CN101233208A - Near-infrared absorbing material and use thereof - Google Patents

Abstract

Disclosed is a near-infrared absorbing material having a repeating unit represented by the following general formula [1] or [2]. Also disclosed is a near-infrared absorbent composed of such a near-infrared absorbing material. Further disclosed are a near-infrared absorbing composition containing such a near-infrared absorbing material or near-infrared absorbent, and an optical filter (In the formulae, M represents a metal atom; R<1> and R<4> independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group; R<2> and R<3> independently represent a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted alkylene group; and R<1> and R<2> as well as R<3> and R<4> may combine together to form a ring; Y<1>-Y<4> respectively represent a direct bond or a heteroatom; and A represents a direct bond or a divalent organic residue.).

Description

Near-infrared-absorbing material and uses thereof

Technical field

The present invention relates to a kind of new dithiacyclopentene (dithiole) class near-infrared-absorbing material, comprise described near-infrared-absorbing material near infrared ray absorption, comprise near-infrared absorbing composition, near-infrared absorbing film, laminate and the optical filter of described near-infrared-absorbing material or near infrared ray absorption.

Background technology

Usually, the organic nickel complex compound has absorption near infrared 950nm～1200nm scope, and has the excellent character as near infrared ray absorption.Its main purposes is to be used to have absorption, the optical filter of isolating the semiconductor light-sensing device of near infrared ray function, the near-infrared absorbing film or the near-infrared absorbing plate of shielding hot line in the energy-conserving action, to select utilizing sunlight is the agricultural near-infrared absorbing film of purpose, utilize the recording medium of near-infrared absorbing heat, the near-infrared shielding film that e-machine is used, the near infrared ray film of photograph usefulness, eye-protection glasses, sunglasses, the hot radiation shielding film, the optical recording pigment, the optical character reading and recording, prevent secret document copy, Electrophtography photosensor, laser welding etc.In addition, the denoising spectral filter that also can effectively use, the spectral filter that the CMOS image sensor is used as the CCD photographic camera.

In the plasma display (PDP), owing to can produce the neon body isolychn of 800～1050nm in advance, therefore will produce the problem of the flase operation of the machine that uses the near infrared ray telepilot, so need an energy absorption near infrared ray and the good spectral filter of visible light transmittance rate.The pigment that is used for this spectral filter must have high thermal stability and high-light-fastness, causes the problem that spectral filter colourity changes, the near-infrared absorbing ability reduces because of material worsens through long-time generation, becomes problem to be solved.

In addition, in the optical apparatus such as photographic camera or Kamera, for optical signalling being converted to electric signal, so use silicon diode device, CMOS (CMOS) or charge coupling device (CCD) etc.These light-electric conversion device (being designated hereinafter simply as optics) so compare with the vision sensitivity 400～700nm of human eyes, has stronger induction because its photoresponse scope is 300～1100nm near infra red region.Usually, in the opticinstruments such as photographic camera or Kamera, need sense the light of the wavelength of human visual impression response scope, preferably be no more than the wavelength light of this scope, otherwise the circulation ratio that will hinder photometry or color.Therefore, in this case, need an optical filter that can see through visible light and effectively absorb the light of removing near infrared range.

The spectral filter that is used for described CCD, CMOS, can enumerate on resin and (for example disperse the phosphoric acid ester copper compound, with reference to patent documentation 1～5), (for example have low combined optical spectral filter by function and vision sensitivity debugging functions, with reference to patent documentation 6), by with phosphine (phosphine) oxide compound as the monomer composition and the spectral filter that the polymeric resin is constituted (for example, with reference to patent documentation 7) etc., but these weather resistance, light transmission may not satisfy the requirement of spectral filter.

On the other hand, as well known dithiacyclopentene is the complex compound near infrared ray absorption, known have two (two benzylthio-s (dithiobenzyl)) the nickel complex compound (for example, with reference to patent documentation 8,9), two (1,2-acenaphthylene dithio diene (acenaphthylenedithiolato)) the nickel complex compound (for example, with reference to patent documentation 10), the 4-tertiary butyl-1,2-diphenyl disulfide cyclopentenes nickel complex (for example, with reference to patent documentation 11), have two (two benzylthio-s) nickel complex compound (for example, with reference to patent documentation 12) of alkoxyl group.In addition, in the polymer dithiacyclopentene class complex compound, known have dithio diene (dithiolate) nickel high-molecular complex (for example, with reference to patent documentation 13), two thiol-ene (dithiolene) complex compound polymkeric substance (for example, with reference to patent documentation 14) etc.Two thiol-ene complex compound polymkeric substance have the following wavelength absorption scope of short wavelength of absorption 800nm, are not suitable for general near-infrared-absorbing material purposes.In addition, owing to do not have substituting group, therefore has the deliquescent shortcoming of shortage in the complexing object chain position.And then and then, multinuclear shape thiol complex (for example, with reference to patent documentation 15) or 4 Phosphonium (phosphonium), two (cis-1,2-ethene dithio diene) the nickel salt derivative (for example, with reference to patent documentation 16), dithio diene metal complex with secondary alkyl (for example, with reference to patent documentation 17) also can be used as long wavelength's absorbing material, but the intermiscibility of and shortage and resin lower for the solvability of solvent, or in lower temperature, have fusing point and lack thermotolerance etc., lack practicality.

In the same manner, as the near-infrared absorbing compound, known phthalocyanine.Such a phthalocyanine, known have (for example have substituent phthalocyanine compound or naphthalene cyanine compound, with reference to patent documentation 18), have amino phthalocyanine compound (for example, with reference to patent documentation 19～23), fluorine-containing phthalocyanine compound (for example, with reference to patent documentation 24,25) etc.

In addition, known various two quaternary ammoniums (diimmonium) but be that pigment is that wide region absorbs long wavelength (950nm～1100nm), and the fabulous material (for example, with reference to patent documentation 26～29) of visible light light transmission.And this pigment also has the advantage of high resolution, resin intermiscibility.But, do not meet thermotolerance, sunproof requirement.

Be used in the near infrared absorbing coloring matter of above-mentioned near-infrared-absorbing material, usually, it is dissolved into after the solvent, is applied to substrates such as plastics again with mixed with resin, perhaps add with resin form film like after the hot milling, laminar, tabular or other shape is used.Therefore, for above-mentioned near infrared absorbing coloring matter, require the solvability of solvent or and the intermiscibility of resin etc.And then above-mentioned near infrared ray absorption is owing to also using outdoor, so near infrared absorbing coloring matter itself is also required to have high-durability, thermostability etc.

Patent documentation 1:WO99/26951 communique

Patent documentation 2:WO99/26952 communique

Patent documentation 3: TOHKEMY 2000-7871 communique

Patent documentation 4:WO98/55885 communique

Patent documentation 5: TOHKEMY 2000-38396 communique

Patent documentation 6: Japanese kokai publication hei 8-146216 communique

Patent documentation 7: TOHKEMY 2000-98130 communique

Patent documentation 8: Japanese kokai publication sho 63-227597 communique

Patent documentation 9: Japanese kokai publication sho 64-61492 communique

Patent documentation 10: No. 2923084 communique of Japanese Patent

Patent documentation 11: Japanese kokai publication sho 63-307853 communique

Patent documentation 12: Japanese kokai publication hei 2-264788 communique

Patent documentation 13: Japanese kokai publication hei 4-198304 communique

Patent documentation 14: No. 5089585 specification sheets of United States Patent (USP)

Patent documentation 15: TOHKEMY 2005-181966 communique

Patent documentation 16: the special fair 6-72147 communique of Japan

Patent documentation 17: TOHKEMY 2005-232158 communique

Patent documentation 18: Japanese kokai publication hei 10-78509 communique

Patent documentation 19: TOHKEMY 2004-18561 communique

Patent documentation 20: TOHKEMY 2001-106689 communique

Patent documentation 21: TOHKEMY 2000-63691 communique

Patent documentation 22: No. 2746293 communique of Japanese Patent

Patent documentation 23: No. 3226504 communique of Japanese Patent

Patent documentation 24: No. 2907624 communique of Japanese Patent

Patent documentation 25: No. 3014221 communique of Japanese Patent

Patent documentation 26: Japanese kokai publication hei 05-247437 communique

Patent documentation 27: TOHKEMY 2005-325292 communique

Patent documentation 28: No. 3699464 communique of Japanese Patent

Patent documentation 29: TOHKEMY 2003-096040 communique

Summary of the invention

The problem that invention will solve

In the past as the substituted benzene dithiacyclopentene nickel complex class of near infrared absorbing coloring matter, phthalocyanines, anthraquinone class, two two benzyl sulfhydrate nickel complex classes etc. when cooperation is used near infrared ray absorption, not talkative its showed gratifying effect.For example, phthalocyanines replaces by various substituting groups, can improve the solvability in solvent, but its photostabilization, poor heat stability as a result.In addition, so since absorption spectrum but to be the wavelength region of sharp curve absorption near infrared ray little.In addition, substituted benzene dithiacyclopentene nickel complex class is easier to make, and have characteristics such as persistence is better, but solvability is less in solvent, and can produce the problem with the intermiscibility deterioration of resin.

That is to say that solubleness diminishes in solvent, near infrared ray absorption is dissolved in solvent when using, be difficult to make glass, paper or resin surface to contain sufficient pigment and interdict near infrared ray as substrate.When increasing film thickness for the pigment that contains abundant amount, can be by stacked between pigment molecular and in visible-range, present new absorption band, and then then reduced the transmitance of visible light.In addition, if intermolecular interaction increases, the result will cause reducing the near-infrared absorbing characteristic.In addition, if with the near infrared ray absorption mix monomer, when this monomer of polymerizing curable is used as the near-infrared absorbing member, solubleness in monomer also diminishes, be difficult to contain the pigment of abundant amount, in addition, if when making it contain pigment more than the solubleness for the pigment that contains the abundant amount of surpassing, because undissolved pigment, the opaque phenomenon of part can take place near infrared ray absorption layer.And then, if during the intermiscibility variation of above-mentioned near infrared ray absorption and resin, can produce the problem of the layer that can't obtain to have uniform near-infrared absorbing characteristic.

Therefore, the object of the present invention is to provide the solvability in a kind of easy manufacturing, the solvent good, good, simultaneously the near-infrared-absorbing material of wide model of near-infrared absorbing scope and good endurance with the consistency of resin.

In addition, other purpose of the present invention is to provide a kind of near infrared ray absorption with above-mentioned excellent specific property.

In addition, another object of the present invention is to provide a kind of near-infrared-absorbing material that possesses above-mentioned excellent specific property or near-infrared absorbing composition of near infrared ray absorption of containing.

In addition, other purpose of the present invention is to provide a kind of near-infrared-absorbing material that possesses above-mentioned excellent specific property or the long-pending body of near infrared ray absorption layer or film of near infrared ray absorption of comprising in one deck at least.

In addition, other purpose of the present invention is to provide a kind of near-infrared-absorbing material that possesses above-mentioned excellent specific property or optical filter of near infrared ray absorption of comprising.

The means of dealing with problems

That is to say, the present invention relates to following near-infrared-absorbing material, comprise the near infrared ray absorption of described near-infrared-absorbing material, the near-infrared absorbing composition that comprises described near-infrared-absorbing material or described near infrared ray absorption, the long-pending body of near infrared ray absorption layer, near-infrared absorbing film, near-infrared absorbing member and optical filter.

(1) a kind of near-infrared-absorbing material, it has the repeating unit shown in following general formula (1) or (2):

General formula (1)

General formula (2)

(in general formula (1) and (2), M represents atoms metal, R ¹And R ⁴Expression independently of one another replaces or unsubstituted aryl, replacement or unsubstituted heteroaryl or replacement or unsubstituted alkyl R ²And R ³Expression independently of one another replaces or unsubstituted arylidene, replacement or unsubstituted heteroarylidene or replacement or unsubstituted alkylidene group, in addition, and R ¹And R ², R ³And R ⁴Also can mutually combine and form ring, Y ¹～Y ⁴Expression is combination or heteroatoms directly, and wherein, A represents organic residue of directly combination or divalence).

(2) the 1st near-infrared-absorbing material as described, wherein, the repeating unit shown in the general formula (1) is the repeating unit shown in the following general formula (3), in addition, the repeating unit shown in the general formula (2) is the repeating unit shown in the following general formula (4):

General formula (3)

General formula (4)

(in general formula (3) and the general formula (4), M, R ¹, R ², R ³, R ⁴Identical with A) with definition content in described the 1st.

