absorbing film! /. A laminate or a single film having a near-infrared absorbing layer containing the near-infrared absorbing material of the present invention is preferably used as an optical filter. [0129] As described above, in the near-infrared absorbing composition of the present invention, the near-infrared absorbing material of the present invention is made into a near-infrared absorbing composition together with a binder resin as necessary, and is applied onto a substrate. Thus, a layer containing a near-infrared absorbing material can be formed into a laminate. A laminated body can be used for an optical filter, an optical reflecting plate, an optical diffusion plate, etc., for example. In addition to the binder resin, other light-absorbing dyes such as other near-infrared absorbing materials represented by the general formula (11), stabilizers, solvents, adhesive resins, other auxiliary components, If necessary, the laminate layer may be formed by using components that form other functional layers.

 [0130] In the near-infrared absorbing composition of the present invention, when constituting an oil-based coating agent, the binder resin may be an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, An aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, a polybule resin, a polybulal alcohol resin, a polybulum modified resin, and a copolymer resin thereof can be exemplified. In the case of forming an aqueous coating agent, natural polymer materials such as gelatin, casein, starch, cellulose derivatives, and alginic acid are used. As the binder resin, an appropriate resin or copolymer may be selected depending on whether the coating agent is oily or aqueous. When using a near-infrared absorbing material as a coating agent, the glass transition temperature of these resins is preferably 80 ° C. or higher in view of the durability of the formed coating layer. In addition, when used as an adhesive, a glass transition temperature of room temperature or lower, for example, 0 ° C. or lower is desirable from the viewpoint of adhesive physical properties.

[0131] Further, examples of the organic solvent constituting the oil-based coating agent include halogen-based, alcohol-based, keton-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, Eutel-based solvents, and the like. Can be mentioned. On the other hand, as a method for preparing an aqueous coating agent, the near-infrared absorbing material of the present invention is pulverized to obtain fine particles of several micrometers or less, and the fine particles are placed in an uncolored acrylic polymer emulsion. A method of dispersal.

[0132] Examples of other light-absorbing dyes other than the near-infrared absorbing material represented by the general formula (11) include cyanine-based, quinoline-based, coumarin-based, thiazole-based, oxonol-based, azulene-based, squarylium. , Azomethine, azo, benzylidene, xanthene, lid opening Examples include cyanine-based, naphthalocyanine-based, naphthoquinone-based, anthroquinone-based, triphenylmethane-based, dimonium-based, and dithiol metal complex-based compounds.

 [0133] As the other light-absorbing dyes, nickel complex dyes and / or phthalocyanine dyes and / or dimonium dyes, which are near-infrared absorbing materials, are preferable. The addition amount of these other light-absorbing dyes to the near-infrared absorbing material of the present invention is preferably 20 to 500 parts by weight, more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the near-infrared absorbing material of the present invention. It is. In view of the absorption spectrum, it is preferable that the film has a visible light transmittance of 70 to 80% or more and a transmittance in the near infrared region of 10% or less.

 [0134] The nickel complex dye is preferably represented by the following general formula (8). Furthermore, the nickel complex dye may be an ionized compound with a monovalent cation.

[0135] General formula (8):

 [Chemical 20]

(In the formula, ⁹ to represents O or S or NR, R represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, and R 6 ° to R ⁶³ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group, and the substituents in the same ligand are bonded to each other to form a conjugated or non-conjugated ring. It may be formed.)

 [0137] The nickel complex dyes having the structure of the general formula (8) are specifically the following: American Dye Source, Ink (Laser Dyes & Near Infrared Dyes) d ADS845MC, ADS870MC, ADS880MC, ADS890MC, Examples include, but are not limited to, ADS920MC and A DS990MC.

[0138] Further, in the nickel complex dye having the structure of the general formula (8), near infrared absorptivity in which R ^{29 to} R ³² are all S, and R ⁶ ° to R ⁶³ are substituted phenyl groups An example of a dye Table 3 shows. These near-infrared absorbing dyes in Table 3 are dyes that may be formed as a by-product when synthesizing a near-infrared absorbing material having a repeating unit of the general formula (1) of the present invention. Therefore, even when a near-infrared absorbing dye represented by the general formula (8) is produced as a by-product when synthesizing a near-infrared absorbing material having a repeating unit of the general formula (1), Can be used as the near-infrared absorbing material of the present invention without separation

[Table 3]

.9.S90/.00Zdf/X3d Z9 t6S6蘭 OOZ OAV

一方、フタロシアニン系色素としては、下記一般式（9)で表されるものが好ましい。 一般式 (9):

.9.S90 / .00Zdf / X3d Z9 t6S6 orchid OOZ OAV

On the other hand, as the phthalocyanine dye, those represented by the following general formula (9) are preferable. General formula (9):

[Chemical 21]

[In the formula, M ¹ represents a metal atom, R ^{33 to} R ⁴⁸ each represents a hydrogen atom or a substituent, and M ¹ may further have a substituent.]

 [0142] Specific examples include, but are not limited to, IETC Color IR-10, IR-12, IR-14 manufactured by Nippon Shokubai Co., Ltd.

[0143] Further, the dye having a structure represented by the following general formula (10) is preferable as the dimonium dye. General formula (10):

[Chemical 22]

(In the formula, X— represents a halogen ion, an inorganic acid ion or an organic acid ion.)

[0144] In the general formula (10), examples of the X- halogen ion include iodine ion, chlorine ion, chlorine ion, and fluorine ion. Examples of inorganic acid ions include hexafluoroantimonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, and nitrate ion. Examples of the organic acid ion include acetate ion, trifluoroacetate ion, methanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion and the like. Examples of commercially available products include IRG-022, IRG-023, IRG-0 manufactured by Nippon Kayaku Co., Ltd. 40 and the like, but are not limited thereto.

[0145] Examples of the various stabilizers used for the purpose of stabilizing the near-infrared absorbing material of the present invention and the other light-absorbing dyes with respect to light or heat include, for example, hydride quinone derivatives. (See U.S. Pat. No. 3,935,016 and U.S. Pat. No. 3,982,944), Hydone quinone diether derivative (see U.S. Pat. No. 4,254,216), phenol derivative (see JP-A 54-21004), spiroindane or Derivatives of methylenedioxybenzene (see British Patent Application Publication No. 2077455, British Patent 2062888), Chroman, Spirochroman or Coumaran derivatives (US Pat. No. 3,432,300, US Pat. No. 3573050, US) Japanese Patent No. 3574627, US Patent No. 376 4337, Japanese Patent Laid-Open No. 52-152225, Japanese Patent Laid-Open No. 53-20327, Japanese Patent Laid-Open No. 53-17729, Japanese Patent Laid-Open No. 61-90156 Hydroquinone monoether or paraaminophenol derivatives (see British Patent 1347556, British Patent 2066 975, Japanese Patent Publication No. 54-12337, Japanese Patent Publication No. 55-6321), Bisphenol derivatives (See U.S. Pat. No. 3700455, Japanese Patent Publication No. 48-31625), Metal Complex (see U.S. Pat. No. 4245018, JP-A-60-97353), Nitroso Compound (JP-A-2-300288) And a diinmoyuum compound (see U.S. Pat. No. 4,656,12), a nickel complex (see JP-A-4 146189), and an antioxidant (see European Patent 820057). Further, the optical filter of the present invention may contain an aromatic nitroso compound, an aminium compound, an iminium compound, a bisiminium compound, a transition metal chelate compound, etc. as a quencher such as singlet oxygen. In the range that does not obstruct the effect of the infrared absorbing material, use a quencher anion such as a bisthiolate metal complex lanion.

 [0146] The addition amount of other light-absorbing dyes and various stabilizers to the near-infrared absorbing material of the present invention is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the near-infrared absorbing material of the present invention. More preferably 50 to 150 parts by weight. In view of the absorption spectrum, the ratio is preferably such that the visible light transmittance is 70 to 80% or more and the transmittance in the near infrared region is 10% or less when used as a film.

[0147] As described above, the near-infrared absorbing material of the present invention is not only a coating agent but also an adhesive or an adhesive. Can be used as power S. The coating agent of the present invention may contain additives such as ultraviolet absorbers and antioxidants. The use of the coating agent of the present invention is not particularly limited as long as it is intended for surface coating of a substrate. According to the coating agent of the present invention, a coating film having near infrared absorptivity is formed. Can do.

[0148] When the near-infrared absorbing composition of the present invention is used as an adhesive, an adhesive binder may be used as a solder. Examples of the adhesive binder include acrylic, urethane and rubber. As monomers that can be used as acrylics, acrylic monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2- Ethylhexenoyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octa nolate (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl ( (Meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, acrylate, icosyl (meth) acrylate, helicosyl (meth) acrylate, docosyl (meth) acrylate, (meth) acrylic acid And the like in the present invention. In view of securing adhesive properties, it is preferable to use an acrylic monomer having a carbon number of ~ 12 for copolymerization, and more preferably butyl (meth) acrylate, 2-ethylhexyl ( (Meta) Atallate, which can be used alone or in combination of two or more for the purpose of obtaining desirable physical properties as an adhesive.

 [0149] The weight average molecular weight (Mw) of an acrylic copolymer obtained by copolymerizing an acrylic monomer, an acrylic monomer having an alkylene oxide chain, and other monomers in the above adhesive binder is 50,000 to 100. A low molecular weight acrylic copolymer having a molecular weight of 50,000 to 200,000 is more preferable.

[0150] Further, the pressure-sensitive adhesive comprising the pressure-sensitive adhesive binder and the near-infrared absorbing material of the present invention is coated on the base material by a known method to form a pressure-sensitive adhesive sheet as a laminate. In addition to the base material described later, paper, metal, cloth, etc. are used as the base material used here. Adhesive sheet that does not require a base material if the adhesive binder power can be used alone It becomes. Moreover, the form by which an adhesive is coated on both surfaces of a base material may be sufficient. However, the pressure-sensitive adhesive on one side may not include the pressure-sensitive adhesive of the present invention.