(3) the 1st near-infrared-absorbing material as described, wherein, the repeating unit shown in the general formula (1) is exactly the repeating unit shown in the following general formula (5), and in addition, the repeating unit shown in the general formula (2) is exactly the repeating unit shown in the following general formula (6):

General formula (5)

General formula (6)

(in the formula, M, R ¹, R ², R ³, R ⁴Identical with A) with definition content in described the 1st.(4) the 1st near-infrared-absorbing material as described, wherein, the repeating unit shown in the general formula (1) is exactly the repeating unit shown in the following general formula (7), and in addition, the repeating unit shown in the general formula (2) is exactly the repeating unit shown in the following general formula (8):

General formula (7)

[changing 7]

General formula (8)

[changing 8]

(in the formula, M, R ¹, R ², R ³, R ⁴Identical with A) with definition content in described the 1st.

(5) arbitrary near-infrared-absorbing material of the 1st to 4 as described, wherein, M is nickel, platinum, cobalt, palladium or copper.

(6) arbitrary near-infrared-absorbing material of the 1st to 5 as described, wherein, R ¹～R ⁴At least one for having substituent group.

(7) arbitrary near-infrared-absorbing material of the 1st to 6 as described, wherein, R ¹And R ²And/or R ³And R ⁴In conjunction with forming conjugation or unconjugated ring.

(8) arbitrary near-infrared-absorbing material of the 1st to 7 as described, wherein, A be will from-NHCO-,-CONH-,-NHCOO-,-OCONH-,-O-,-S-,-NH-,-COO-,-OCO-,-SO ₂-,-CO-,-C=C-,-N=N-,-the group arbitrary combination selected in S-S-, replacement or unsubstituted arylidene, replacement or unsubstituted heteroarylidene, replacement or unsubstituted alkylidene group and the group that replacement or unsubstituted amino constituted and the organic residue of divalence that forms.

(9) the 8th near-infrared-absorbing material as described, wherein, A is the group shown in the following general formula (9):

[changing 9]

(in the formula, X ¹～X ³Be independently of one another directly in conjunction with or expression-NHCOO-,-OCONH-,-O-,-S-,-NH-,-COO-,-OCO-,-SO ₂-,-CO-,-C=C-,-N=N-or-S-S-, n ¹And n ²Expression 0 or natural number).

(10) arbitrary near-infrared-absorbing material of the 1st to 9 as described, wherein, described near-infrared-absorbing material has the different repeat units more than 2 kinds.

(11) a kind of near infrared ray absorption, it comprises described the 1st to 10 arbitrary near-infrared-absorbing material.

(12) a kind of near-infrared absorbing composition, it comprises at least a described the 11st near infrared ray absorption.

(13) the 12nd near-infrared absorbing composition as described, wherein, described near infrared ray absorption comprises the near infrared ray absorption more than 2 kinds.

(14) arbitrary near-infrared absorbing composition of the 12nd or 13 as described wherein, further comprises the near infrared ray absorption outside described the 11st near infrared ray absorption.

(15) the 14th near-infrared absorbing composition as described, wherein, the near infrared ray absorption outside described the 11st near infrared ray absorption is to be that pigment, phthalocyanine are that pigment and two quaternary ammoniums (diimmonium) are at least a near infrared ray absorption of selecting the pigment from nickel complex.

(16) the 13rd or 14 near-infrared absorbing composition as described wherein, is included in the near infrared ray absorption in the described near-infrared absorbing composition, comprises at least 2 kinds of near infrared ray absorptions with different maximum near-infrared absorbing wavelength.

(17) arbitrary near-infrared absorbing composition of the 12nd～16 as described, wherein, described near-infrared absorbing composition further comprises adhesive resin.

(18) arbitrary near-infrared absorbing composition of the 12nd～17 as described wherein, further comprises solvent in the described near-infrared absorbing composition.

(19) arbitrary near-infrared absorbing composition of the 12nd～18 as described, wherein, described near-infrared absorbing composition is a coating composition.

(20) arbitrary near-infrared absorbing composition of the 12nd～19 as described, wherein, described near-infrared absorbing composition is adhesion or adhesive composite.

(21) arbitrary near-infrared absorbing composition of the 12nd～19 as described, wherein, described near-infrared absorbing composition is that laser welding is used composition with composition, hot radiation shielding with composition or liquid-crystal display (LED) with composition, laser labelling (laser marking).

(22) a kind of laminate, it forms for form the layer that comprises described the 1st～10 arbitrary near-infrared-absorbing material on base material.

(23) the 22nd laminate as described, wherein, the layer that comprises described near-infrared-absorbing material is become by described the 12nd～20 arbitrary near-infrared absorbing composition.

(24) a kind of infrared ray absorbing membrane, it comprises described the 1st～10 arbitrary near-infrared-absorbing material.

(25) a kind of optical filter, it comprises described the 22nd or 23 laminate.

(26) the 25th optical filter as described, wherein, described optical filter is plasma display, liquid-crystal display, CCD photographic camera or CMOS image sensor optical filter.

The invention effect

By the present invention, can obtain that a kind of easy manufacturing, the solvability in solvent are good, good with the consistency of resin, the near-infrared absorbing scope wide and the near-infrared-absorbing material of good endurance.

In addition, by the present invention, can obtain a kind of the have near infrared ray absorption of described excellent specific property, the near-infrared absorbing composition that comprises described near infrared ray absorption, the long-pending body of near infrared ray absorption layer, near-infrared absorbing film, near-infrared absorbing member and optical filter.And these optical filters preferably can be used for plasma display, liquid-crystal display, CCD photographic camera or CMOS image sensor.

Description of drawings

Fig. 1 represents the absorption spectrum of P-1.

Fig. 2 represents the absorption spectrum of the laminate of P-1.

Fig. 3 represents the absorption spectrum of the laminate of P-23.

Fig. 4 represents the absorption spectrum of the laminate of P-43.

Fig. 5 represents the absorption spectrum of the laminate of the use P-23 among the embodiment 3.

Fig. 6 represents the absorption spectrum of the laminate of the use P-43 among the embodiment 8.

Embodiment

The present invention relates to a kind of the have near-infrared-absorbing material of the novelty of the repeating unit shown in above-mentioned general formula (1) or (2), the near infrared ray absorption that uses this material, near-infrared absorbing composition, the long-pending body of near infrared ray absorption layer, near-infrared absorbing film, near-infrared absorbing member and optical filter.And, preferably can enumerate the repeating unit shown in above-mentioned general formula (3)～(8) as the repeating unit shown in above-mentioned general formula (1) or (2).

In the near-infrared-absorbing material of the novelty of repeating unit with described general formula (1)～(8), R ¹, R ⁴Expression independently of one another replaces or unsubstituted aryl, replacement or unsubstituted heteroaryl or replacement or unsubstituted alkyl, is preferably to replace or unsubstituted phenyl, replacement or unsubstituted thienyl, replacement or unsubstituted alkyl.

Below describe the R in general formula (1)～(8) more in detail ¹, R ⁴Each group.

R in general formula (1)～(8) ¹, R ⁴Replacement or unsubstituted aryl, so long as replace or unsubstituted aryl gets final product, there is no specific restriction.Replace or unsubstituted aryl, for example can enumerate phenyl, the 2-5-xylyl, diphenylene, triphenylenyl, tetraphenylenyl, the 3-nitrophenyl, 4-first sulfur phenenyl (methylthiophenyl), 3,5-dicyanogen methyl isophorone phenyl, adjacent-, between-and right-tolyl, xylyl, adjacent-,-and right-propyl phenyl, trimethylphenyl, pentalenyl (pentalenyl), indenyl, naphthyl, anthryl, the Azulene base, heptalenyl (heptalenyl), acenaphthylenyl, non-that thiazolinyl (phenalenyl), fluorenyl (fluorenyl), anthryl (anthryl), anthraquinonyl (anthraquinoyl), 3-methyl anthryl, phenanthryl, pyrenyl, benzo phenanthryl (chrysenyl), 2-ethyl-1-benzophenanthrene (chrysenyl) basic Pi base (picenyl) perylene base (perylenyl), 6-Lv perylene base, pentaphene base (pentaphenyl), pentacenyl (pentacenyl), neighbours' phenylene (tetraphenylenyl), hexaphene base (hexaphenyl), hexacenyl (hexacenyl), rubicenyl (rubicenyl), cool base (coronenyl), trinaphthylenyl (trinaphthylenyl), heptaphene base (heptaphenyl), heptaphenyl (heptacenyl), pyranthrenyl (pyranthrenyl), ovalenyl (ovalenyl) etc.

In addition, the R in general formula (1)～(8) ¹, R ⁴Replacement or unsubstituted heteroaryl, so long as replace or unsubstituted heteroaryl gets final product, there is no specific restriction.Replace or unsubstituted heteroaryl, for example can enumerate sulfinyl (thionyl); furyl (furyl); pyrryl (pyrrolyl); imidazolyl (imidazolyl); pyrazolyl; pyridyl; pyrazinyl; between pyrimidyl; pyridazinyl; indyl (indolyl); quinolyl (quinolyl); isoquinolyl; phthalazinyl; quinoxalinyl; quinazolyl; carbazyl; acridyl; phenazinyl; furfuryl group; isothiazolyl; isoxazolyl; furazan base (furazanyl); the Phenazoxine base; benzothiazolyl; benzoxazolyl; benzimidazolyl-; the 2-picolyl; 3-is cyanopyridine-based etc.

And then, the R in general formula (1)～(8) ¹, R ⁴Replacement or unsubstituted alkyl, so long as replace or unsubstituted alkyl gets final product, there is no specific restriction.In addition, alkyl can also can be the cycloalkyl of cyclisation for a straight chain formula or a chain type.If concrete expression replaces or unsubstituted alkyl, methyl, ethyl, propyl group, butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, 2-ethylhexyl, heptyl, octyl group, iso-octyl, octadecyl (stearyl), trichloromethyl, trifluoromethyl, cyclopropyl, cyclohexyl, 1 then can have been enumerated, 3-cyclohexadienyl, 2-cyclopentenes-1-base, 2,4-cyclopentadiene-1-subunit (ylidenyl) etc.

On the other hand, the R of general formula (1)～(8) ²And R ³Expression independently of one another replaces or unsubstituted arylidene, replacement or unsubstituted heteroarylidene or replacement or unsubstituted alkylidene group, perhaps R ¹And R ², R ³And R ⁴Also can mutually combine and form ring.In general formula (1)～(8), R ²And R ³Be preferably and replace or unsubstituted phenylene, replacement or unsubstituted inferior thienyl replacement or unsubstituted alkylidene group.Further preferred situation is R ¹And R ²Or R ³And R ⁴Formation can have substituent conjugation or unconjugated ring.If form unconjugated ring, preferably the carbonatoms with C2～C6 forms.In addition, if when forming the situation of conjugated ring, then preferably comprise alkene, benzene, thiophene.

Below will be at R ², R ³Base is done more detailed description.

R in general formula (1)～(8) ²And R ³Replacement or unsubstituted arylidene, so long as replace or unsubstituted arylidene gets final product, there is no specific restriction.Replace or unsubstituted arylidene, preferably carbon is 6～60 the monocycle or the replacement or the unsubstituted arylidene of condensed ring, and being more preferably carbonatoms is 6～40, more preferably 6～30 replacement or unsubstituted arylidene.If more specifically expression replaces or do not replace arylidene, then can enumerate replacement or unsubstituted phenylene, biphenylene, naphthalene two bases, anthracene two bases, phenanthroline two bases, pyrene two bases, triphenylene two bases, benzo phenanthroline two bases, perylene two bases, five inferior benzene two bases (pentaphenylenediyl), pentacene two bases etc.

In addition, R in general formula (1)～(8) ²R ³Replacement or unsubstituted heteroarylidene, so long as replacement or unsubstituted heteroarylidene get final product, then there is no specific restriction, but be preferably carbonatoms and be 4～60 the monocycle or the replacement or the unsubstituted aromatic heterocyclic group of condensed ring, at least one the carbonatoms that more preferably contains nitrogen-atoms, Sauerstoffatom or sulphur atom is 4～60 the replacement or the aromatic heterocyclic group of unsubstituted monocycle or condensed ring, and more preferably carbonatoms is the aromatic heterocyclic group of 4～30 replacement or unsubstituted 5 yuan or 6 yuan.If specifically expression replacement or not substituted aromatic heterocyclic group for example can have been enumerated replacement or unsubstituted pyrroles two bases, furans two bases, inferior thienyl, pyridine two bases, pyridazine two bases, pyrimidine two bases, pyrazine two bases, quinoline two bases, isoquinoline 99.9 two bases, cinnolines two bases, quinazoline two bases, quinoxaline two bases, phthalazines two bases, pteridine two bases, acridine diacyl, azophenlyene two bases, phenanthroline two bases etc.

And then, R in general formula (1)～(8) ²And R ³Replacement or unsubstituted alkylidene group, so long as replace or unsubstituted alkylidene group gets final product, then there is no specific restriction.In addition, alkylidene group also can be the ring alkylidene group of side chain or cyclisation except straight chain.If concrete expression replaces or unsubstituted alkylidene group, methylene radical, ethylidene, propylidene, butylidene, inferior sec-butyl, the inferior tertiary butyl, pentylidene, hexylidene, inferior 2-ethylhexyl, inferior heptyl, octylene, inferior iso-octyl, inferior octadecyl, trichlorine methylene radical, cyclohexylidene etc. can have been enumerated.

In addition, the substituting group of each group is represented halogen atom (for example can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc.), replacement or unsubstituted alkyl, replacement or unsubstituted alkoxyl group, replacement or unsubstituted alkylthio, cyano group, amino, list or two substituted-amino, hydroxyl, sulfydryl, replacement or unsubstituted aryloxy, replacement or unsubstituted arylthio, replacement or unsubstituted aryl, replacement or unsubstituted heteroaryl among the present invention, in addition, substituting group also can and adjacent substituting group between form and replace or unsubstituted conjugation or unconjugated ring.

As substituent replacement or unsubstituted aryl, can list for example phenyl, diphenylene, triphenylenyl, tetraphenylenyl, the 3-nitrophenyl, 4-toluene sulfenyl, 3, the two benzonitrile bases of 5-, adjacent-, between-and right-tolyl, xylyl, adjacent-,-and right-cumyl, trimethylphenyl, pentalenyl, indenyl, naphthyl, anthryl (anthracenyl), the Azulene base, heptalenyl, acenaphthenyl, non-that thiazolinyl, fluorenyl, anthryl (anthryl), anthraquinonyl, 3-methyl anthryl, phenanthryl, pyrenyl, the benzo phenanthryl, 2-ethyl-1-benzo phenanthryl; Pi base; perylene base, 6-Lv perylene base, the pentaphene base, pentacenyl, neighbours' phenylene, the hexaphene base, hexacenyl, rubicenyl, cool base, trinaphthylenyl, the heptaphene base, heptaphenyl, pyranthrenyl, ovalenyl etc.

In addition, as substituent replacement or unsubstituted heteroaryl, it is cyanopyridine-based etc. for example can to list thienyl, furyl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, quinazolyl, carbazyl, acridyl, phenazinyl, furfuryl group, isothiazolyl, isoxazolyl, furazan base (fuanzanyl), Phenazoxine base, benzothiazolyl, benzoxazolyl, benzimidazolyl-, 2-picolyl, 3-.

As substituent single or two substituted-amino, can list for example methylamino-, dimethylamino, ethylamino, diethylin, dipropyl amino, dibutylamino, diphenylamino, two (acetyl-o-methyl) amino, two (acetyl oxygen ethyls) amino, two (acetyl oxygen propyl group) amino, two (acetyl oxygen-butyl) amino, dibenzyl amino etc.

As substituent replacement or unsubstituted alkyl, can list for example methyl, ethyl, propyl group, butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, 2-ethylhexyl, heptyl, octyl group, iso-octyl, octadecyl, trichloromethyl, trifluoromethyl, cyclopropyl, cyclohexyl, 1,3-cyclohexadienyl, 2-cyclopentenes-1-base, 2,4-cyclopentadiene-1-subunit etc.

As substituent replacement or unsubstituted alkoxyl group, can list for example methoxyl group, oxyethyl group, propoxy-, n-butoxy, sec-butoxy, tert.-butoxy, pentyloxy, hexyloxy, 2-ethyl hexyl oxy, octadecane oxygen base, trichlorine methoxyl group etc.

As substituent replacement or unsubstituted alkylthio, for example can list methylthio group, ethylmercapto group, rosickyite base, butylthio, secondary butylthio, uncle's butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl etc.

As substituent replacement or unsubstituted aryloxy, for example can list phenoxy group, right-tertiary butyl phenoxy group, 3-fluorophenoxy etc.

As substituent replacement or unsubstituted arylthio, can list for example thiophenyl, 3-fluorobenzene sulfenyl etc.

In the above-mentioned substituting group, preferred carbonatoms is 1～20 alkyl or the single or two substituted-amino of alkoxyl group.In addition, adjacent substituting group also can form aliphatics ring, aromatic ring carbon, heteroaromatic or the heterocycle that can contain Sauerstoffatom, nitrogen-atoms, sulphur atom etc. of 5～7 yuan of rings each other, and also can there be substituting group the optional position of these rings.

In addition, the Y of general formula (1) or (2) ¹～Y ⁴Represent direct combination, or represent heteroatomss such as Sauerstoffatom, nitrogen-atoms, sulphur atom, be preferably sulphur atom.In described general formula (1) and (2), Y ¹～Y ⁴Directly in conjunction with the time, form the repeating unit of general formula (3) or (4) expression; Y ¹, Y ⁴Be sulphur atom, Y ², Y ³Directly in conjunction with the time, form the repeating unit of general formula (5) or (6) expression; Y ¹～Y ⁴If be sulphur atom entirely, form the repeating unit of general formula (7) or (8) expression.These all can be used as the good material of near infrared ray absorption.

Below, in general formula (1) or (2)-Y ¹-R ¹,-Y ⁴-R ⁴Preferred embodiment be shown in the table 1-1, the table 1-2, but in the near-infrared-absorbing material of the present invention-Y ¹-R ¹,-Y ⁴-R ⁴Be not to be limited to this.And ,-Y ¹-R ¹And/or-Y ⁴-R ⁴In R ¹, R ⁴If aryl, then aryl-Y ¹-or-Y ⁴-the ortho position on when substituting group is arranged, can obtain the material good to the solvability of solvent, therefore preferred.

[table 1]

Table 1-1

Table 1-2

In addition, be preferred group-Y among following table 2-1, the table 2-2 ²-R ²-,-Y ³-R ³-example, but group-Y ²-R ²-,-Y ³-R ³-be not to be defined in example among table 2-1, the table 2-2.In addition, if-Y ²-R ²-,-Y ³-R ³-R ², R ³Be aryl, then aryl-Y ²-or-Y ³-the ortho position on have substituent words, just can obtain the material good to the solvability of solvent, therefore preferred.

[table 2]

Table 2-1

Table 2-2

In addition, in general formula (5)～(8), R ¹, R ⁴Be preferably and comprise above-mentioned table 1-1, the table material that 1-2 enumerated, the material of being recorded in and showing 3-1, showing 3-2.

[table 3]

Table 3-1

Table 3-2

And then, in general formula (5)～(8), R ², R ³Be preferably and comprise above-mentioned table 2-1, the table example that 2-2 enumerated, the example of being recorded in and showing 4-1, showing 4-2.R ², R ³Be preferably and comprise sulphur bridge (sulfido) key group, arylidene, heteroarylidene, alkylidene group.More preferably has sulphur bridge key group.

[table 4]

Table 4-1

Table 4-2

In general formula (1)～(8), A represents organic residue of directly combination or divalence.The organic residue of the divalence of A, for example can by arbitrary combination from-NHCO-,-CONH-,-NHCOO-,-OCONH-,-O-,-S-,-NH-,-COO-,-OCO-,-SO ₂-,-CO-,-C=C-,-N=N-,-S-S-, replace or unsubstituted arylidene, replace or unsubstituted heteroarylidene, replace or unsubstituted alkylidene group, and the group of selecting in replacement or the group that unsubstituted amino constituted forms, but preferably comprise the organic residue of divalence shown in the above-mentioned general formula (9), or comprise and replace or unsubstituted arylidene, replace or unsubstituted heteroarylidene, replace or unsubstituted alkylidene group, ether, sulphur bridge key group, the ammonia ester bond group, the amido bond group, carbonyl, ester group or amino, or the appropriate combination of described group.

Replacement or the unsubstituted arylidene of A in general formula (1)～(8) also can be replacement or unsubstituted arylidene arbitrarily.Arylidene preferably carbonatoms is 6～60 the monocycle or the arylidene of condensed ring, and more preferably carbonatoms is 6～40, and further preferred carbonatoms is 6～30 arylidene.Specifically can enumerate phenylene, diphenylene, naphthalene two bases, anthracene two bases, phenanthroline two bases, pyrene two bases, triphenylene two bases, benzo phenanthroline two bases, perylene two bases, pentaphene two bases, pentacene two bases etc., and described group also can have substituting group arbitrarily.

In addition, the replacement of A or unsubstituted heteroarylidene also can be replacement or unsubstituted heteroarylidene arbitrarily.It is 4～60 the monocycle or the aromatic heterocyclic group of condensed ring that heteroarylidene is preferably carbon element unit number, at least one the carbonatoms that more preferably comprises nitrogen-atoms, Sauerstoffatom or sulphur atom is 4～60 the monocycle or the aromatic heterocyclic group of condensed ring, and more preferably carbonatoms is 4～30 5 yuan or 6 yuan aromatic heterocyclic group.Concrete aromatic heterocyclic group can be enumerated and replace or unsubstituted pyrroles two base bases, furans two bases, inferior thienyl, pyridine two bases, pyridazine two bases, pyrimidine two bases, pyrazine two bases, quinoline two bases, isoquinoline 99.9 two bases, cinnolines two bases, quinazoline two bases, quinoxaline two bases, phthalazines two bases, pteridine two bases, acridine two bases, azophenlyene two bases, phenanthroline two bases etc., and described group also can have substituting group arbitrarily.

The replacement of A or unsubstituted alkylidene group also can be replacement or unsubstituted alkylidene group arbitrarily.Alkylidene group specifically can have been enumerated methylene radical, ethylidene, propylidene, butylidene, inferior sec-butyl, the inferior tertiary butyl, pentylidene, hexylidene, inferior 2-ethylhexyl, inferior heptyl, octylene, inferior iso-octyl, inferior octadecyl, inferior trichloromethyl, cyclohexylidene etc., and described base also can have substituting group arbitrarily.

In addition, the substituting group among the above-mentioned A can be enumerated and R ¹～R ⁴The identical material of material of middle explanation.

Following table 5-1, table 5-2 represent the example of A, but A is defined in this.

[table 5]

Table 5-1

Table 5-2

Among the present invention, the near-infrared-absorbing material that has with the repeating unit shown in general formula (1)～(8) can be mixture of polymers or non-conjugated polymeric thing, also can be conjugated polymers.In addition, near-infrared-absorbing material of the present invention also can be the homopolymer or the multipolymer that have with the repeating unit shown in general formula (1) and/or the general formula (2).With regard to multipolymer, can be the multipolymer of the different repeat units more than two kinds that repeating unit comprised shown in general formula (1) or the general formula (2), or by with repeating unit shown in general formula (1) or the general formula (2) and the multipolymer that repeating unit was become except that general formula (1) or general formula (2).Described multipolymer can be random copolymers, segmented copolymer or graft copolymers, and the polymer that also can have these configured intermediate for example has the random copolymers of block.As the copolymer composition outside the repeating unit shown in general formula of the present invention (1) or the general formula (2) is to have the terminal compound of polymerizability reaction, for example can enumerate the compound that has two-OH base in same intramolecularly at least, in same intramolecularly have halogen group and-compound of OH base, the compound that has a plurality of halogen groups in same intramolecularly, the compound that has a plurality of-COOH base in same intramolecularly, the compound that has a plurality of-COCl base in same intramolecularly, in same intramolecularly have-OH base and-compound of COOH base, has a plurality of-NH in same intramolecularly ₂The base compound, have-NH in same intramolecularly ₂The compound of basic reaching-COOH base etc.

If near-infrared-absorbing material of the present invention from thermotolerance, photostabilization viewpoint, is not particularly limited weight-average molecular weight, but for example by the gel permeation chromatography method in polystyrene conversion, be preferably about 1,000～10,000.