 [0151] The pressure-sensitive adhesive comprising the pressure-sensitive adhesive binder and the near-infrared absorbing material of the present invention is coated on a substrate by a known method to form a pressure-sensitive adhesive sheet as a laminate. In addition to the base material described later, paper, metal, cloth, and the like are used as the base material used here. In addition, when the adhesive binder can form a sheet alone, it becomes an adhesive sheet that does not require a substrate. Moreover, the form by which an adhesive is coated on both surfaces of a base material may be sufficient. However, the case where the adhesive of one surface does not contain the adhesive of the present invention may be used.

 [0152] The addition amount of the near-infrared absorbing material of the present invention to the binder resin is preferably 0.0 to 20 parts by weight of the near-infrared absorbing material with respect to 100 parts by weight of the resin. Or 0.;! ~ 15 parts by weight. If this proportion is less than 0.01 parts by weight, light in the near-infrared region cannot be efficiently absorbed, whereas if it exceeds 20 parts by weight, the dispersibility of the near-infrared absorbing material can be reduced. Decreases and transparency (visible light transmission) is impaired.

 [0153] The adhesive in the present invention is a processed material having near infrared absorption comprising the near-infrared absorbing material and adhesive of the present invention. The adhesive of the present invention can be prepared by dissolving or dispersing the near-infrared absorbing material of the present invention in an appropriate medium having adhesiveness.

 [0154] As a configuration of the optical filter of the present invention, each layer such as an undercoat layer, an antireflection layer, a hard coat layer, and a lubricating layer may be provided on the substrate as necessary. Examples of the method of incorporating the near-infrared absorbing material of the present invention, the above other light-absorbing dyes and various stabilizers into the optical filter of the present invention include, for example, a method of incorporating a substrate or any arbitrary layer, a substrate Alternatively, a method for coating each arbitrary layer, a method for mixing with a polymer binder or adhesive between each layer, a pressure-sensitive adhesive, a method for providing a near-infrared absorbing layer containing the near-infrared absorbing material of the present invention separately from each of the above layers, etc. Is mentioned. The near-infrared absorbing material of the present invention is suitable for a method of mixing a polymer binder, adhesive, or pressure-sensitive adhesive between layers and a method of providing a near-infrared absorbing layer.

[0155] The amount of the near-infrared absorbing material of the present invention used per unit area of the optical filter; 000 mg / m ² , preferably 5 to 100 mg / m ² . If the amount used is less than lmg / m ² , the near-infrared absorption effect cannot be fully exerted, and if it is used over 1000 mg / m ² , the color of the filter becomes too strong and the display quality etc. This is not preferable because there is a possibility that the brightness may be lowered and the brightness may be lowered.

[0156] Examples of the material for the base material include inorganic materials such as glass; or, for example, diacetylenoresolerose, triacetinolecenerose (TAC), propionylcellulose, butyrinoresenorelose, and acetylenopro. Cenorelose ester such as pionorescenolose and nitrosenololose; polyamide; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polyethylene 1, 2 diphenoxetane 4, 4'-dicanoloxylate, polybutylene terephthalate, etc. Polyesterol of polystyrene; Polyolefins such as polyethylene, polypropylene, and polymethylpentene; Acrylic resins such as polymethylmetatalylate; Polycarbonate; Polyesterolone; Polyetherenolesnolephone; Polyetherenoketone Polyetherols Norre imide; polyoxypropylene polymeric materials such as ethylene and the like. For optical filter use, the substrate is preferably a transparent support. The transmittance of the transparent support is 80% or more, preferably S, and more preferably 86% or more. The haze is preferably 2% or less, more preferably 1% or less. The refractive index is preferably 1.45-1.70.

 [0157] In these base materials, a light-absorbing dye, an antioxidant, a light stabilizer, an ultraviolet absorber, organic fine particles, and the like can be added. The power can be applied.

 [0158] Examples of the inorganic fine particles include inorganic fine particles such as silicon dioxide, titanium dioxide, barium sulfate, calcium carbonate, talc, and kaolin.

[0159] Examples of the various surface treatments 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.

[0160] The undercoat layer is a layer used between the base material and the near-infrared absorbing layer when the near-infrared absorbing layer containing the near-infrared absorbing material of the present invention is provided. The undercoat layer is made of glass It is formed as a layer containing a polymer having a transition temperature of −60 to 60 ° C., a layer having a rough surface on the near infrared absorbing layer side, or a layer containing a polymer having affinity with the polymer of the near infrared absorbing layer. An undercoat layer is provided on the surface of the base material on which the near-infrared absorbing layer is not provided to improve the adhesive force between the base material and the layer provided thereon (for example, an antireflection layer or a hard coat layer). The undercoat layer may be provided to improve the affinity between the optical filter and the adhesive for attaching the optical filter and the image forming apparatus. The thickness of the undercoat layer is preferably 2ηιη to 20〃ιη force S, more preferably 5nm to 5〃m force S, more preferably 20nm to 2〃m force, more preferably 501 111 to 1 カ 111, more preferably 80nm to 300nm. Most preferred. The undercoat layer containing a polymer having a glass transition temperature of −60 to 60 ° C. adheres the base material and the near-infrared absorbing layer due to the adhesiveness of the polymer. Polymers having a glass transition temperature of 60 to 60 ° C include, for example, butyl chloride, vinylidene chloride, butyl acetate, butadiene, neoprene, styrene, black-prene, acrylic ester, methacrylic ester, acrylonitrile or methyl butyl ether. It can be obtained by polymerization or copolymerization thereof. The glass transition temperature is preferably 50 ° C or lower, more preferably 40 ° C or lower, more preferably 30 ° C or lower, and further preferably 25 ° C or lower. Further, it is most preferably 20 ° C or less. The elastic modulus at 25 ° C of the undercoat layer is preferably 1 to 1 OOOMPa, more preferably 5 to 800 MPa, and even more preferably 10 to 500 MPa. The undercoat layer having a rough surface adheres the base material and the near-infrared absorbing layer by forming a near-infrared absorbing layer on the rough surface. The undercoat layer having a rough surface can be easily formed by applying a polymer latex. The average particle size of the latex is preferably 201 111 to 3 111, and more preferably 501 111 to 1 111. Examples of the polymer having an affinity for the binder polymer of the near-infrared absorbing layer include acrylic resins, cellulose derivatives, gelatin, casein, starch, polybutyl alcohol, soluble nylon, and polymer latex. In the optical filter of the present invention, two or more undercoat layers may be provided. In the undercoat layer, a solvent that swells the substrate, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like may be added.

In the antireflection layer, a low refractive index layer is essential. Refractive index of the low refractive index layer Is lower than the refractive index of the transparent support. The refractive index of the low-refractive index layer is 1.20 to 1.55. The force S is preferable, and 1.30 to 1.50 is more preferable. The thickness of the low refractive index layer is preferably 50 to 400 nm, more preferably 50 to 200 nm. The low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Laid-Open Nos. 57-34526, 3-130103, 6-115023, 8-313702, 7-168004). Layers described in JP-A-5-208811, JP-A-6-299091, and JP-A-7-168003), or layers containing fine particles (JP-B-60-59250) And JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, and JP-A-9-288201). In the layer containing fine particles, voids can be formed in the low refractive index layer as microvoids between the fine particles or within the fine particles. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, more preferably 5 to 35% by volume.

In order to prevent reflection in a wide wavelength region, in the antireflection layer, in addition to the low refractive index layer, a layer having a high refractive index (medium ′ high refractive index layer) is preferably laminated. The refractive index of the high refractive index layer is preferably 1.65-2.40, more preferably 1 · 70 to 2 · 20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is 1.50 to 1.90, preferably S, more preferably 1.55 to 1.70. The thickness of the medium / high refractive index layer is preferably 51 111 to 100 111, more preferably lOnm lO ^ m, and most preferably 301 111 to 1 111. The haze of the medium / high refractive index layer should be 5% or less. S is preferable, and 3% or less is more preferable, and 1% or less is most preferable. The medium'high refractive index layer can be formed using a polymer binder having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. It is Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents also have a high refractive index. Use a polymer formed by the polymerization reaction of a monomer that allows radical curing by introducing a double bond That's it.

 [0163] In order to obtain a higher refractive index, inorganic fine particles may be dispersed in the polymer binder. The refractive index of the inorganic fine particles is 1.80-2.80. The inorganic fine particles are preferably formed from metal oxides or sulfides. Examples of metal oxides or sulfides include titanium oxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Among these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The inorganic fine particles are mainly composed of oxides or sulfides of these metals, and can further contain other elements. Here, the main component means a component having the largest content (% by weight) among the components constituting the inorganic fine particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. In addition, inorganic materials that are film-forming and can be dispersed in a solvent or are themselves liquid, such as alkoxides of various elements, salts of organic acids, and coordination compounds bonded to coordination compounds (eg, chelate compounds). ), An active inorganic polymer or the like can be used to form a middle-high refractive index layer.

 [0164] The surface of the antireflection layer can be provided with an antiglare function (function of scattering incident light on the surface and preventing the scenery around the film from moving to the film surface). For example, by forming fine irregularities on the surface of the transparent film and forming an antireflection layer on the surface, or forming an antireflection layer on the surface and then forming irregularities on the surface with an embossing roll, antiglare An antireflection layer having a function can be obtained. An antireflection layer having an antiglare function generally has a haze of 3 to 30%.

[0165] The hard coat layer has a hardness higher than that of the transparent support. The hard coat layer preferably contains a crosslinked polymer. The hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (for example, an ultraviolet spring curable resin). In addition, a hard coat layer is formed from a silica-based material.