M in general formula of the present invention (1)～(8) still is preferably nickel, cobalt, platinum, palladium or copper, more preferably nickel so long as atoms metal then there is no specific restriction.

The R of general formula of the present invention (1)～(8) ¹And R ⁴Be preferably and replace or unsubstituted phenyl, replacement or unsubstituted thienyl, carbon number are replacement or unsubstituted alkyl below 20, R ²And R ³Be preferably replacement or unsubstituted phenyl, the replacement that comprises sulphur bridge key group or unsubstituted phenylene, replacement or unsubstituted inferior thienyl, the carbon number is replacement or the unsubstituted alkylidene group below 20.

In addition, above-mentioned general formula (1) and general formula (2), general formula (3) and general formula (4), general formula (5) and general formula (6), general formula (7) and general formula (8) respectively are constitutional isomer, can not use with making any distinction between, therefore any near infrared ray absorption that all can be used as uses, and also can be not use as the mixture of constitutional isomer discretely.In addition, also unit copolymerization that can be as required that the near-infrared absorbing scope is different, or the polymkeric substance that the near-infrared absorbing scope is different is mixed with each other.The concrete expression of table 6 is used for the used unitary example of structure of polymkeric substance, and still polymkeric substance of the present invention there is no and is defined in following representation example.In addition, because table 6 is only represented the structure of unit cell, do not represent its polymeric species.

[table 6]

Table 6

Near-infrared-absorbing material with repeating unit shown in general formula of the present invention (1) or general formula (2), general formula (3) or general formula (4), general formula (5) or general formula (6), general formula (7) or the general formula (8) can be made according to for example following synthesis type (scheme).

Wherein, the compound of the Formula B～E in the synthesis type for example can be according to Journal of AmericanChemical Society, 87:7, and the synthetic method of No. 5089585 communique record of April 5,1965 or United States Patent (USP) is made.In addition, the compound of general formula F～H can be made by the synthetic method that the spy opens 2005-232158 communique record.Q is equivalent to the part of A in general formula (1)～(8) in the formula.

＜synthesis type 1 〉

[changing 10]

＜synthesis type 2 〉

[changing 11]

＜synthesis type 3 〉

[changing 12]

＜synthesis type 4 〉

[changing 13]

＜synthesis type 5 〉

[changing 14]

＜synthesis type 6 〉

[changing 15]

＜synthesis type 7 〉

[changing 16]

＜synthesis type 8 〉

[changing 17]

Synthesizing in the above-mentioned synthesis type, for example carry out in the following manner.

(synthesis condition example)

Under nitrogen atmosphere, in dimethyl formamide, dimethyl sulfoxide (DMSO), methyl ethyl ketone isopolarity solvent,, be preferably and use 8 equivalents～20 equivalents to use NaOH, KOH, K to be 2 equivalents～50 equivalents with respect to B～H ₂CO ₃, Na ₂CO ₃, alkali such as triethylamine, arise from 40 ℃～150 ℃ with the glycol that contains Q, diamines, diacid chloride, dibromide one, be preferably heated and stirred in 50 ℃～100 ℃, then can synthesize compound with the repeating unit in the bracket.Filter out after the insolubles, in alcohols such as methyl alcohol, ethanol by recrystallization with its taking-up.

Have the near-infrared-absorbing material of repeating unit shown in described general formula (1) or (2) or comprise the near infrared ray absorption of the present invention of this kind near-infrared-absorbing material, so long as need the purposes of near-infrared absorbing, then can be used for any purposes, and its user mode, use-pattern are not subjected to the restriction of near-infrared-absorbing material structure yet.That is to say, near-infrared-absorbing material of the present invention or near infrared ray absorption can with optical absorption pigment or the UV light absorber such as other near infrared ray absorption except that the near-infrared-absorbing material that comprises repeating unit shown in general formula (1) or the general formula (2), complementary materials such as stablizer such as antioxidant use together, in addition, near-infrared-absorbing material of the present invention or near infrared ray absorption, can be dissolved in solvent together with these complementary compositions or be scattered in solvent or water in, or, necessary words can be dissolved in solvent together with adhesive resin etc. be scattered in solvent or water in and form near-infrared absorbing composition (coating agent), it is coated base material etc. can form near infrared ray and inhale layer, if adhesive resin can form self supportive film, also can coat on the separability base material and form after the film, come stripping film to be used as near-infrared absorbing film from the separability base material again.At this moment, coating composition can be oiliness, water-based, solution, pasty state.

In addition, replace forming as mentioned above near infrared ray absorption layer, also can in other functional layers such as tackiness agent or bond layer, UV-absorbing layer, hard coat, base material, contain near infrared ray absorption of the present invention, and make these layers have the near-infrared absorbing characteristic.For example, contain near-infrared-absorbing material of the present invention or near infrared ray absorption in adhering agent layer or the bond layer in order to make, adding near-infrared-absorbing material of the present invention or near infrared ray absorption in known tackiness agent or the adhesive composite in the past, just can obtain to have the tackiness agent or the caking agent of near-infrared absorbing characteristic, can use this have tackiness agent of near-infrared absorbing characteristic or adhesive coating or the adhesive linkage that caking agent forms near infrared ray absorbing, should be used as near-infrared absorbing film by layer.At this moment, words if necessary also can contain described other composition.In addition, if be necessary, also can be included in and form near infrared ray line absorption film or shaping thing in the shaping resin.Laminate or monomer film with the near infrared ray absorption layer that comprises described near-infrared-absorbing material of the present invention or near infrared ray absorption are preferred for optical filter.

As mentioned above, near-infrared absorbing composition of the present invention is by near-infrared-absorbing material of the present invention or near infrared ray absorption, with the pigment of employed other light absorption as required, stablizer, adhesive resin, solvent, tackiness resin, other ancillary component, as required be used to form other functional layer become to assign to constitute.

Described other light absorption pigment for example can have been enumerated cyanines system, quinoline system, coumarin series, thiazole system, oxonols (oxonol) is, Azulene system, side's acid (squarylium) is, azomethine system, azo system, Ben Yajiaji (benzylidene) is, xanthene (xanthene) is, phthalocyanine system, naphthalene cyanines system, naphthoquinones system, anthraquinone system, tritane system, two quaternary ammoniums (diimmonium) are, with the dithiacyclopentene metal complex based compound beyond the metal complex shown in described general formula (1) or (2) etc.

It itself is that the nickel complex pigment and/or the phthalocyanine of near infrared ray absorption is pigment and/or two quaternary ammoniums (diimmonium) pigment that above-mentioned other light absorption pigment is preferably.These other light absorption pigment is with respect near infrared ray absorption 100 weight parts of the present invention, to be preferably 20～500 weight parts, more preferably 50～200 weight parts to the addition of near infrared ray absorption of the present invention.Visible light transmissivity when preferred utilization merging absorption spectrum forms film is more than 70～80%, and the transmitance of near infra red region is below 10%.

Above-mentioned nickel complex pigment can be enumerated the pigment of the structure of following general formula (10), and these also can further form the ionization compound with the univalent positively charged ion.

General formula (10)

[changing 18]

[R in the formula ⁹～R ¹²Expression O or S or N].

Nickel complex pigment with above-mentioned general formula (10) structure specifically can have been enumerated American DyeSource, Ink (Laser Dyes﹠amp; Near Infrared Dyes) ADS845MC, the ADS870MC that is sold, ADS880MC, ADS890MC, ADS920MC, ADS990MC etc., but be not limited to these.

In addition, the example of the following general formula (11) preferably enumerated of naphthalene cyanines pigment.

General formula (11)

[changing 19]

(M ₁The expression atoms metal, R in the formula ¹³～R ²⁸Expression hydrogen atom or substituting group, M ₁Also can further have substituting group).

Particularly, イ one ェ Network ス power ラ one IR-10, IR-12, the IR-14 etc. that have Nippon Catalytic Chem Ind to make, but naphthalene cyanines pigment is not to be defined in these.

And then two quaternary ammoniums (diimmonium) pigment preferably comprises the material of the structure of following general formula (12).

General formula (12)

[changing 20]

(in the formula, X ^-Expression halide-ions, inorganic acid ion or organic acid ion).

In the above-mentioned general formula (12), as X ^-Halide-ions, for example can enumerate iodide ion, bromide anion, chlorion, fluorion etc.In addition, inorganic acid ion for example can have been enumerated hexafluoro-antimonic acid ion, high chloro acid ion, Tetrafluoroboric acid ion, phosphofluoric acid ion, nitrate ion etc.Organic acid ion for example can have been enumerated acetato-, trifluoroacetic acid ion, methanesulfonic ion, trifluoromethayl sulfonic acid ion, Phenylsulfonic acid ion, toluenesulphonic acids ion etc.IRG-022, IRG-023 that Japanese chemical drug limited-liability company makes, IRG-040 etc. for example can be enumerated in the commercial goods, but are not to be defined in these.

In addition, as being used near infrared ray absorption of the present invention or above-mentioned other light absorption pigment, to reach light or hot stability is the above-mentioned various stablizers of purpose, for example can enumerate hydroquinone derivatives (No. 3935016 specification sheets of United States Patent (USP), No. 3982944 specification sheets of United States Patent (USP)), quinhydrones monoether derivative (No. 4254216 specification sheets of United States Patent (USP)), phenol derivatives (spy opens clear 54-21004 communique), (UK Patent Application discloses specification sheets No. 2077455 for spiral shell indane (spiroindane) or methylene-dioxy benzene derivative, No. 2062888 specification sheets of English Patent), chroman (chroman), the derivative of spiral shell chroman (spiro chroman) or coumarane (No. 3432300 specification sheets of United States Patent (USP), No. 3573050 specification sheets of United States Patent (USP), No. 3574627 specification sheets of United States Patent (USP), No. 3764337 specification sheets of United States Patent (USP), the spy opens clear 52-152225 communique, the spy opens clear 53-20327 communique, the spy opens clear 53-17729 communique, the spy opens clear 61-90156 communique), the derivative of quinhydrones monoether or p-aminophenol (No. 1347556 specification sheets of English Patent, No. 2066975 specification sheets of English Patent, special public clear 54-12337 communique, the spy opens clear 55-6321 communique), 2,2 '-biphenol derivative (No. 3700455 specification sheets of United States Patent (USP), special public clear 48-31625 communique), metal complex (No. 4245018 specification sheets of United States Patent (USP), the spy opens clear 60-97353 communique), nitroso compound (spy opens flat 2-300288 communique), two quaternary ammonium compounds (No. 465612 specification sheets of United States Patent (USP)), nickel complex (spy opens flat 4-146189 communique), antioxidant (No. 820057 specification sheets of European patent) etc.In addition, in the optical filter of the present invention, as quenchers such as singlet oxygen (quencher), also can comprise aromatic series nitroso compound, ammonium salt (aminium), imonium salt (iminium) compound, two imonium salt (iminium) compound, transition metal chelate compound etc., and in the scope that does not hinder near infrared ray absorption effect of the present invention, also can use quencher ion such as two sulfo-diene metal complex negatively charged ion.

The additive capacity of the complementary light absorption pigment except near infrared ray absorption of the present invention that is used near infrared ray absorption of the present invention or various stablizers etc., for near infrared ray absorption 100 weight parts of the present invention, be preferably 20～200 weight parts, more preferably 50～150 weight parts.Visible light transmissivity when preferred utilization merging absorption spectrum forms film is more than 70～80%, and the transmitance of near infra red region is below 10%.

As mentioned above, near infrared ray absorption of the present invention can come together to form coating composition with adhesive resin as required.By this coating composition being applied on the base material, forming the layer that comprises near infrared ray absorption, can form laminate with base material.This laminate, for example optical filter, optical reflection plate, optical diffusing plate etc. be can be used in by selection base material kind, or agricultural near-infrared absorbing film, hot line blocking film, eye-protection glasses, sunglasses, electronics photograph photoreceptor etc. also can be used in.In addition, near infrared absorbent of the present invention also can be used as the recording medium that is used to utilize near-infrared absorbing heat, optical recording with pigment, optical character reading and recording with material, prevent secret document manifolding with layer, the near infrared ray absorption of laser welding waits and uses.

It is that resin, poly-(methyl) methyl acrylate are resin, acrylic resin, melmac, urethane resin, aromatic ester resin, polycarbonate resin, aliphatic poly olefin resin, aromatic series polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, PE modified resin, polychlorostyrene ethenoid resin, styrene-butadiene-copolymer, polystyrene resin, polyamide resin and these copolymer resins etc., but are not to be defined in this that described adhesive resin for example can be enumerated aliphatic ester.Also natural macromolecular materials such as gelatin, casein, starch, derivatived cellulose, alginic acid can have been enumerated in addition.These adhesive resins are to be that oiliness or water-based are selected suitable resin, multipolymer according to coating composition.

Constitute the organic solvent of oiliness coating agent, can enumerate halogen system, ethanol system, ketone system, ester system, fatty hydrocarbon system, fragrant hydrocarbon system, ether series solvent and these mixed solvent.In addition, as the coating agent modulator approach of water-based, for example can enumerate micronization processes near infrared ray absorption of the present invention obtain below several microns micropartical, make described micropartical be distributed to method in the undyed acrylic acid polymer emulsion.

Near-infrared absorbing composition of the present invention also can use the tackiness tackiness agent to be used as tackiness agent as under the situation of tackiness agent.As the tackiness tackiness agent, acrylic acid series, ammonia ester system, rubber system etc. can have been enumerated.As the monomer that can be used as acrylic acid series, can enumerate Acrylic Acid Monomer, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, (methyl) vinylformic acid heptyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester, (methyl) vinylformic acid heneicosyl ester, (methyl) vinylformic acid docosyl ester, (methyl) vinylformic acid etc.In order to obtain the physical properties as the hope of tackiness agent, these can suitably select two or more alone or in combination the use.In the present invention, aspect the rerum natura of guaranteeing to adhere, consider, preferably be that 4～12 acrylic monomer assigns to be used as being copolymerized into, and more preferably (methyl) butyl acrylate, (methyl) 2-EHA assigned to be used as being copolymerized into carbonatoms.

With regard to above-mentioned tackiness tackiness agent, the weight-average molecular weight (Mw) that co-polypropylene acid is monomer, have formed acrylic copolymers such as the acrylic monomer of oxirane chain and other monomer is preferably 5～1,000,000, the based copolymer of 5～200,000 low molecular weight propylene acid more preferably.

And then, comprise tackiness tackiness agent and the formed tackiness agent of near infrared ray absorption of the present invention, be to utilize known method to be applied on the base material and form tackiness agent thin slice as laminate.In this employed base material, except the base material that the back is narrated, also can use paper, metal, cloth etc.In addition, if when the tackiness tackiness agent can constitute thin slice separately, then form the tackiness agent thin slice that does not need base material.In addition, also can be the form that tackiness agent is arranged in the two sided coatings of base material.But, also can be that the tackiness agent of wherein one side does not comprise the situation of tackiness agent of the present invention.

Near infrared ray absorption of the present invention is to the addition of the adhesive resin that contains the tackiness adhesive resin, and the addition of near infrared ray absorption is preferably 0.01～20 weight part for described resin 100 weight parts, more preferably 0.1～15 weight part.When if this ratio is lower than 0.01 weight part, the effective wavelength light of absorption near infrared ray scope just then, in addition, the infringement transparency sometimes (visible rays perviousness) if will reduce the dispersiveness of near infrared ray absorption when surpassing 20 weight parts.

Adhesive composite in the present invention is the work material with near infrared ray absorbing that comprises near infrared ray absorption of the present invention and caking agent.And as the adhesive composite of near-infrared absorbing composition of the present invention, be can be with near-infrared-absorbing material of the present invention by dissolving or be distributed to modulate in the suitable medium with cementability and form.

Near-infrared-absorbing material of the present invention or near infrared ray absorption preferably can be used as the pigment that constitutes optical filter and use.And the method for formation optical filter, for example can enumerate, with near-infrared-absorbing material of the present invention or near infrared ray absorption, above-mentioned other light absorption pigment or various stablizer, the method that in base material that constitutes optical filter or random layer, contains, be coated on the method on base material or the random layer, be mixed into the method in the polymer binder of each interlayer or caking agent, the jointing material, will comprise near infrared ray absorption layer such as near infrared ray absorption of the present invention and be arranged on method of above-mentioned each layer etc. in addition.In forming under the situation of near infrared ray absorption layer on the base material, following coating also can be set on base material as required, prevent each layers such as reflecting layer, hard coat, lubricant film.Near infrared ray absorption of the present invention is can preferably be used in constituting to sneak into the method that polymer binder or caking agent, tackiness agent are provided with near infrared ray absorption layer between the optical lightscreening lamella.

Near-infrared-absorbing material of the present invention or near infrared ray absorption are used under the situation of optical filter, and its usage quantity is that the per unit area content of optical filter is generally 1～1000mg/m ², be preferably 5～100mg/m ²If usage quantity is lower than 1mg/m ²Situation under just can't give full play to the near-infrared absorbing effect, and if usage quantity surpasses 1000mg/m ²Situation under, then the tone of spectral filter is crossed by force and probably and can be reduced display quality etc., and then, the reduction of lightness may appear, therefore be unfavorable.

For example can enumerate inorganic materials such as glass as above-mentioned substrate material; Or cellulose ester such as diacetyl cellulose, tri acetyl cellulose (TAC), propionyl Mierocrystalline cellulose, butyryl radicals Mierocrystalline cellulose, ethanoyl propionyl Mierocrystalline cellulose, Nitrocellulose; Polymeric amide; Polycarbonate; Polyethylene terephthalate, PEN, polybutylene terephthalate, poly--1,4-hexanaphthene ethylidene terephthalate, polyoxyethylene glycol-1,2-biphenoxyl ethane-4, polyester such as 4 '-dicarboxylic ester, polybutylene terephthalate; Polystyrene; Acrylic resins such as polyolefine such as polyethylene, polypropylene, polymethylpentene, polymethacrylate; Polycarbonate; Polysulfones; Polyethersulfone; Polyetherketone; Polyetherimide; Macromolecular materials such as polyoxyethylene.If as the words of optical filter purposes then base material be preferably transparent supporting body, the transmitance of transparent supporting body is preferably more than 80%, further preferably surpasses 86%.Mist value (Haze) is preferably below 2%, more preferably below 1%.Specific refractory power is preferably 1.45～1.70.

In these the base material, can add light absorption pigment, antioxidant, photostabilizer, UV light absorber, inorganic fine particles etc. as required, in addition, can carry out various surface treatments these base materials.

Above-mentioned inorganic fine particles can be enumerated inorganic fine particles such as silicon-dioxide, titanium dioxide, barium sulfate, lime carbonate, talcum, kaolin.In addition, medicine processing, mechanical treatment, Corona discharge Treatment, flame treating, uviolizing processing, high frequency processing, glow discharge processing, active plasma treatment, laser treatment, mixing acid processing, ozone Oxidation Treatment etc. can have been enumerated as above-mentioned various surface treatments.

Above-mentioned coating down is, contain in setting under the situation of near infrared ray absorption layer of near-infrared-absorbing material of the present invention or near infrared ray absorption, be used in the layer between base material and the near infrared ray absorption layer for the tackiness that will improve base material and near infrared ray absorption layer etc.Above-mentioned down coating be contain second-order transition temperature be the surface of-60 ℃～60 ℃ polymer layer, near infrared ray absorption layer side be quarry-faced layer or contain polymkeric substance with near infrared ray absorption layer have affinity polymkeric substance layer.In addition, at the substrate surface that is not provided with near infrared ray absorption layer coating down can be set, thereby improve base material and the bonding force that is arranged at the layer (for example preventing reflecting layer, hard coating layer) on the base material, in addition, following coating also can be designed for and improve adhesion optical filter and the tackiness agent of image processing system and the affinity of optical filter.The thickness of following coating is preferably 2nm～20 μ m, 5nm～5 μ m more preferably, and 20nm～2 μ m more preferably, 50nm～1 μ m more preferably most preferably is 80nm～300nm again.Comprise second-order transition temperature and utilize the tackiness adhesion base material and the near infrared ray absorption layer of polymkeric substance for the following coating of-60～60 ℃ polymkeric substance.Second-order transition temperature is that-60～60 ℃ polymkeric substance can be resultant by the polymerization or their copolymerization of for example vinylchlorid, Ethylene Dichloride, vinyl-acetic ester, divinyl, chloroprene rubber, vinylbenzene, chloroprene, acrylate, methacrylic ester, vinyl cyanide or methylvinylether.Above-mentioned second-order transition temperature is preferably below 50 ℃, and is more preferably below 40 ℃, further preferred below 30 ℃, further preferred below 25 ℃ again, most preferably below 20 ℃.Following coating is preferably 1～1000MPa in 25 ℃ spring rate, and more preferably 5～800MPa especially is preferably 10～500MPa.The surface is formed with near infrared ray absorption layer for quarry-faced coating down on asperities, thus adhesion base material and near infrared ray absorption layer.And the surface can easily form by the coated polymeric latex for quarry-faced coating down.The median size of latex is preferably 20nm～3 μ m, more preferably 50nm～1 μ m.As binder polymer the polymkeric substance of affinity is arranged, can enumerate acrylic resin, derivatived cellulose, gelatin, casein, starch, polyvinyl alcohol, soluble nylon, high molecular emulsion etc. with near infrared ray absorption layer.In addition, following coating more than 2 also can be set in optical filter of the present invention.In following coating, also can add and allow base material swollen solvent, matting agent, tensio-active agent, static inhibitor, coating additive or hard coat agent etc.

In addition, in the reflecting layer low-index layer must be arranged in above-mentioned preventing.The specific refractory power of low-index layer is lower than the specific refractory power of above-mentioned transparent supporting body.The specific refractory power of low-index layer is preferably 1.20～1.55, and more preferably 1.30～1.50.The thickness of low-index layer is preferably 50～400nm, more preferably 50～200nm.Low-index layer can (spy opens clear 57-34526 number as the floor that comprises the low fluoropolymer of specific refractory power, Te Kaiping 3-130103 number, Te Kaiping 6-115023 number, Te Kaiping 8-313702 number, Te Kaiping 7-168004 number communique record), by colloidal sol-(spy opens flat 5-208811 number to solidify the formed floor of (Sol-Gel) method, Te Kaiping 6-299091 number, Te Kaiping 7-168003 number communique is put down in writing) or comprise the particulate sublayer (special public clear 60-59250 number, Te Kaiping 5-13021 number, Te Kaiping 6-56478 number, Te Kaiping 7-92306 number, each communique record of Te Kaiping 9-288201 number) forms.In comprising atomic layer, can in low-index layer, form the space and be used as micropore between micropartical or in the micropartical.Comprise atomic layer and preferably have the voidage of 3～50 volume %, be more preferably voidage with 5～35 volume %.

In order to prevent the reflection of wide wavelength region, except preventing to add in the reflecting layer the low-index layer the preferred higher layer (middle and high index layer) of lamination specific refractory power in above-mentioned.The specific refractory power of high refractive index layer is preferably 1.65～2.40, and more preferably 1.70～2.20.In the specific refractory power of index layer be adjusted into the intermediate value of the specific refractory power of the specific refractory power of low-index layer and high refractive index layer.In the specific refractory power of index layer be preferably 1.50～1.90, more preferably 1.55～1.70.The thickness of middle and high index layer is preferably 5nm～100 μ m, and more preferably 10nm～10 μ m most preferably are 30nm～1 μ m.The mist value of middle and high index layer is preferably below 5%, more preferably below 3%, most preferably is below 1%.Middle and high index layer can use the polymer binder that has than higher specific refractory power to form.As the higher polymkeric substance of specific refractory power, can enumerate polystyrene, styrol copolymer, polycarbonate, melmac, phenolic resin, Resins, epoxy, with ring-type (ester ring type or aromatic series) isocyanic ester and the formed urethane of polyol reaction etc.The polymkeric substance or the halogen atom that has except that fluorine element of ring-type (aromatic series, hetero ring type, ester ring type) base with other is also very high as the specific refractory power of substituent polymkeric substance.Also can use by importing two keys by the formed polymkeric substance of the monomer polymerization of free-radical curable.