[0166] A lubricating layer may be formed on the surface of the antireflection layer (low refractive index layer). The lubricating layer has a function of imparting slipperiness to the surface of the low refractive index layer and improving scratch resistance. Lubrication layer is polio It can be formed using luganosiloxane (for example, silicone oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or derivative thereof. The thickness of the lubricating layer is preferably 2 to 20 nm.

 [0167] The near-infrared absorbing layer, undercoat layer, antireflection layer, hard coat layer, lubricating layer and the like can be formed by a general coating method. Application methods include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and etatrusion coating using a hopper (described in US Pat. No. 2681294). Etc. Two or more layers may be formed by simultaneous application. The same day temple application method ί KOTSULE (May, U.S. Patents 2761791, 2941898, 3508947, 3526528 and Yuji Harasaki "Coating Engineering", page 253 (published by Asakura Shoten in 1973) There is a description.

 [0168] By using the optical filter of the present invention, visible rays of sunlight can be effectively transmitted and heat rays can be cut reliably. In addition, because of its excellent durability, the ability to block heat rays is not impaired even when exposed to sunlight for a long time.

 [0169] The optical filter of the present invention can be suitably used as a visibility correction filter for a CCD (for example, a photoelectric conversion element made of a silicon photodiode) in an imaging apparatus (image input apparatus). Here, “Visibility correction filter for CCD” includes a lid, a lens, a protective plate, etc., in addition to a visibility correction filter arranged alone in the optical path to the CCD. Examples of imaging devices equipped with CCDs include video cameras, digital cameras, board cameras, color scanners, color fax machines, color copiers, and color videophones. According to the imaging device including the optical filter of the present invention, the incident light to the CCD (silicon photodiode) can be substantially limited to light in the visible region. As a result, accurate photometry ( (Exposure operation) can be performed, and the reproduction of the red component is not hindered.

The optical filter according to the present invention can be suitably used as a visibility correction filter for an imaging device (image input device) equipped with a CMOS image sensor or an artificial retina. According to the CMOS image sensor and artificial retina equipped with the optical filter of the present invention, and an imaging device including these, the same effects as those of the above-described CCD can be obtained. ¾] Can play fruit.

 [0171] The optical filter of the present invention can be suitably used as a noise cut filter in an environment where an infrared communication device (communication device using light of 850 to 950 nm as a medium) is used. According to the noise-cutting filter, the near infrared source (for example, a machine using near infrared rays such as an automatic door and a remote controller) is covered, and the infrared ray from the source is cut off, so that Generation of noise can be surely prevented.

 [0172] Further, by arranging the optical filter of the present invention in front of the panel of the plasma display device or the liquid crystal panel display device, it is possible to efficiently cut near infrared rays emitted from the panel. As a result, there will be no malfunction of the remote control caused by near-infrared rays around the display device!

 [0173] In recent years, resin molded products are frequently used as parts in various fields such as automobile parts from the viewpoint of weight reduction and cost reduction. Further, from the viewpoint of increasing the productivity of the resin molded product, a method is often employed in which the resin molded product is divided into a plurality of parts in advance and these divided molded products are joined to each other. Conventionally, the resin materials are joined by overlapping a transparent resin material that is transmissive to the laser and an absorbent resin material that is permeable to the laser, and then from the transparent resin material side. This is performed by a laser welding method in which the contact surfaces of the permeable resin material and the absorbent resin material are heated and melted by irradiating a laser, and the two are integrally bonded. In the conventional laser welding method, when joining the same or different types of resin members, there are two types of resin members to be joined: those that absorb the laser and those that do not absorb the laser. There was a difference, and there was a limit to the intended use of the joined resin members. Specifically, resin materials that are non-absorbing to the laser are white or transparent laser-transmitting colors, and the absorbing members are black laser-absorbing colors such as carbon black. It was supposed to occur. That is, when such resin materials of different colors are joined, the apparent joining force is felt weak and the joints are conspicuous.

[0174] If the material of the present invention is used, the laser that has passed through the permeable resin material reaches the contact surface of the absorbent resin material and is absorbed, and the laser absorbed in this contact surface accumulates as energy. Is done. As a result, the contact surface of the absorbent resin material is heated and melted, and this absorption is performed. The heat transfer from the contact surface of the absorptive resin material heats and melts the contact surface of the permeable resin material. In this state, if the contact surfaces of the permeable resin material and the absorbent resin material are pressure-bonded to each other, they can be joined together. Since this material has good visible light transmittance, it can reduce the color tone difference from the laser-transmissible resin material and has a large molar extinction coefficient in absorption in the near-infrared region. The resin composition having sufficient bonding strength can be provided by reliably welding the contact surfaces of the permeable resin material and the absorbent resin material.

 [0175] Recently, as a method of performing marking easily and efficiently, marking by laser light irradiation has been actively performed. This marking method by laser light irradiation is such that characters or illustrations that are irradiated with laser light are discolored by heat energy, and characters and illustrations can be identified by light scattering.

 [0176] For example, in JP-A-9-302236, laser marking is possible by irradiating a resin composition comprising a leuco dye, a color-forming auxiliary component and a thermoplastic resin with a laser beam after molding. It is disclosed. However, since the reaction of the coloring component occurs due to heat during kneading, the coloring component is limited and the degree of freedom in coloring is restricted. Japanese Patent Application Laid-Open No. 11 92632 discloses a technique for performing laser marking on the surface of a resin molded product by irradiating an epoxy resin containing a copper compound and a nickel compound as a color former with laser light. In this case, the marking is limited to black. Japanese Patent Application Laid-Open No. 8-120133 discloses a resin composition capable of chromatic laser marking in which a compound such as titanium black is blended with a rubber reinforced bull-based resin. It is limited to Bull resin and its application development is limited.

 [0177] The near-infrared absorbing material of the present invention has high! /, Visible light transmittance and high! /, And near-infrared absorbing ability, so that it can be marked with a low-power active energy ray and is used for highly transparent marking. A composition can be provided. In addition, clear, high-speed and high-precision characters and illustrations can be easily and quickly marked.

[0178] Furthermore, LEDs are currently used in various fields in RGB three colors with high efficiency and high brightness. However, it generates a relatively large amount of energy but generates a heat source. The diode equipment has the problem that it is always exposed to high temperatures. The cause of heat generation is due to the radiant heat and infrared generation of the diode. The near-infrared absorbing material of the present invention is excellent in near-infrared absorbing ability and has high visible light transparency, so that infrared rays can be cut without changing the emission color of the LED. In addition, because it has high heat resistance and high light resistance, the near-infrared absorption ability will not deteriorate even if this material is used for LEDs for a long time. If the near-infrared absorbing material of the present invention is used, heat generation due to light emission of the diode can be suppressed.

 [0179] The optical filter of the present invention is preferably arranged as a display filter or a filter for a CCD or CMOS image sensor, and its arrangement method is not limited at all.

 Example

 [0180] The present invention is described in detail below with reference to production examples and examples. However, the present invention is not limited in any way by the following examples.

[0181] [Production Example 1] Synthesis of Compound 1

 [Chemical 23]

[0182] In a four-necked flask under a nitrogen stream, 2 ', 5'-dimethylphenyldioxal, (70 g,

 388 mmol), (2-bromoethinole) benzene (72 g, 388 mmol), and dichloroethane 500 ml were charged, and titanium tetrachloride (110 g, 583 mmol) was slowly added dropwise thereto, followed by stirring at room temperature for 3 hours. After completion of the reaction, water was added for extraction, evaporation was performed, and recrystallization was performed with hexane. Yield 60%.

 [0183] [Production Example 2] Synthesis of Compound 2

[Chemical 24]

[0184]

 200 ml of oxane was added to the four-necked flask and refluxed for 2 hours under a nitrogen atmosphere. After the reaction, filtration was performed, and an aqueous solution of NiCl · 6Η0 (111.2 g, 47 mmol) was added to the filtrate, followed by re-refluxing for 2 hours. After completion of the reaction, water and methanol were added and stirred for a while, followed by filtration and collection. Yield 45%.

 [0185] [Production Example 3] Synthesis of P-1

 [Chemical 25]

製造列 2で合成したィ匕合物 2 (0. 9g、 1. 06mmol)と 2, 2—ビス（4ーヒドロキシー 3 , 5ージクロ口フエ二ノレ）プロノ ン（0. 388g、 1. O6mmol)および K C〇 ( 1. 16g、 8.

Compound 2 (0.9 g, 1.06 mmol) synthesized in production sequence 2, 2,2-bis (4-hydroxy-3,5-dichlorodiphenyl) pronone (0.388 g, 1. O6 mmol) and KC〇 (1.16g, 8.

44 mmol) and 40 ml of DMF were added to a four-necked flask and stirred at 80 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, filtration and evaporation were carried out, and the resulting solution was dropped into a water / methanol = 1/2 solution and washed. The target product was recovered by filtration. Yield 68%. [0187] [Production Example 4] Synthesis of Compound 3

 [Chemical 26]

[0188] Compound 3 was synthesized in the same manner as in Production Example 1 except that phenyldalixal was used as a raw material. Yield 46%.

[0189] [Production Example 5] Synthesis of Compound 4

 [Chemical 27]

 Compound 4

[0190] Compound 3 synthesized in production line 4 (3.0 g, 9.4 mmol), pentalith) ¾¾lin (12. 53 g, 28.2 mmol) dioxane 50 ml in a four-necked flask In addition, it was refluxed for 2 hours in a nitrogen atmosphere. After the reaction, filtration was performed, and an aqueous solution of NiCl · 6Η0 (1.12 g, 4.7 mmol) was added to the filtrate, followed by refluxing again for 2 hours. After completion of the reaction, water and methanol were added and stirred for a while, followed by filtration and collection. Yield 45%.