And then, in order to obtain higher specific refractory power, also can in polymer binder, disperse inorganic fine particles.The specific refractory power of inorganic fine particles is preferably 1.80～2.80.Inorganic fine particles is preferably formed by metal oxide or sulfide.As metal oxide or sulfide, for example can enumerate sons such as titanium oxide (for example mixed crystal, anatase octahedrite, the non-crystal structure of rutile (rutile), rutile/anatase (Anatase)), stannic oxide, Indium sesquioxide, zinc oxide, zirconium white, zinc sulphide.Be preferably titanium oxide, stannic oxide and Indium sesquioxide in these.The main component of inorganic fine particles is exactly the oxide compound or the sulfide of these metal, can comprise other element.In this, the meaning of so-called main component is the maximum composition of amount (weight %) in constituting the inorganic particles subconstiuent.And other element can have been enumerated examples such as Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S.In addition, also can utilize the overlay film plasticity and can be scattered in and form middle and high index layer in the solvent, or its use this as aqueous inorganic materials for example various elements alkoxide, organic acyl chlorides, combine the coordination compound (for example chelate compound) of formation, active inorganic polymer etc. with the coordination compound and also can form middle and high index layer.

Above-mentionedly prevent to have in the surface, reflecting layer cloudy surface and handle (anti-glare) function (allow the incident light scattering and prevent that scenery around the film is displaced to the function of film surface) in the surface.Prevent the reflecting layer thereby for example on the surface of transparent film, be formed with trickle concavo-convex on the surface, being formed with, or form and to prevent after the reflecting layer, form on the surface by the embossing cylinder more concavo-convex, thereby the reflecting layer that prevents that obtains having the cloudy surface processing capacity.The reflecting layer that prevents with cloudy surface processing capacity has 3～30% mist value usually.

Above-mentioned hard coating layer has the hardness higher than the hardness of transparent supporting body.Hard coating layer preferably comprises crosslinked polymkeric substance.And hard coating layer can use polymkeric substance, oligopolymer or the monomer (for example ultraviolet curing resin) of acrylic acid series, ammonia ester system, epoxy system to be formed.In addition, also can form hard coating layer by the silicon-dioxide based material.

Also can form lubricant film in above-mentioned preventing on the surface, reflecting layer (low-index layer).Lubricant film has the function of giving smoothness and improving resistance to rupture on the low-refraction laminar surface.Lubricant film can use organopolysiloxane (for example silicone oil), natural cured, oil is cured, higher fatty acid metal-salt, fluorine base lubricant or derivatives thereof form.The thickness of lubricant film is preferably 2～20nm.

Above-mentioned near infrared ray absorption layer, down coating, prevent that reflecting layer, hard coating layer, lubricant film etc. from can form by common coating process.Coating process can be enumerated infiltration coating method (dip coating), airblade coating method (air-knife coaing), curtain formula coating method (curtain coating), cylinder coating method (rollcoating), wire bar coating method (wire bar coating), intaglio plate coating method (gravure coating), use extrusion process (extrusion) method (with reference to No. 2681294 specification sheets of United States Patent (USP)) of funnel (hopper) etc.Also can by synchronous coating form more than 2 the layer.The patent of relative synchronous coating method records United States Patent (USP), and " coating engineering " the 253rd page (1973 towards the distribution of storehouse bookstore) shown in No. 2761791, each specification sheets and former rugged brave Mr. of No. the 2941898th, United States Patent (USP), No. the 3508947th, United States Patent (USP), No. the 3526528th, United States Patent (USP).

If near-infrared-absorbing material of the present invention is used in the welding of resin material, can engage by the tone difference that laser radiation is dwindled between resin material, in addition, really welding to each other contact surface and obtain sufficient adhesion strength.That is to say,, be extensive use of the part that resin forming article is used as various fields such as auto parts in recent years from the viewpoint of lightweight and cost degradation.In addition, from the ideas such as high production of resin forming article, frequent employing is divided into resin forming article a plurality of parts in advance and is shaped, and then bonding these are cut apart the means of shaping thing mutually.Bonding between resin material, undertaken by subordinate's laser welding method: coinciding mutually has the perviousness resin material of perviousness and laser is had after the absorbefacient absorbent resin material laser in the past, coming the binding surface of heating and melting perviousness resin material and absorbent resin storeroom from described perviousness resin material one side by the irradiation of laser, is one with both by welding.And then, in the laser thawing method in the past, during of the same race or different types of resin component element engages, because engaged resin component element is for having two kinds of absorbefacient resin component element and non-absorbent resin component elements to laser, so on tone, will produce error, thus to bonding resin component element use limit to some extent.Particularly, for laser, non-absorbent resin material is that white or transparent laser see through look, and absorbefacient member is the laser absorption look of black series such as carbon black, so will produce apparent inharmonious.The resin material of bonding different colours like this that is to say, if can feel that not only the relatively poor while of surface bonding power also can produce the very eye-catching problem of adhesive portion.

If use material of the present invention, the binding surface that will arrive the absorbent resin material by the laser in the perviousness resin material is absorbed, and is saved as a kind of energy by the laser that binding surface absorbed.As a result, not only can heat and dissolve the binding surface that absorbs resin material, also can come the binding surface of heating and melting perviousness resin material simultaneously by thermal conduction from the binding surface of this absorbent resin material.Under this state, if the binding surface of crimping perviousness resin material and absorbent resin storeroom just can be bonded as one both.This material is because visible light transmissivity is good, so can dwindle aberration with the laser-transmissible resin material, owing in the absorption of near infra red region, have bigger molar absorptivity, can come the binding surface of certain welding perviousness resin material and absorbent resin storeroom and then a kind of resin combination with abundant bonding strength can be provided in addition by irradiating laser.

If use optical filter of the present invention, can effectively see through the visible rays of sunlight and can stop hot line really.In addition, because good endurance, so even long-term exposure can not damaged the hot line blocking capability yet in sunlight.

Optical filter of the present invention can suitably be used for the vision sensitivity correction spectral filter of the CCD (for example by electrooptical device that silicon photo diode constituted) of camera (image input unit).Here, " the vision sensitivity correction spectral filter that is used for CCD " the vision sensitivity correction spectral filter in the light path that is configured in CCD separately, also comprises cover plate, lens and protecting sheet etc.In addition, Kamera, digital camera, minicam (board camera), color scanner, colour facsimile apparatus, color copy machine, colour photophone device etc. for example can have been enumerated as the camera that carries CCD.If by carrying the words of the camera that optical filter of the present invention produces, just the incident light toward CCD (silicon photo diode) substantially can be limited in the light of visual range, the result just can carry out the reproduction that correct photometry (exposing operation) can not hinder red part simultaneously.

Optical filter of the present invention can suitably be used in the vision sensitivity correction spectral filter as the camera (image input unit) that carries CMOS image sensor or artificial nethike embrane.Utilization possesses to be had the CMOS of optical filter of the present invention image sensor and artificial nethike embrane and is equipped with these formed device for image, can produce the effect identical with above-mentioned CCD.

In addition, optical filter of the present invention can suitably be used in the noise filter in the employed environment of infrared communications set (is the communicator of medium with 850～950nm light wave).If by relevant noise filtering light device, will cover near infrared generation source (for example automatically-controlled door, telepilot etc. use near infrared machinery), blocking is from the infrared rays in described generation source, thus the noise that produces in can preventing from really to communicate by letter.

In addition, by optical filter of the present invention being arranged on the front of the panel of plasma display apparatus or liquid crystal panel displays device, can effectively remove the near infrared ray that shines out from described panel.As a result, can in around the described display equipment, not produce because the flase operation of the telepilot that the near infrared ray factor caused etc. yet.

Optical filter of the present invention preferably disposes as the spectral filter that the spectral filter of indicating meter special use or CCD, CMOS image sensor are used, and its collocation method is without any restriction.

And then, but LED is high-level efficiency and high brightness luminescent and can utilize in each field at present by the RGB three primary colors.But, because it is the pyrotoxin that is used for producing bigger energy, so use the machine of this type of diode to have the problem that often is exposed under the high temperature.The reason of heating causes because of radiant heat, the infrared rays of diode.Near-infrared-absorbing material of the present invention and near infrared ray absorption since its not only near-infrared absorbing is effective but also have higher visible light see-through, just can not stop infrared rays so do not need to change the LED illuminant colour.In addition, owing to itself have the hot and high-light-fastness of anti-height, even in LED, use this material also can not reduce the near-infrared absorbing ability for a long time.Like this, the LED composition of near-infrared-absorbing material of the present invention and near infrared ray absorption is arranged, can suppress the heat that the LED lumination of light emitting diode is produced by use.

In addition, very in voguely recently utilize the mark that irradiation produces of laser light to be used as simple and effective marking method.Utilize this laser light of irradiation to produce in the marking method, the part of light-struck literal of laser or illustration shape can change color because of thermal energy, or just can distinguish literal or illustration according to scattered light.

But for example special open flat 9-302236 communique and disclose the resin combination that will comprise colourless pigment, color development ancillary component and thermoplastic resin and be shaped after, the irradiation by laser light just can produce laser labelling again.But the heat when stirring by mixing can cause the reaction of color development composition, so limit the degree of freedom of color development composition and restriction color development.In addition, the spy opens flat 11-92632 communique and has put down in writing for containing copper based compound and the nickel series compounds Resins, epoxy as chromogenic reagent, by the irradiation of laser light, forms the technology of laser labelling on the surface of resin forming product.But this situation is defined in the mark of black.Te Kaiping 8-120133 communique has been put down in writing and cooperated the black resin combination that can form color laser marking that waits compound and obtain of titanium in the reinforcing rubber ethenoid resin, but resin is defined in the reinforcing rubber ethenoid resin in this case, and the application scope is also limited to some extent.

Material of the present invention is owing to have high visible transmittance and high near-infrared absorbing ability, so can utilize the active energy beam of low output to carry out mark and provide the transparency high marking composition.In addition, also can be with both simple and quick a kind of distinctnesses and at a high speed and the literal of high degree of accuracy or the figure of illustration of marking.

Embodiment

Below, will describe the present invention in detail by Production Example and embodiment.But the present invention will not be subjected to the qualification of following examples etc.

Synthesizing of [Production Example 1] compound 1

[changing 21]

Compound 1

Under nitrogen gas stream, in four-hole boiling flask, add a hydration phenyl oxalic dialdehyde (glyoxal) (4.56g, 30mmol), bromo ethyl phenenyl (11.1g, 60mmol), ethylene dichloride 60ml,, in room temperature, stirred 3 hours to wherein slowly dripping titanium tetrachloride (8.54g, 45mmol).After adding the entry extraction after reaction finishes, evaporate, utilize the hexane recrystallization, form above-claimed cpd 1.Yield is 46%.

Synthesizing of [Production Example 2] compound 2

[changing 22]

In 4 mouthfuls of flasks, add and utilize 1 synthetic benzoin of Production Example derivative compound 1 (3.0g, 9.4mmol), thiophosphoric anhydride (12.53g, 28.2mmol), dioxan 50ml, refluxed 2 hours down in nitrogen environment.Filter after the reaction, in filtered liquid, add NiCl ₂.6H ₂O (1.12g, the 4.7mmol) aqueous solution carries out 2 hours backflow once more.After reaction finishes, add water, methyl alcohol, reclaim above-claimed cpd 2 through filtering after the stirring after a while.Yield is 45%.

[Production Example 3] P-1's is synthetic

[changing 23]

In 4 mouthfuls of flasks, add and utilize 2 synthetic compounds 2 of Production Example (0.8g, 1.06mmol) and dihydroxyphenyl propane (0.24g, 1.06g) and K ₂CO ₃(1.16g, 8.44mmol), DMF40ml stirred 8 hours down for 80 ℃ in nitrogen environment.Reaction finishes after-filtration evaporates, and it is splashed in water/methyl alcohol=1/2 solution then, adds a spot of HCl aqueous solution again and cleans.Reclaim object P-1 after filtering.Yield is 50%.

Fig. 1 represents the absorption spectrum of P-1 in chloroform.As can be seen from Figure 1, P-1 can absorb less visible light and have bigger absorption near infra red region.

Synthesizing of [Production Example 4] compound 3

[changing 24]

Compound 3

Under nitrogen gas stream, in four-hole boiling flask, add 3,5-dimethylphenyl oxalic dialdehyde (70g, 388mmol), bromo ethyl phenenyl (72g, 388mmol), ethylene dichloride 500ml, to wherein slowly dripping titanium tetrachloride (110g, 583mmol), in room temperature, stirred 3 hours.After adding the entry extraction after reaction finishes, evaporate, utilize the hexane recrystallization, form above-claimed cpd 3.Yield is 60%.