 [0191] [Production Example 6] Synthesis of P-21

[Chemical 28]

[0192] P-21 was synthesized by the same method as in Production Example 3 except that Compound 4 and bishydroxyphenylcyclohexane were used. Yield 80%

[0193] [Production Example 7] Synthesis of P-2

 Synthesis was carried out according to the method of Production Example 3 except that 1,2-bis [2 (4-hydroxyphenyl) 2-propyl] benzene was used in place of 2,2bis (4-hydroxy-3,5 dichlorophenyl) propane. Yield 70%.

 [0194] [Production Example 8] Synthesis of P-4

[0195] Synthesis was carried out according to the method of Preparation Example 3 except that 4-4 '-(1,3-dimethylbutylidene) diphenol was used in place of 2,2bis (4-hydroxy-3,5 dichroic phenyl) propane. Yield 75%.

 [Production Example 9] Synthesis of Compound 5

 [Chemical 29]

[0197] Synthesis was carried out according to the method of Production Example 1 except that [N- (2 promoethyl) N eth / le] dilin was used instead of (2 bromoethynole) benzene. Yield 43%.

[0198] [Production Example 10] Synthesis of Compound 6 [Chemical 30]

[0199] Compound 6 was synthesized in the same manner as in Production Example 2 except that compound 5 was used instead of compound 1. Yield 41%.

[0200] [Production Example 11] Synthesis of P-6

 [Chemical 31]

[0201] Synthesis was performed in the same manner as in Production Example 3, except that 1,3-bis [2 (4-hydroxyphenyl) -2-propyl] benzene and Compound 6 were used. Yield 77%.

 [0202] [Production Example 12] Synthesis of Compound 7

 [Chemical 32]

H_SB「 化合物 7 ジメチルフエニルダリオキサールの代わりに O—メチルフエニルダリオキサ ールを用いる以外製造例 1と同様の方法にて化合物 7を合成した。収率 63%

H _S B “Compound 7 O-methylphenyldaroxax instead of dimethylphenyldarixal Compound 7 was synthesized in the same manner as in Production Example 1 except that the above method was used. Yield 63%

 [0204] [Production Example 13] Synthesis of Compound 8

 [Chemical 33]

[0205] Compound 8 was synthesized in the same manner as in Production Example 2, except that compound 7 was used instead of compound 1. Yield 20%.

[Production Example 14] Synthesis of Compound 9

 [Chemical 34]

[0207] Compound 9 was synthesized in the same manner as in Production Examples 12 and 13, except that o-chlorophenyl dalixal was used in place of o-methyl phendial oxal. Yield 36%

 [Production Example 15] Synthesis of compounds 10 to 12

[Chemical 35]

 Compound 1 0 Compound

 Compound 1 2

[0209] Compound 10 (Yield 23%), Compound 11 (Yield) were prepared in the same manner as in Production Examples 1-2 and 12-14 except that phenylpropyl bromide was used instead of (2-bromoethyl) benzene. 29%) and compound 12 (yield 33%) were synthesized.

[0210] [Production Example 16] Synthesis of P-22

 P-22 was synthesized in the same manner as in Production Example 3 except that compound 8 was used instead of compound 2. Yield 85%.

[0211] [Production Example 17] Synthesis of P-23

 P-23 was synthesized in the same manner as in Production Example 3 except that Compound 9 was used instead of Compound 2. Yield 82%.

[0212] [Production Example 18] Synthesis of P-24

 P-24 was synthesized in the same manner as in Production Example 3 except that Compound 10 was used instead of Compound 2. Yield 85%.

[0213] [Production Example 19] Synthesis of P-25

 P-25 was synthesized in the same manner as in Production Example 3 except that Compound 11 was used instead of Compound 2. Yield 80%.

[0214] [Production Example 20] Synthesis of P-26

 P-26 was synthesized in the same manner as in Production Example 3 except that Compound 12 was used instead of Compound 2. Yield 81%.

[0215] [Production Example 21] Synthesis of P-27 P-27 was synthesized in the same manner as in Production Example 11 except that Compound 8 was used instead of Compound 6. Yield 78%.

[0216] [Production Example 22] Synthesis of P-28

 P-28 was synthesized in the same manner as in Production Example 11 except that Compound 9 was used instead of Compound 6. Yield 79%.

[0217] [Production Example 23] Synthesis of P-29

 P-29 was synthesized in the same manner as in Production Example 11 except that compound 10 was used instead of compound 6. Yield 90%.

[0218] [Production Example 24] Synthesis of P-30

 P-30 was synthesized in the same manner as in Production Example 11 except that Compound 11 was used instead of Compound 6. Yield 84%.

[0219] [Production Example 25] Synthesis of P-31

 P-31 was synthesized in the same manner as in Production Example 11 except that compound 12 was used instead of compound 6. Yield 81%.

[0220] [Production Example 26] Synthesis of P-32

 In Production Example 11, compound 8 was used instead of compound 6, and the same procedure except that bis (2-methyl 4-hydroxyphenol) sulfide was used instead of 1,3-bis [2 (4-hydroxyphenyl-2-propinole) benzene. P-32 was synthesized. Yield 82%.

[0221] [Production Example 27] Synthesis of P-33

 In Preparation Example 11, compound 9 was used instead of compound 6, and the same procedure was performed except that bis (2-methyl 4-hydroxyphenyl) sulfide was used instead of 1,3-bis [2 (4-hydroxyphenyl-2-propinole) benzene. P-33 was synthesized. Yield 87%.

[0222] [Production Example 28] Synthesis of P-34

 In Production Example 11, Compound 8 is used instead of Compound 6, and 4, 4 '-(1, 3-dimethylbutylidene) diphenol instead of 1,3-bis [2 (4-hydroxyphenyl-2-propinole) benzene. P-34 was synthesized in the same manner except that was used. Yield 89%.

[0223] [Production Example 29] Synthesis of P-35

In Production Example 11, instead of Compound 6, Compound 9 was replaced with 1, 3-bis [2 (4-hydroxyphen P-35 was synthesized in the same manner except that 4,4 '-(1,3 dimethylbutylidene) diphenol was used instead of benzene-2-propynole) benzene. Yield 80%.

[0224] [Production Example 30] Synthesis of P-36

 In Production Example 11, compound 10 is used instead of compound 6, and 4,4 '-(1,3-dimethylbutylidene) diphenol instead of 1,3-bis [2 (4 hydroxyphenol 2-propinole) benzene. P-36 was synthesized in the same manner except that was used. Yield 83%.

[0225] [Production Example 31] Synthesis of P-37

 In Production Example 11, Compound 11 was substituted for Compound 6, and 4,4 '-(1,3-Dimethylbutylidene) diphenol instead of 1,3-bis [2 (4 hydroxyphenol 2-propinole) benzene P-37 was synthesized in the same manner except that was used. Yield 85%.

[0226] [Production Example 32] Synthesis of P-38

 In Production Example 11, Compound 12 was replaced with Compound 6, and 4, 4 ′-(1, 3-dimethylbutylidene) diphenol instead of 1,3-bis (2 (4 hydroxyphenol 2-propinole) benzene. P-38 was synthesized in the same manner except that was used. Yield 81%.

[0227] [Production Example 33] Synthesis of P-39

 In Production Example 11, compound 2 is used instead of compound 6, and 2,2,1bis (4hydroxyphenyl) hexafluoropropane is used instead of 1,3-bis [2 (4 hydroxyphenyl-2-propinole) benzene. P-39 was synthesized in the same manner as above. Yield 78%.

[0228] [Production Example 34] Synthesis of P-42

 In Production Example 11, compound 2 was used instead of compound 6, and 2,2,1-bis (4hydroxy-1,3,5 dimethylphenyl) propane was used instead of 1,3-bis [2 (4 hydroxyphenyl-2-propynole) benzene. P-42 was synthesized in the same manner except that it was used. Yield 75%.

[Production Example 35] Synthesis of Compound 13

化合物 1 3 [Chemical 36]

Compound 1 3

[0230] In Production Example 1, instead of (2-bromoethyl) benzene, N- (3 bromopropyl)

) Synthesis was carried out in the same manner except using aniline! /, And the resulting product was used in place of Compound 1 and synthesized according to Preparation Example 2 to obtain Compound 13. Yield 15%.

[0231] [Production Example 36] Synthesis of P-46

 It was synthesized in the same manner as in Production Example 11 except that Compound 13 was used instead of Compound 6!

P-46 was obtained. Yield 67%.

[0232] [Production Example 37] Synthesis of Compound 14

 [Chemical 37]

化合物 1 4 製造例 9において、 [N— (2 ブロモェチル）—N ェチル]ァニリンの代わりに [N 一（3 ブロモプロピル） N—プロピノレ]ァニリンを、 2，， 5，ージメチルフエニルダリオ キサールの代わりに o メチルフエニルダリオキサールを用いた以外同様に合成を行 つた。生成物を化合物 5の代わりに用いた以外製造例 10と同様の方法で化合物 14 を合成した。収率 22%。

Compound 1 4 In Production Example 9, instead of [N— (2 bromoethyl) -N ethyl] aniline, [N mono (3 bromopropyl) N-propynole] aniline was replaced with 2,5, -dimethylphenyldioxal. The synthesis was carried out in the same way except that o-methylphenyldioxal was used instead. Compound 14 was prepared in the same manner as in Production Example 10 except that the product was used in place of Compound 5. Was synthesized. Yield 22%.

 [0234] [Production Example 38] Synthesis of P-47

 P was synthesized in the same manner as in Production Example 11 except that Compound 14 was used instead of Compound 6. Yield 78%.

 [Production Example 39] Synthesis of Compound 15

 [Chemical 38]

[0236] Compound 15 was synthesized in the same manner as in Production Example 37 except that 4-methoxyphenylglyoxal was used in place of black-mouthed phenyloxal.

[0237] [Production Example 40] Synthesis of P-48

 Compound 15 (20 mmol), bishydroxydiphenylmethane (2 ImmoL K 2 CO 2 210 mmol) were heated and stirred at 80 ° C. in DMF under nitrogen atmosphere. Filtration was performed after completion of the reaction, and the filtrate was added dropwise to 2 L of water, and the precipitate was filtered to recover P-48. Yield 75%.

 [0238] [Production Example 41] Synthesis of P-56

 P-56 was synthesized in the same manner as in Production Example 3 using Compound 2 (20 mmol), Compound 6 (20 mmol) and 1,3 bis [2 (4 hydroxyphenyl) 2 propyl] benzene (20 mmol). Yield 67%

 [0239] [Production Example 42] Synthesis of P-59

 Compound 2 (15 mmol), 2, 2, 1bis (4 hydroxy-1,3,5 dimethylphenol) propan (15 mmol), Compound 13 (15 mmol), 1,3 bis [2 (4 hydroxyphenyl) 1 2 — Propyl] benzene (15 mmol) and K 2 CO 2 (200 mmol) in DMF under nitrogen atmosphere

 twenty three

The mixture was heated and stirred at 80 ° C. After completion of the reaction, filtration is performed, and the filtrate is dropped into 2 L of water. The precipitate was filtered and P-59 was recovered. Yield 73%

[0240] [Production Example 43] Synthesis of P 60

 Compound 12 (15mmol), Compound 14 (15mmol), 1,3bis [2 (4hydroxyphenol) 2-propyl] benzene (30mmol), and K 2 CO 3 (300mmol) in nitrogen atmosphere

 twenty three

 In the lower DMF, the mixture was heated and stirred at 80 ° C. After completion of the reaction, filtration was performed, and the filtrate was added dropwise to 3 L of water, and the precipitate was filtered to recover P-60. Yield 83%

[0241] [Production Example 44] Synthesis of P-61

 Compound 10 (15 mmol), Compound 15 (15 mmol), Tetrachloro-bis bisphenol A (15 mmol), Bishydroxydiphenylmethane (15 mmol) and K 2 CO 3 (300 mmol) were nitrogenated.

 twenty three

 The mixture was heated and stirred at 80 ° C in DMF under atmosphere. After completion of the reaction, filtration is performed, and the filtrate is washed with water.

2. Dropped into 5 L and filtered the precipitate to recover P-61. Yield 85%

[0242] [Production Example 45] Synthesis of P-62

 2, 2 instead of bis (4-hydroxy 3, 5 dichroic mouth)

Synthesis was carried out according to the method of Production Example 3 except that 2 ethylhexylidene) diphenol was used. Yield 75%

[0243] [Production Example 46] Synthesis of P-64

 2, 2 instead of bis (4-hydroxy 3, 5 dichroic mouth)

2-Ethylhexylidene) diphenol was used, and P-64 was synthesized according to the method of Preparation Example 3 except that compound 12 was used instead of compound 2. Yield 79%

[0244] [Production Example 47] Synthesis of PP 1

[Chemical 39]

窒素雰囲気下、メタノール 500ml中でテトラチアペンタレン 2, 5 ジオン（5. 0g 2 4mmol)を撹拌しているところに、 20°Cにてナトリウムメトキシド（2· 6g、 48mmol)を 加え、 90分撹拌した。そこへ 1 ブロモブタン（6. 6g、 48mmol)滴下し、 4時間反応 させた。そこへさらにナトリウムメトキシド（2. 6g、 48mmol)を加え、 2時間撹拌後、 Ni CI 6H 0 (2. 9g、 2. 9mmol)を 50mlメタノールに溶かした溶液をゆっくり滴下した。 さらに 4時間撹拌し、テトラエチルアンモニゥムブロマイドを 3· Ommol加え、空気をバ ブリングしながら 1時間撹拌した。得られたバルタをろ過してアセトン 300mlに溶かし 、 100mlに溶力もた I (6mmol)を滴下した。 1時間撹拌すると緑色の沈殿が生じ、ろ

Tetrathiapentalene 2,5 dione (5.0 g 2) in 500 ml of methanol under nitrogen atmosphere 4 mmol) was stirred, sodium methoxide (2.6 g, 48 mmol) was added at 20 ° C., and the mixture was stirred for 90 minutes. 1 Bromobutane (6.6 g, 48 mmol) was added dropwise thereto and reacted for 4 hours. Sodium methoxide (2.6 g, 48 mmol) was further added thereto, and after stirring for 2 hours, a solution of Ni CI 6H 0 (2.9 g, 2.9 mmol) dissolved in 50 ml methanol was slowly added dropwise. The mixture was further stirred for 4 hours, 3 · Ommol tetraethylammonium bromide was added, and the mixture was stirred for 1 hour while bubbling air. The obtained Balta was filtered and dissolved in 300 ml of acetone, and I (6 mmol) having a solvent power was added dropwise to 100 ml. After stirring for 1 hour, a green precipitate forms and

 2

 I went over. The filtrate was recrystallized with a solution of black mouth form / methanol = 6: 4 to obtain PP-1. Yield 44%.

[0246] [Production Example 48] Synthesis of PP-2

 1 PP-2 was synthesized in the same manner as in Production Example 47 except that 1-bromohexane was used instead of 1 bromobutane. Yield 35%.

[0247] [Production Example 49] Synthesis of PP-3

 1 PP-3 was synthesized in the same manner as in Production Example 47 except that 1-bromo-2-ethylhexane was used instead of 1 bromobutane. Yield 45%.

[0248] [Production Example 50] Synthesis of PP-5

 PP-5 was synthesized in the same manner as in Production Example 47, except that 1-bromo-4 trifluorobutane was used instead of 1 bromobutane. Yield 41%.

[0249] [Production Example 51] Synthesis of PP-8

 1 PP-8 was synthesized in the same manner as in Production Example 47 except that bromomethylcyclohexane was used instead of bromobutane. Yield 31%.

[0250] [Production Example 52] Synthesis of PP-10

 PP-10 was synthesized in the same manner as in Production Example 47, except that 1-bromo-2-ethoxyethane was used instead of 1-bromobutane. Yield 31%.

[0251] [Production Example 53] Synthesis of PP-11

 PP-11 was synthesized in the same manner as in Production Example 47 except that trimethylsilyl chloride was used in place of 1-bromobutane. Yield 51%.

[0252] [Production Example 54] Synthesis of PP-14 1 PP-14 was synthesized in the same manner as in Production Example 47 except that (2 bromoethyl) benzene was used instead of bromobutane. Yield 33%.

[0253] [Production Example 55] Synthesis of PP-15

 1 PP-15 was synthesized in the same manner as in Production Example 47 except that benzyl bromide was used instead of bromobutane. Yield 48%.

[0254] [Production Example 56] Synthesis of PP-16

 1 16-16 was synthesized in the same manner as in Production Example 47 except that α-bromo-o-xylene was used instead of bromobutane. Yield 42%.

[0255] [Production Example 57] Synthesis of ΡΡ-17

 1 PP-17 was synthesized in the same manner as in Production Example 47 except that α-bromo-m-xylene was used instead of 1-bromobutane. Yield 40%.

[0256] [Production Example 58] Synthesis of PP-18

 1 α-18 was synthesized in the same manner as in Production Example 47 except that α-bromo-p-xylene was used instead of bromobutane. Yield 44%.

[0257] [Production Example 59] Synthesis of ΡΡ-19

 1 19-19 was synthesized in the same manner as in Production Example 47 except that 2,4 dimethylbenzyl bromide was used instead of bromobutane. Yield 33%.

[0258] [Production Example 60] Synthesis of ΡΡ-20

 1 19-19 was synthesized in the same manner as in Production Example 47, except that 2,5 dimethylbenzyl bromide was used instead of bromobutane. Yield 27%.

[0259] [Production Example 61] Synthesis of ΡΡ-21

 1 Synthesis of 21-21 was carried out in the same manner as in Production Example 47 except that 3,4-dimethylbenzyl bromide was used instead of bromobutane. Yield 25%.

[0260] [Production Example 62] Synthesis of ΡΡ-22

 1 22-22 was synthesized in the same manner as in Production Example 47, except that ο-black benzylbromide was used instead of bromobutane. Yield 34%.

[0261] [Production Example 63] Synthesis of ΡΡ-23

1 Production examples except using 2,4 diclonal benzylbromide instead of bromobutane Fi-23 was synthesized in the same way as 47. Yield 33%.

[0262] [Production Example 64] Synthesis of PP-24

 1 PP-24 was synthesized in the same manner as in Production Example 47, except that p-chlorobenzyl bromide was used instead of bromobutane. Yield 53%.

[0263] [Production Example 65] Synthesis of PP-25

 1 PP-25 was synthesized in the same manner as in Production Example 47 except that m-clonal benzylbromide was used instead of bromobutane. Yield 43%.

[0264] [Production Example 66] Synthesis of PP-26

 1 PP-26 was synthesized in the same manner as in Production Example 47 except that p-fluorobenzyl bromide was used instead of bromobutane. Yield 36%.

[0265] [Production Example 67] Synthesis of PP-27

 1 PP-27 was synthesized in the same manner as in Production Example 47 except that o-fluorobenzyl bromide was used instead of bromobutane. Yield 39%.

[0266] [Production Example 68] Synthesis of PP-29

 1 PP-29 was synthesized in the same manner as in Production Example 47 except that bromophenoxymethane was used instead of bromobutane. Yield 40%.

[0267] [Production Example 69] Synthesis of PP 30

 1 -30 was synthesized in the same manner as in Production Example 47 except that β-bromophenetole was used instead of bromobutane. Yield 42%.