Synthesizing of [Production Example 5] compound 4

[changing 25]

Compound 4

In 4 mouthfuls of flasks, add and utilize 4 synthetic benzoins of Production Example derivative compound 3 (50g, 94mmol), thiophosphoric anhydride (12.5g, 56mmol), dioxan 200ml, refluxed 2 hours down in nitrogen environment.Filter after the reaction, in filtered liquid, add NiCl ₂.6H ₂O (11.2g, the 47mmol) aqueous solution carries out 2 hours backflow once more.Reaction finishes the back and adds water, methyl alcohol, filters after stirring after a while, reclaims above-claimed cpd 4.Yield is 45%.

[Production Example 6] P-23's is synthetic

[changing 26]

In 4 mouthfuls of flasks, add and utilize 5 synthetic compounds 4 of Production Example (1.5g, 1.8mmol), decanediol (0.32g, 1.8mmol), K ₂CO ₃(1.16g, 8.44mmol) and DMF (dimethyl formamide) 40ml stirred 8 hours down for 80 ℃ in nitrogen environment.Reaction finishes after-filtration, evaporates, and then it is splashed in the solution of water/methyl alcohol=1/2, adds a spot of HCl aqueous solution again and cleans.Reclaim the above-mentioned P-23 of object after filtering.Yield is 50%.

[embodiment 1]

Measure the solubleness in toluene of P-23 of P-1, Production Example 6 gained of following compound 5, compound 6 (opening flat 2-264788 communique) and Production Example 3 gained with reference to the spy.It the results are shown in table 3.

[changing 27]

Compound 5 compounds 6

[table 7]

Table 7

Material	Solubleness in toluene (wt%)
		Compound 5	0.8
Compound 6	2.0
		P-1	5.0
P-23	6.0

As shown in Table 7, compare P-1 of the present invention and P-23 solvability excellence with compound 5, compound 6.

[embodiment 2]

In polystyrene (Mw=100, the 000) solution (solvent toluene) of each solid part 25%,, coat the PET film to be about 2% to come mixing cpd 5, compound 6, P-1 and P-23 with respect to solid part.Mensuration by following＜mist value〉detect the mist value of these films.It the results are shown in table 4.

The mensuration of＜mist value 〉

The mensuration of mist value utilizes the Haza Mater NDH2000 of NIPPON DENSHOKU system to carry out.

[table 8]

Table 8

Material	The mist value
		Compound 5	6.0
Compound 6	3.5
		P-1	2.0
P-23	1.5

By above-mentioned table 8 as can be known, compare with compound 5, compound 6, P-1 and P-23 have lower mist value.This result means that intermiscibility, solvability P-1 and the P-23 for resin is better than other material.

[embodiment 3]

Polystyrene (Mw=100 in each solid part 25%, 000) in the solution (solvent toluene), being about 1.0% to come mixing cpd 5, compound 6, P-1 and P-23 with respect to solid part, in addition, each mixes 2% two quaternary ammoniums (diimmonium) pigment (Japanese chemical drug joint-stock company make IRG-022), coats the PET film.These films are measured the mist value with the method identical with embodiment 2.It the results are shown in table 9.

[table 9]

Table 9

Material	The mist value
		Compound 5	2.0
Compound 6	1.5
		P-1	0.8
P-23	0.8

By above-mentioned table 9 as can be known, compare with compound 5, compound 6, P-1 and P-23 have lower mist value.

[embodiment 4]

Acrylic acid series sticky material (monomer composition: butyl acrylate 60%, isobutyl acrylate 30%, vinylformic acid 3%, ethyl acrylate 7% in each solid part 25%, solvent composition: ethyl acetate 80%, toluene 20%) in, to be about 2.0% to come mixing cpd 5, compound 6, P-1 and P-23 with respect to solid part, coat the PET film.Detect the mist value for these films with the method identical with embodiment 2.It the results are shown in table 10.

[table 10]

Table 10

Material	The mist value
		Compound 5	8.0
Compound 6	4.5
		P-1	2.5
P-23	2.0

By above-mentioned table 10 as can be known, compare with compound 5, compound 6, P-1 and P-23 have lower mist value.

[embodiment 5]

In polymethylmethacrylate (Mw=100, the 000) solution (solvent toluene) of 25% solid part, to be about 2% to mix P-1 and P-23 with respect to solid part, coat the PET film after, carry out 3 minutes dryings with 80 ℃.These films are carried out 48 hours moisture-proof heat experiment, mist value, the form and aspect (y value) of each film before and after the test experience under the condition of 100 ℃ of humidity 90%, temperature.Calculate the changing value (Δ y) of experiment front and back for form and aspect.It the results are shown in table 11.Wherein, the detection of mist value is carried out with the method identical with embodiment 2, and the detection of form and aspect (y value) is undertaken by following method.

The detection of＜form and aspect (y value) 〉

The detection of form and aspect (y value) is that the color colour-difference meter CR-300 with the MINOLTA system carries out.

[comparative example 1]

Two (3-methacryloxypropyl) phosphonic acids of thorough mixing 19g, the methyl methacrylate of 50g, the Diethylene Glycol dimethacrylate of 30g, the alpha-methyl styrene of 2.0g, in this mix monomer, add the dry-out benzene Tubercuprose of 5.0g, mix stirring down in 60 ℃ of environment, can obtain uniform blue mixing solutions.In this mixing solutions, add 3.4 parts of radical initiator tert-butyl hydroperoxide-2-ethylhexanoate, filter with glass filter.Each makes its cast poymerization with 50 ℃ 15 hours, 70 ℃ 8 hours, 100 ℃ heating that heat up in 2 hours.It is the tabular of 1mm that formed polymkeric substance is cut into thickness, and lapped face is made into optical filter (opening the 2000-98130 communique with reference to the spy) at last.For this spectral filter, under the condition of 100 ℃ of humidity 90%, temperature, carry out 48 hours moisture-proof heat experiment, with method similarly to Example 5, measure or calculate mist value, the foxy value (Δ y value) of each film before and after the experiment.It the results are shown in table 11.

[table 11]

Table 11

Spectral filter	Mist value (before the test)	Mist value (test back)	Δ y value
				P-1	2.0	2.2	0.001
P-23	1.36	1.41	0.001
				Comparative example 1	3.70	6.5	0.03

Learn from table 11, the mist value of the spectral filter of use P-1 and P-23 is littler than the mist value of spectral filter in the comparative example 1, and then, use the mist value of the spectral filter of P-1 and P-23 before and after experiment, almost not change, and the mist value of comparative example increases after experiment a lot, and P-1 and P-23 mist value compared to comparative example changes smaller as can be known.In addition, learn that foxy value (Δ y value) also is that the value of P-1 and P-23 is little from table 11.In addition, the spectral filter of comparative example 1 is known CCD in the past, the used spectral filter of CMOS, is learnt by The above results, compares the less and weather resistance of spectral filter mist value of the present invention with the spectral filter that in the past CCD, CMOS use.

Synthesizing of [Production Example 7] compound 7

[changing 28]

Compound 7

Under nitrogen environment, for potassium isopropyl xanthate (25g, 143mmol), acetone 80ml, add methyl dichloroacetate (10.2g, 71.5mmol), carry out refluxing in 5 hours and stir.Reaction is returned to room temperature after finishing, and filters, removes solvent, in 0 ℃～5 ℃ formed paste is splashed in the 1.5L vitriol oil.Rise again to room temperature, inject the frozen water of 4L at leisure thereafter.Cross filter solid,, obtain above-claimed cpd 7 by the formed paste of recrystallizing methanol.Yield is 75%.

Synthesizing of [Production Example 8] compound 8

[changing 29]

Compound 8

With respect to compound 7 (5g, 24mmol), in nitrogen environment,, add the NaOCH of 1M in below 20 ℃ ₃/ CH ₃OH (48ml, 48mmol) carries out stirring in 10 minutes.To wherein adding dibromo-propanol (5.2g, 24mmol)), after carrying out stirring in 3 hours under the room temperature, inject 300ml water, extract with chloroform.Extraction liquid is sloughed solvent, carry out recrystallization with methyl alcohol (methanol) again, obtain compound 8.Yield is 80%.

Synthesizing of [Production Example 9] compound 9

[changing 30]

Compound 9

Under 60 ℃ of nitrogen environments, will utilize 8 synthetic compounds 8 of Production Example (5g, 21mmol), sodium methylate (3.4g, 63mmol) and methyl alcohol (250ml) to stir.In reaction solution, add the Nickel dichloride hexahydrate (5g, 21mmol) be dissolved in the 100ml methyl alcohol afterwards, stir with 60 ℃ and return to room temperature after 4 hours.In reaction solution, add 1%HCl aqueous solution 50ml, stir, filter, obtain compound 9.Yield is 68%.

[Production Example 10] P-43's is synthetic

[changing 31]

In four-hole boiling flask, add with 9 synthetic compounds 9 of Production Example (1.5g, 3.1mmol), dibromo-decane (0.9g, 3.1mmol), K ₂CO ₃(1.16g, 8.44mmol) and dimethyl formamide (DMF; 40ml), stirred 8 hours down in 80 ℃ of nitrogen environments.Filter, evaporate filtered liquid after reaction finishes, with its solution that splashes into water/methyl alcohol=1/2, add a spot of HCl aqueous solution, the washing reaction thing filters and is recovered to the above-mentioned P-43 of object.Yield is 50%.

[embodiment 6]

Polymethylmethacrylate (Mw=200 in each solid part 25%, 000) solution (solvent: ethyl acetate/toluene 1: 1), to be about 2% to mix following compound 10, compound 11 (opening the 2005-232185 communique), compound 12 (with reference to No. 3699464 communique of patent) and P-43 with respect to solid part, coat the PET film with reference to the spy.For these films, with 100 ℃ of heat-resistant experiments that carry out 400 hours and 800 hours respectively,, measure the transmitance of the very big absorbing wavelength of compound for each film before and after the experiment, calculate its difference (Δ T).It the results are shown in table 12.

[changing 32]

Compound 10 compounds 11 compounds 12

[table 12]

Table 12

	Compound 10	Compound 11	Compound 12	P-43
					400 hours Δ T (%)	10	17	11	5
800 hours Δ T (%)	20	19	17	8

Learn by table 12, compare P-43 good heat resistance of the present invention with compound 10, compound 11, compound 12.

[embodiment 7]

Acrylic acid series sticky material (monomer composition: butyl acrylate 60%, isobutyl acrylate 30%, vinylformic acid 3%, ethyl acrylate 7% in each 25% solid part, solvent composition: ethyl acetate 80%, toluene 20%) in, to be about 2.0% to come mixing cpd 10, compound 11, compound 12 and P-43 with respect to solid part, coat the PET film.For these films, under 80 ℃ of temperature, humidity 80% condition, carry out the moisture-proof heat experiment of 24 hours and 48 hours respectively, for each film before and after the experiment, measure the transmitance of the very big absorbing wavelength of compound, calculate its difference (Δ T).It the results are shown in table 13.

[table 13]

Table 13

	Compound 10	Compound 11	Compound 12	P-43
					24 hours Δ T (%)	20	15	30	9
48 hours Δ T (%)	32	21	42	12

Learn by table 13, compare the good heat resistance of P-43 of the present invention in tackiness agent with compound 10, compound 11, compound 12.

[embodiment 8]

Polymethylmethacrylate (Mw=200 in each 25% solid part, 000) solution (solvent: ethyl acetate/toluene=1: 1), being about 2% to come mixing cpd 10, compound 11, compound 12 and P-43 with respect to solid part, and mix 1.0% sulfo-cyclopentenes nickel (thiolnickel) pigment (compound 5) separately, coat the PET film.For these films, under 80 ℃ of temperature, humidity 80% condition, carry out the moisture-proof heat experiment of 24 hours and 48 hours respectively, each film before and after the test experience is in the transmitance of 850nm and 1000nm, and the difference (Δ T) of calculating the transmitance of each wavelength is (%).It the results are shown in table 14.

[table 14]

Table 14

	Compound 10		Compound 11		Compound 12		P-43
									Wavelength (nm)	850	1000	850	1000	850	1000	850	1000
24 hours Δ T (%)	17	15	13	10	9	5	3	2
									48 hours Δ T (%)	15	17	15	19	15	13	3	5

By above-mentioned table 14 as can be known, even when mixing two kind pigments, with compound 10, compound 11, compound 12 relatively, P-43 good heat resistance of the present invention.