[0268] [Production Example 70] Synthesis of Compound 16 to Compound 18 and ΡΡ-32

[Chemical 40]

[0269] (Synthesis of Compound 16)

 Under a nitrogen atmosphere, 500 ml of DMF and dichloroacetone (50 g, 442 mmol) and p-methinolebenzene-zole (110 g, 884 mmol) were potassium carbonate (264 g, 2 mol) free of calorie and stirred at 60 ° C. for 4 hours. The insoluble part was filtered, and the filtrate was added dropwise to 2000 ml of water. The white precipitate was recrystallized (hexane) to obtain Compound 16. Yield 80%.

 [0270] (Synthesis of Compound 17)

 Under a nitrogen atmosphere, Compound 16 (30 g, 104 mmol) was dissolved in 100 ml of dichloromethane, and bromine (17 g, 104 mmol) was added dropwise thereto. After the reaction for 3 hours, the organic layer was washed twice with water, and after removing the solvent under reduced pressure, Compound 17 was obtained by methanol recrystallization. Yield 88%.

 [0271] (Synthesis of Compound 18)

In a nitrogen atmosphere, compound 17 (30 g, 82 mmol) was dissolved in acetone, and potassium isopropoxyxanthate (15 g, 82 mmol) was added thereto, followed by stirring for 3 hours. The insoluble part was filtered, and the filtrate was concentrated under reduced pressure, and then added dropwise to 700 ml of concentrated sulfuric acid at 0 to 5 ° C. After dropping, the temperature was returned to room temperature and the reaction was performed for 2 hours. The reaction solution was added dropwise with stirring to 2000 ml of ice water to form a yellow precipitate. This was filtered, and the filtrate was recrystallized with methanol to obtain Compound 18 in a yield of 55%. [0272] (Synthesis of PP 32)

 32-32 was synthesized with reference to Production Example 45 using Compound 18 and NiCl · 60, tetraethylammonium, and iodine under a nitrogen atmosphere. Yield 55%.

[0273] [Production Example 71] Synthesis of ΡΡ-35

 ρ-35 was synthesized in the same manner as in Production Example 71 except that ο-black benzenethiol was used instead of ρ-methylbenzenethiol. Yield 33%.

[0274] [Production Example 72] Synthesis of ΡΡ-38

 1 38-38 was synthesized in the same manner as in Production Example 47 except that phenacyl bromide was used instead of bromobutane. Yield 30%.

[0275] [Production Example 73] Synthesis of ΡΡ-39

 1 Synthesis of ΡΡ-39 was carried out in the same manner as in Production Example 47 except that jodoethane was used instead of bromobutane. Yield 35%.

[0276] [Production Example 74] Synthesis of ΡΡ-42

 [Chemical 41]

[0277] While stirring tetrathiapentalene 2,5 dione (5.0 g, 24 mmol) in 500 ml of methanol under a nitrogen atmosphere, sodium methoxide (2.6 g, 48 mmol) was added at 20 ° C. Karo, stirred for 90 minutes. Thereto, Joadethane (6.8 g, 24 mmol) was added dropwise and reacted for 4 hours. Sodium methoxide (2.6 g, 48 mmol) was further added thereto, and after stirring for 2 hours, a solution of NiCl 6 H 0 (2.9 g, 2.9 mmol) dissolved in 50 ml methanol was slowly added dropwise. The mixture was further stirred for 4 hours, 3.Ommol of tetrabutylphosphonium bromide was added, and the mixture was stirred for 1 hour while bubbling air. The obtained solid was filtered to obtain PP-42. Yield 49%. [0278] Table 4 shows melting points of the compounds synthesized in the above production examples;! -18.

[0279] [Table 4]

[0280] [Example 1]

 The molecular weights Mw and Mn and the near-infrared maximum absorption wavelength of some of the near-infrared absorbing materials represented by the general formula (1) of the present invention were measured below. The results are shown in Tables 5-1 and 5-2.

 The molecular weight was measured using a high-speed GPC manufactured by Tosoh Corporation; HLC8120GPC with a solvent THF and UV detection at 254 nm (polystyrene conversion). The near-infrared absorption wavelength was measured with a spectrophotometer V-570 manufactured by JASCO.

[0281] [Table 5] 1

表 5 - 2

Table 5-2

 [0282] Table 6 shows SP values in various solvents. (Hideki Yamamoto, “SP Value Fundamentals' Application and Calculation Method”, Information Organization Co., Ltd., April 3, 2006, 4th edition) No.8;! -84)

[0283] [Table 6]

[0284] [Example 2]

 Hereinafter, Comparative Compound 1, Comparative Compound 2 (see the publication of JP-A-2-264788 for the production method), Comparative Compound 3 (see US Pat. No. 5,089,585 for the production method) and some of the present invention Table 7 shows the solubility of near-infrared absorbing materials in toluene and ethyl acetate. The solubility test was conducted as follows. That is, the materials and the solvent were added to the sample bottle, stirred for a whole day and night at various concentrations, and the solubility in various solvents was examined.

[0285] [Chemical 42]

Comparative compound 1 Comparative compound 2 Comparative compound 3

Material Solubility in toluene (w t%) Solubility in ethyl acetate (w t%) Comparative compound 1 0. 35 0. 009

 Comparative compound 2 0. 9 0. 05

 Comparative compound CO 3 0. 1 Insoluble

 P—1 10 or more 0.8

 P—2 10 or more 0.28

 P—6 10 or more 0.29

 P-22 10 or more 0.7

 P—23 10 or more 0.7

 P-24 10 or more 0.5

 P- 25 10 or more 1. 0

 10 or more 0.6

 P- 27 10 or more 0.7

 P- 28 10 or more 0.9

 P—29 10 or more 0.9

 P—30 10 or more 0.7

 10 or more 1.2

 P—32 10 or more 0.8

 P—33 10 or more 1.5

 P—34 10 or more 1. 3

 P—35 10 or more 1. 1

 P- 36 10 or more 0.9

 P- 37 10 or more 0.9

 P-38 10 or more 0.5

 P—39 10 or more 0.6

 P—40 10 or more 1. 4

 P-46 3. 2 1. 0

 P-47 2. 9 2. 2

 P-48 2. 2 1. 1

 P- 56 10 or more 0.5

 P— 57 5. 5 0. 5

 P- 60 4. 0 2. 0

 P- 61 3. 5 2. 5

 P- 62 10 or more 2. 0

P-64 10 or more 2.2 From Table 7 above, it can be seen that the near-infrared absorbing material of the present invention has high solubility in solvents. In addition, by comparing the solubility of Comparative Compound 1 and Comparative Compound 2, the presence of a substituent in the aryl group increases δρ and increases the solubility in ethyl acetate. I understand. Furthermore, from the comparison of the solubility of Comparative Compound 1, Comparative Compound 2 and Comparative Compound 3 with the near-infrared ray absorbing material of the present invention, the improvement of the solubility with the near-infrared absorbing material of the present invention is ¹ — [CH] — X ² — Ar ¹ — Y— Ar ² — X ³ — [CH] — X ⁴ —

 2 η 2 η

 It can be seen that this is due to the introduction of a valent group. In addition, substituted or unsubstituted phenylene groups and alkylene groups improve solubility in nonpolar solvents, and polar groups such as ester groups, carbonyl groups, and imino groups improve solubility in polar solvents. I understand that. That is, it can be seen that the SP value of the near-infrared absorbing material of the present invention is close to the SP value of the resin and the solvent.

 [0288] [Example 3]

 Table 8 shows the solubility of Comparative Compound 1, Comparative Compound 2, Comparative Compound 3 and several near-infrared absorbing materials of the present invention in various solvents. In the table, the solubility of near-infrared absorbing material is less than 0.01 wt%, X is 0.01 wt% or more and less than 0.20 wt%, △ is 0.2 wt% or more and less than 1.0 wt% is ◯, 1. 0wt% or more is marked as ◎. MEK represents methyl ethyl ketone, T represents toluene, E represents ethyl acetate, and T / E = 3/7 represents a solution in which the weight ratio of toluene to ethyl acetate is 3: 7! / RU

[0289] [Table 8]

Material Toluene Ethyl acetate Acetone Τ Τ / Ε = 3/7 Τ / Ε = 2/8 T / E = l / 9 Comparative compound 1 XX ∆ XX Comparative compound 2 〇 〇 X Δ 0 Δ X Comparative compound 3 Δ XX Δ XXX

P- 1 ◎ ○ △ ◎ ◎ ○ Δ

P- 2 © ○ Ο ◎ ○ Δ

 © 〇 Δ 〇 Ο 〇 〇

Ρ-22 ◎ 〇 △ ◎ 〇 〇 〇

Ρ— 23 ◎ 〇 △ ◎ 〇 〇 〇

Ρ-24 ◎ Ο △ ◎ 〇 〇 〇

Ρ-25 ◎ ◎ Δ ◎ 〇 〇 〇

26- 26 ◎ 〇 Δ ◎ ◎ 〇 〇

Ρ- 27 ◎ 〇 Δ ◎ ◎ 〇 〇

Ρ— 28 ◎ 〇 △ ◎ ο 〇 〇

Ρ- 29 ◎ 〇 △ ◎ 〇 〇 〇

Ρ— 30 ◎ ○ △ ◎ ○ ○ Ο

Ρ- 31 ◎ ◎ △ © ◎ ◎ 〇

Ρ— 32 ◎ 〇 X ◎ 〇 〇 〇

Ρ- 33 ◎ ◎ Δ © ◎ ◎ ◎

Ρ— 34 ◎ ◎ △ ◎ ◎ ◎

Ρ— 35 ◎ ◎ 〇 ◎ ◎ ◎ ο

Ρ— 36 ◎ 〇 Δ ◎ 〇 Ο ο

Ρ-37 ◎ 〇 △ 〇 〇 〇

Ρ— 38 ◎ 〇 △ ο 〇 〇

Ρ- 39 ◎ Ο Δ ◎ 〇 〇 〇

Ρ— 40 ◎ ο Δ Ο 〇 Ο 〇

Ρ- 45 ◎ ◎ △ ◎ ο ◎ 〇

Ρ-46 ◎ ◎ X ◎ ◎ 〇

Ρ— 47 © X 〇 ◎ ◎ 〇

Ρ- 48 ◎ ◎ X Ο ◎ ◎ ◎

Ρ- 56 ◎ ○ ○ ◎ ◎ ○ Δ

Ρ— 57 ◎ ο X △ 〇 Ο 〇

Ρ— 60 ◎ ◎ △ ◎ ◎ ◎ 〇

Ρ— 6 1 ◎ ◎ X ◎ ◎ 〇

Ρ— 62 ◎ ◎ △ 〇 © 〇

Ρ— 64 ◎ ◎ Δ ◎ 〇 © 〇 From Table 8, Comparative Compound 1, Comparative Compound 2 and Comparative Compound 3 have SP value of 7.0 < It can be seen that δ <9.0, 0.1 <δ <5.5, and 0.1 <δ <5.0 are not satisfied. Dph

The results shown in Table 8 indicate that “one X ¹ — [CH] X ² — Ar ¹ — Y—

 2 n

Among the divalent groups of Ar ² — X ³ — [CH] — X ⁴ , substituted or unsubstituted phenylene and alkylene groups improve solubility in nonpolar solvents, resulting in ester groups and carbonyl groups. A polar group such as an imino group improves the solubility in a polar solvent! For example, in P-1, it is found that 7 · 0 <δ <9.0

, 0.1 <δ <5.5, 0.1 <δ <5.0.

 P h

 [Example 4]

 [Chemical 43]

比較化合物 4 Mn = 4 0 0 0 ( G P C ： ポリスチレン換算）

Comparative compound 4 Mn = 4 0 0 0 (GPC: polystyrene equivalent)

[0292] Comparative compound 1, comparative compound 2, comparative compound 3, and comparative compound 4 (see US Pat. No. 6,489,399 for the production method), P1, P-2, P-6, P-38, P-56 and P-62 were mixed with polymethylmethacrylate (HMw = 200, 000) with a solid content of 25% (solvent: ethyl acetate: toluene = 2: 1), and about 2% of the solid content was mixed with PET film. Coated. Table 9 shows the Haze value and transmittance (% T) at the near-infrared maximum absorption wavelength (λmax) of this film. The Haze value was measured with a Haze Meter NDH2000 manufactured by NIPPONN DENSHOKU.

[0293] [Table 9] Material H aze value (%)% T in ^ ma Comparative compound 1 7.0 4 0

 Comparative compound 2 5. 0 3 3

 Comparative compound 3 1 4. 0 3 5

 Comparative compound 4 0. 9 7 0

 P— 1 1. 1 9

 1. 4 7

 P— 6 2. 2 1 1

 P— 3 8 1. 3 1 3

 P-5 6 1. 8 8

 P— 6 2 1. 5 1 0

[0294] From Table 9 above, it is understood that the Haze value of the coating agent is lowered and the near-infrared absorption is increased by increasing the compatibility with the solvent and the resin. In Comparative Compound 4, the ratio of the near-infrared absorption site in the weight of the material is small, so the film containing this has a weak near-infrared absorption ability.

 [0295] [Example 5]

 Comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, P-1, P-2, P-6, P-38, P-56, P-62 are acrylic adhesives with a solid content of 25% ( Monomer composition: 60% butyl acrylate, 30% isobutyl acrylate, 3% acrylic acid, 7% hexyl acrylate 7%, solvent composition: 80% ethyl acetate, 20% toluene) After mixing at 0%, the film was applied to a PET film with a film thickness of 20 m, dried at 90 ° C for 2 minutes, and the adhesive surface was further laminated with a PET film. Table 10 shows the Haze value, visible light, and λ max transmittance for this film. The Haze value was determined by the same method as in Example 4. Visible light and λ max transmittance were measured with a spectrophotometer V-570 manufactured by JASCO.

[0296] [Table 10] Material fee H aze value (%) visible light transmittance (%) A _{ma x} transmittance (%)

 Comparative compound 1 1 8 5 0 30 Comparative compound 2 1 6 5 0 2 0 Comparative compound 3 1 6 4 5 1 7 Comparative compound 4 0. 8 8 5 6 6

 P— 1 1. 5 80 5

 P-2 2. 5 70 1 0

 P- 6 1. 8 8 2 7

 P- 38 1. 4 8 0 9

 P— 5 6 2. 9 7 5 1 3

 P- 6 2 1. 3 7 8 1 0

In Table 10 above, the visible light transmittance is the average transmittance at 450 nm to 650 nm, and λ max is the maximum absorption wavelength. Although the adhesive film containing Comparative Compound 4 has a low Haze value, it is a structural material obtained by extending an olefin resin from a dye for a long time, so that the weight ratio of the near-infrared absorbing portion is small. Therefore, since the film containing this is further diluted with resin, the near-infrared absorption capacity of max is weak. In other cases, it can be seen from Table 10 that the higher the compatible film, the lower the Haze value, the higher the visible light transmittance, and the higher the absorption rate at λ max.

 [0298] [Example 6]

 The film of Example 5 was tested under the conditions of humidity 95%, temperature 80 ° C., and 48 hours. Table 11 shows the Haze values before and after and the transmittance change Δ% H directly at the maximum absorption wavelength.

[0299] [Table 11] Material Haze value (before test) Haze value (after test) Δ% Τ

 Comparative compound 1 1 8 2 2 2 0

 Comparative compound 2 1 6 2 1 2 5

 Comparative compound 3 1 6 1 9 1 0

 Comparative compound 4 0. 8 5. 3 20

 P— 1 1. 5 2. 5 2. 0

 P— 2 2. 5 3. 0 2. 5

 P— 6 1. 8 1. 9 1. 5

 P- 38 1. 4 1. 7 2. 0

 P— 56 2. 9 3. 2 3. 0

P- 6 2 1. 3 1. 4 1. 8 [0300] From Table 11, the change in Haze value before and after the test and the change in transmittance at the maximum absorption wavelength Δ% T is more than that of Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4 , Ρ-6, Ρ-38, Ρ-56, and Ρ-62 have a smaller force S and are highly durable against humidity and temperature.

 [0301] [Example 7]

 The film of Example 5 was tested at a temperature of 80 ° C. for 500 hours, and Table 12 shows the before and after Haze values and the transmittance change Δ% T at the maximum absorption wavelength.

[0302] [Table 12]

[0303] From Table 12, Haze value before and after the test and change in transmittance at maximum absorption wavelength Δ% T are more than those of Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, Ρ—1, Ρ—2, Ρ-6, Ρ-38, Ρ-56, Ρ-62 are better than J.

 [0304] [Example 8]

In the film of Example 5, UV-absorbing PET film (Tijin Tetron Film, manufactured by Teijin DuPont Film Co., Ltd.) is mounted, and a 24-hour light resistance test is performed with xenon—100 W / m ² , temperature 60%, humidity 60%. Table 13 shows the Haze value before and after the test and the transmittance change Δ% T at the maximum absorption wavelength.

[0305] [Table 13] Material H aze value (before test) H aze value (after test) ΐτ Comparative compound 1 18 19 10

 Comparative compound 2 16 19 13

 Comparative compound 3 16 20 11

 Comparative compound 4 0. 8 1. 9 15

 P—cn 1 1. 5 1. 5 1

 P— 2 2. 5 2. 6 0. 3

 1. 8 1. 8 0. 2

 P— 38 1. 4 1. 7 1. 0

 P— 56 2. 9 3. 3 2. 1

 P- 62 1. 3 1. 5 0. 7

[0306] From Table 13 above, the change in transmittance Δ% T between before and after the test, compared to Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, and Comparative Compound 4, is HΡ value and Maximum absorption wavelength. Ρ-6, Ρ-38, Ρ-56, Ρ-62 are more powerful and have excellent durability.

 [Example 9]

 When the same tests as in Examples 6 to 8 were performed on each of the films prepared in Example 4, similar results were obtained.

[0308] According to Examples;! To 7, the near-infrared absorbing material of the present invention has a SP length of 7.0 <6 <9.0, 0.1 <by adjusting the functional group used in the near-infrared absorbing material. δ <5.5, 0.1 <δ dph

It is clear that the solubility in solvents and the compatibility with resins are improved, and both have excellent durability.

[Example 10]

 [Chemical 44]

 Comparative compound 5

[0310] [Chemical 45]

 Comparative compound 6

[0311] Comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, P-1, P-2, P-6, P-38, P-56, P-62 were mixed with 25% solids polymethyl About 1.5% of solid content in a metatalylate (Mw = 200,000) solution (solvent: ethyl acetate: toluene = 2: 1) and further mixed with the above comparative compound 5 (Japanese Patent No. 3699464) No. publication), comparative compound 6 (JP 2005-232232 publication, JP 2006-195399 publication) or PP-2, PP-3, PP-5, PP-16, PP-20, PP-30 Was mixed with 2% of solid content and applied to PET film. This film was subjected to a heat resistance test at 80 ° C. for 500 hours, and Table 14 shows the Haze value, transmittance change (Δ% T) and color change Ay value at 850 nm and lOOOnm. The Haze value and Δ% T were determined in the same manner as in Example 5, and the chromaticity change Ay value was measured with a MINOLTA chromaticity meter CR-300.

 [0312] [Table 14]

[0313] From Table 14 above, the material P of the general formula (1) of the present invention P -62 and the material represented by the general formula (3) PP-2, PP-3, PP-5, PP-16, PP-20, PP-30, the durability should be dramatically improved. I understand.

 [Example 11]

 When the film prepared in Example 10 was tested under the durability test conditions used in Example 6 and Example 8, the same results as in Example 10 were obtained.

 [0315] [Example 12]

 Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, Comparative Compound 4, P—1, P—2, P—6, P—38, P—56, P—62 2.5%, Comparative Compound 5, Comparison Compound 6 or PP-2, PP-3, PP-5, PP-16, PP-20, PP-30, 3.0%, solid content 25% acrylic adhesive (monomer composition: butyl acrylate 60% , Isobutyl acrylate 30%, Acrylic acid 3%, Acrylic acid 2-ethylhexyl 7%, Solvent composition: Ethyl acetate 80%, Toluene 20%) After coating and drying at 90 ° C for 2 minutes, the adhesive surface was further laminated with PET film. This film was subjected to a heat resistance test at 80 ° C. for 500 hours. Table 15 shows the Haze value, transmittance change (Δ% Τ) and color change Ay value at 850 nm and lOOOnm. The Haze value and Δ% Τ were determined in the same manner as in Example 5. The chromaticity change Ay value was measured with a MINOLTA color chromatograph CR-300.

 [0316] [Table 15]

[0317] From the above table, when the comparative compound is used, the dye deterioration in the adhesive is significant. The material P-l, P-2, P-6, P-38, P-56, P-62 and the material PP-2 represented by the general formula (3) of the general formula (1) of the present invention It can be seen that the durability is dramatically improved when the combination of PP-3, PP-5, PP-16, PP-20 and PP-30.

 [0318] [Example 13]

 When the film prepared in Example 12 was tested under the durability test conditions used in Example 6 and Example 8, the same results as in Example 12 were obtained.

 [0319] From the above, by using a combination of the dye of the general formula (1) and the dye of the general formula (11) according to the present invention, it is possible to create a durable and uniformly transparent filter with little color change. It became clear that.

 [0320] [Example 14]

 Pl, P-1 and its by-products PP-45 mixture and PP-45, 25% solid acrylic adhesive (monomer composition: 60% butyl acrylate, 30% isobutyl acrylate, 3% acrylic acid) 2% hexyl acrylate, 7%, solvent composition: 80% ethyl acetate, 20% toluene) and 2.0% of solid content, and coated on PET film with a film thickness of 25 m at 90 ° C After drying for 2 minutes, the adhesive surface was further laminated with a PET film. This film was subjected to a heat resistance test at 80 ° C. for 500 hours, and its Haze value and transmittance change (Δ% Τ) at near infrared maximum absorption wavelength (850 nm) are shown in Table 16. The Haze value and Δ% T were determined by the same method as in Example 5. The ratio of by-product ΡΡ-45 in Ρ-1 was determined by the peak area ratio of GPC (UV: 290 nm detection). Asked.

 [0321] [Table 16]

上記表より、 P— 1と P— 1およびその副生成物 PP— 45混合物は初期 Haze値に変 わりが無ぐ耐久性も同等である。し力も PP— 45のみ用いた場合では高 Hazeとなり 、耐久性も低下することが分かる。すなわち P— 1、 P— 1と PP— 45 (P— 1合成時の 副生成物）の混合物は区別なく使用することができる。

From the above table, P-1 and P-1 and its by-product PP-45 mixture have the same durability with no change in initial Haze value. It can be seen that when only the load of PP-45 is used, high haze is obtained and durability is also lowered. That is, P-1, P-1 and PP-45 (P-1 Mixtures of by-products) can be used without distinction.

[Example 15]

 In Example 14, PP-44 (near infrared maximum absorption wavelength: 1, OOOnm) was further added to 2. Owt.

When a similar test was performed with addition of%, the same result as in Example 14 was obtained.

Claims

The scope of the claims  Near-infrared absorbing material having a repeating unit represented by the following general formula (1), general formula (1):

(In the formula, M represents a metal atom, one of 1 ^ 1 ^ ° represents a direct bond, the other represents a divalent group represented by the following general formula (2), and the rest Each independently represents a hydrogen atom or a substituent. General formula (2): [Chemical 2] X ^{1 to} CH CH -X ^2- ■ Ar ¹ —— Y—— Ar ² --X ³ --CH ₂ --x ⁴ — (Wherein, ^direct-4 binding or single NHCO CONH NHCOO O CONH OS COO OCO SO CO C = C -, - N = NS- S-, a substituted or unsubstituted imino group, Ar ¹ and Ar ² Represents a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, n represents a natural number, Y represents a direct bond or an unsubstituted alkylene group, NHCO—CONH NHCOO OCONH OS NH —COO OCO SO CO C = CN = N—S—S—, a substituted imino group or the following divalent organic residue A.) Divalent organic residue A: [Chemical 3]

CH ₂ CH (CH ₃ ) ₂ C ₂ H ₅ — CH— C ₄ H ₉ CF ₃  H, C, CH H2C ヽ zCH2 CH ₃ CH-, CF ₃ H ₂  Ten  [2] In the near-infrared absorbing material according to claim 1, I ^ to R, one of the deviations is a direct bond, and R "to R ', one of the deviations is represented by the general formula (2) A near-infrared absorbing material, which is a divalent group. [3] In the near-infrared absorbing material according to claim 1, any one of I ^ to R ⁵ is a direct bond, and any one of R ^{6 to} R ^1Q is represented by the general formula (2). A near-infrared absorbing material, which is a divalent group represented. [4] In the near-infrared absorbing material according to claim 1, one of I ^ to R ⁵ is a direct bond, and the other one of I ^ to R ⁵ is represented by the general formula (2). A near-infrared absorbing material characterized by being a divalent group represented. [5], wherein at least one Xi～x ⁴ in the near infrared absorbing material according to claim 1 is an ether bond and / or Ar ¹ and Ar ² are substituted or unsubstituted phenylene group Near infrared absorbing material. [6] In the near-infrared absorbing material according to claim 1, at least one ether bond and Ar ¹ and Ar ² are substituted or unsubstituted phenylene group to X ⁴ and Y is above two, Near-infrared absorbing material, characterized in that it is any one of valent organic residues A [7] The near-infrared absorbing material according to claim 1, wherein the near-infrared absorbing material is a homopolymer having a repeating unit represented by the general formula (1). Absorbing material. [8] The near-infrared absorbing material according to claim 1, wherein the near-infrared absorbing material is a co-polymer having two or more repeating units represented by the general formula (1) as a repeating unit. A near-infrared absorbing material characterized by being a coalescence.  The near-infrared absorbing material according to claim 2, wherein the divalent group represented by the general formula (2) is bonded to! /, NA! /, And the benzene ring has a substituent at the ortho position. Features near-infrared absorbing material.  A near-infrared absorbing composition comprising a binder resin and the near-infrared absorbing material according to any one of claims 1 to 9.  The near-infrared absorbing composition according to claim 10, wherein the binder resin and the near-infrared absorbing material have Hansen solubility parameters, ie, a dispersion force (δ) and a force generated between permanent dipoles of the molecule (δ). The near-infrared rays are characterized in that the hydrogen bonding force (δ) of the molecule is 7.0 dph δ 9.00, 0.1 δ 5.5, 0.1 δ δ 5.0 dph Absorbent composition.  The near-infrared absorbing composition according to claim 10, wherein the near-infrared absorbing material is mixed in an amount of 0.0;! To 20 parts by weight in 100 parts by weight of the binder resin. Absorbent composition.  11. The near-infrared absorbing composition according to claim 10, wherein the binder resin has a glass transition temperature of 80 ° C. or higher.  11. The near infrared ray absorbing composition according to claim 10, wherein the binder resin has a glass transition temperature of 0 ° C. or lower.  11. A near-infrared absorbing composition according to claim 10, wherein the near-infrared absorbing composition further comprises a solvent.  The near-infrared absorbing composition according to claim 10, wherein the near-infrared absorbing material comprises two or more kinds of near-red light having different near-infrared absorption wavelengths represented by the general formula (1). A near-infrared absorbing composition comprising an external absorption material.  The near infrared ray absorbing composition according to any one of claims 10 to 16, wherein the near infrared ray absorbing composition further comprises a near infrared ray absorbing material represented by the following general formula (11): A near-infrared absorbing composition characterized. General formula (11): [Chemical 4]

(Wherein M ² represents a metal atom, R ⁵ ° to R ⁵³ represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted group. Alternatively, it represents an unsubstituted silyl group or a substituted or unsubstituted acyl group, and two Rs in the same ligand may be bonded to each other to form a ring or may be a monovalent salt. ) [18] In the near-infrared ray composition according to claim 17, R ⁵ ° to R ⁵³ in the general formula (11) are monovalent organic residues represented by the following general formula (12) A near-infrared ray absorbing composition characterized by the above.  General formula (12)  [Chemical 5]

(Wherein X ⁵ represents a direct bond or —O—, —S—, —CO—, a substituted or unsubstituted imino group, n ¹ represents a natural number, n ² represents 0 or a natural number, R ⁵⁴ ˜R ⁵⁸ represents a hydrogen atom or a substituent. [19] The near-infrared absorbing composition according to claim 18, wherein X ⁵ is a direct bond or A near-infrared absorbing composition, which is -0- and n ² is 1. [20] In the scope paragraph 18 or the near-infrared absorbing composition according to paragraph 19 according near-infrared-absorbing composition characterized in that R ⁵⁴ Contact and / or R ⁵⁸ is a substituent. [21] The near-infrared absorbing material according to any one of claims 1 to 9 or the near-infrared absorbing composition according to any one of claims 10 to 20 on a substrate. A laminate comprising a layer containing an object. [22] The laminate according to claim 21, wherein the laminate is an adhesive sheet.  [23] A resin film containing the near-infrared absorbing material according to any one of claims 1 to 9.  [24] An optical filter comprising the laminate according to claim 21 or 22, or the resin film according to claim 23.