[embodiment 9]

In polymethylmethacrylate (Mw=100, the 000) solution of each 25% solid part (solvent toluene), to be about 2% to mix P-23 and P-43 with respect to solid part, coat the PET film after, with 80 ℃ of dryings 3 minutes.For these films, under the condition of 100 ℃ of humidity 90%, temperature, carry out 48 hours moisture-proof heat experiment, with the method identical, detect, calculate each film mist value, foxy Δ y value before and after the experiment with embodiment 5.It the results are shown in table 15.

[comparative example 2]

Polymethylmethacrylate (Mw=100 in 25% solid part, 000) in the solution in (solvent toluene), to be about 2% to mix following compound 13 with respect to solid part based on No. 5089585 specification sheets of United States Patent (USP), coat the PET film after, with 80 ℃ of dryings 3 minutes.For this spectral filter, under the condition of 100 ℃ of humidity 90%, temperature, carry out 48 hours moisture-proof heat experiment, with the method identical, detect, calculate spectral filter mist value, foxy Δ y value before and after the experiment with embodiment 5.It the results are shown in table 15.

[changing 33]

Compound 13 (molecular weight 7000)

[table 15]

Table 15

Spectral filter	Mist value (before the test)	Mist value (test back)	Δ y value
				P-23	1.36	1.41	0.001
P-43	0.95	1.02	0.002
				Comparative example 2	7.5	8.2	0.01

Learn by table 15, use the mist value of the spectral filter of mist value in the comparative example 2 of the spectral filter of P-23 and P-43, and the mist value of the spectral filter of P-23 and P-43 does not almost change in the experiment front and back, yet the mist value in the comparative example 2 is a lot of greatly compared to experiment back P-23 and P-43, and P-23 and P-43 compare the mist value and change less with comparative example.In addition, learn that the foxy value of P-23 and P-43 (Δ y value) is also less than comparative example 2 from table 15.This is because the resin intermiscibility of compound 13 weather resistance low and molecular skeleton is low, this means spectral filter good endurance of the present invention.

Learn that from embodiment 1～9 is clear near infrared ray absorption of the present invention is a kind of solvability to solvent, to the intermiscibility of resin and the material of good endurance.

[P-51's is synthetic]

According to following synthesis type, synthesized P-51 with Production Example 11～13.

[changing 34]

Synthesizing of [Production Example 11] compound 14

Except using the thiophene oxalic dialdehyde to come to replace phenylglyoxal, use chloroethene benzene replaces outside the bromine ethylbenzene and Production Example 1 is similarly synthesized, and obtains above-claimed cpd 14.Yield is 53%.

Synthesizing of [Production Example 12] compound 15

Except the compound 14 that utilizes Production Example 11 to obtain replaces the compound 1 and Production Example 2 is similarly synthesized, obtain above-claimed cpd 15.Yield is 22%.

[Production Example 13] P-51's is synthetic

Except the compound 15 that utilizes Production Example 12 to obtain replaces compound 2, the use tetrachlorobisphenol A replaces outside the dihydroxyphenyl propane and Production Example 3 is similarly synthesized, and obtains P-51.Yield is 80%.

[manufacturing of P-52]

According to following synthesis type, produce P-52 with Production Example 14～16.

[changing 35]

Compound 17

Synthesizing of [Production Example 14] compound 16

Except using 2 '-chlorobenzene oxalic dialdehyde to come to replace phenylglyoxal, use oxyethyl group naphthyl mercaptan to replace outside the bromine ethylbenzene, with 1 identical synthesizing of Production Example, obtain above-claimed cpd 16.Yield is 73%.

Synthesizing of [Production Example 15] compound 17

Except the compound 16 that uses Production Example 14 to obtain replaces the compound 1,, obtain above-claimed cpd 15 with 2 identical synthesizing of Production Example.Yield is 25%.

[Production Example 16] P-52's is synthetic

Except the compound 17 that uses Production Example 15 to obtain replaces compound 2, use dibromo-decane to replace outside the dihydroxyphenyl propane, with 3 identical synthesizing of Production Example, obtain P-52.Yield is 80%.

[P-53's is synthetic]

In following Production Example 17～19 synthetic P-53 with following repeating unit.

[changing 36]

Synthesizing of [Production Example 17] compound 19

[changing 37]

Compound 19

Under 5 ℃ of nitrogen environments, stir ethylene dichloride 100ml and TiCl ₄(30mmol), splash into butyryl chloride (20mmol) at leisure, drip hydrocinnamyl muriate (20mmol) afterwards.Stirred 8 hours after the room temperature of rising again.Slowly will react drop in frozen water, again with the dried over mgso organic layer, remove solvent behind the separatory.Utilize hexane to carry out recrystallization, obtain white solid (above-claimed cpd 18).Under nitrogen environment, this solid is dissolved in the methylene dichloride, under agitation, adds the 20mmol bromine in room temperature.Stir and desolvate after 3 hours, utilize hexane that the xanchromatic oily mater is carried out recrystallization, obtain faint yellow solid (above-claimed cpd 19).Yield is 53%.

Synthesizing of [Production Example 18] compound 20

[changing 38]

Compound 20

Except the compound 19 that uses Production Example 17 to obtain replaces compound 1, use Palladous chloride to replace NiCl ₂6H ₂Outside the O,, obtain compound 20 with 2 identical synthesizing of Production Example.Yield 15%.

[Production Example 19] P-53's is synthetic

[changing 39]

Except the compound 20 that uses Production Example 18 to obtain replaces compound 2, use two chlorine hydroxyl diphenyl sulfides to replace with 3 identical synthesizing of Production Example, obtaining P-53 outside the dihydroxyphenyl propane.Yield is 76%.

[P-54's is synthetic]

Produce P-54 in following Production Example 20～22 with following repeating unit.

[changing 40]

Synthesizing of [Production Example 20] compound 22

[changing 41]

Compound 22

In 5 ℃ of nitrogen environments, stir ethylene dichloride 100ml and TiCl ₄(30mmol), drip methylmercaptan ethyl acyl chlorides (20mmol) at leisure, drip styroyl bromination thing (20mmol) afterwards.Rise again to room temperature, stirred 8 hours.At leisure reaction solution is splashed in the frozen water, with behind the dried over mgso organic layer, desolvate behind the separatory.Carry out recrystallization with hexane, obtain white solid (above-claimed cpd 21).In methylene dichloride, dissolve this solid under the nitrogen environment, stir down, add the 20mmol bromine in room temperature.Desolvated after stirring in 3 hours, recrystallization xanchromatic oily mater is carried out recrystallization, obtain faint yellow solid (above-claimed cpd 22) with hexane.Yield is 70%.

Synthesizing of [Production Example 21] compound 23

[changing 42]

Compound 23

Except using the compound 22 that obtains with Production Example 20 to replace compound 1, use cobalt chloride to replace NiCl ₂6H ₂Outside the O,, obtain above-claimed cpd 23 with 2 identical synthesizing of Production Example.Yield is 11%.

[Production Example 22]

[changing 43]

Except the compound 23 that uses Production Example 21 to obtain replaces with 3 identical synthesizing of Production Example, obtaining P-54 the compound 2.Yield is 78%.

[P-55's is synthetic]

Produce P-55 in following Production Example 23～25 with following repeating unit.

[changing 44]

Synthesizing of [Production Example 23] compound 24

[changing 45]

Compound 24

Except using monobromethane and bromoethanol to replace the dibromo-propanol, all the other synthesize with identical method, separate (hexane: ethyl acetate=2: 1), obtain compound 24 by silica gel column chromatography in Production Example 8.Yield is 20%.

Synthesizing of [Production Example 24] compound 25

[changing 46]

Compound 25

Except using Production Example 23 synthetic compounds 24 to replace the compound 8, all the other obtain compound 25 to synthesize with Production Example 9 identical methods.Yield is 30%.

[Production Example 25] P-55's is synthetic

[changing 47]

Except using Production Example 24 synthetic compounds 25 to replace compound 9, use dibromo-propionic acid to replace outside the dibromo-decane, all the other obtain P-55 to synthesize with Production Example 10 identical methods.Yield is 60%.

[Production Example 26] P-56's is synthetic

[changing 48]

In 90 ℃, with 15mmol Production Example 5 synthetic compounds 4,15mmol Production Example 9 synthetic compounds 9, the bromine decyl alcohol of 15mmol, K ₂CO ₃(150mmol) and the dimethyl formamide of 100ml stirred 6 hours, filtering reacting liquid splashes into filtrate in the 1L1% aqueous hydrochloric acid then.Cross filter solid, carry out slurrying again (reslurry), obtain P-56 with methyl alcohol.Yield is 85%.

[embodiment 10]

Molecular weight Mw, Mn and the very big absorbing wavelength of near infrared ray of below representing some polymkeric substance of the present invention.

High speed GPC, HLC8120GPC that determining molecular weight is to use TOSOH Co., Ltd to make carry out with solvent THF, UV detection 254nm.(polystyrene conversion value).

[table 16]

Table 16

Compound	Mw	Mn	Absorb Bo Long (nm)
				P-1	6000	3500	870
P-2	4200	2300	870
				P-4	2500	1300	990
P-10	7100	4000	870
				P-21	6200	3050	850
P-22	2300	1050	960
				P-23	9000	4500	850
P-24	5500	2000	1070
				P-28	4500	2100	1020
P-31	3500	1900	1100
				P-40	10000	6200	1070
P-43	4200	3300	1040
				P-48	4100	1800	870、1060
P-50	3300	1600	810、1080
				P-51	5300	3100	980
P-52	6300	3500	890
				P-53	2300	1500	815
P-54	3200	1700	1010
				P-55	4000	1800	1005
P-56	4600	2500	860、1060

Utilize possibility on the industry

As mentioned above, near-infrared-absorbing material of the present invention can effectively be used as near infrared ray absorption, near infrared ray absorption of the present invention is compared with at present similar near infrared ray absorption, owing to can give excellent dissolubility and durability, can be used in such as optical filter with composition, laser welding with composition, composition for laser marking, hot radiation shielding material with composition or LED with various purposes such as near infrared ray absorption such as compositions.

Claims (32)

1. the near-infrared-absorbing material that has the repeating unit shown in following general formula (1) or (2),

General formula (1)

General formula (2)

In general formula (1) and (2), M represents atoms metal, R ¹And R ⁴Expression independently of one another replaces or unsubstituted aryl, replacement or unsubstituted heteroaryl or replacement or unsubstituted alkyl R ²And R ³Expression independently of one another replaces or unsubstituted arylidene, replacement or unsubstituted heteroarylidene or replacement or unsubstituted alkylidene group, in addition, and R ¹And R ², R ³And R ⁴Also can mutually combine and form ring, Y ¹～Y ⁴Expression is combination or heteroatoms directly, and wherein, A represents organic residue of directly combination or divalence.

2. near-infrared-absorbing material according to claim 1, wherein, the repeating unit shown in the general formula (1) is the repeating unit shown in the following general formula (3), the repeating unit shown in the general formula (2) is the repeating unit shown in the following general formula (4):

General formula (3)

General formula (4)

In general formula (3) and the general formula (4), M, R ¹, R ², R ³, R ⁴Identical with A with definition in the claim 1.

3. near-infrared-absorbing material according to claim 1, wherein, the repeating unit shown in the general formula (1) is the repeating unit shown in the following general formula (5), the repeating unit shown in the general formula (2) is the repeating unit shown in the following general formula (6):

General formula (5)

General formula (6)

In general formula (5) and the general formula (6), M, R ¹, R ², R ³, R ⁴Identical with A with definition in the claim 1.

4. near-infrared-absorbing material according to claim 1, wherein, the repeating unit shown in the general formula (1) is the repeating unit shown in the following general formula (7), the repeating unit shown in the general formula (2) is the repeating unit shown in the following general formula (8):

General formula (7)

General formula (8)

In general formula (7) and the general formula (8), M, R ¹, R ², R ³, R ⁴Identical with A with definition in the claim 1.

5. according to each described near-infrared-absorbing material in the claim 1 to 4, wherein, M is nickel, platinum, cobalt, palladium or copper.

6. according to each described near-infrared-absorbing material in the claim 1 to 5, wherein, R ¹～R ⁴At least one be to have substituent group.

7. according to each described near-infrared-absorbing material in the claim 1 to 6, wherein, R ¹And R ²And/or R ³And R ⁴In conjunction with forming conjugation or unconjugated ring.

8. according to each described near-infrared-absorbing material in the claim 1 to 7, wherein, A be will from-NHCO-,-CONH-,-NHCOO-,-OCONH-,-O-,-S-,-NH-,-COO-,-OCO-,-SO ₂-,-CO-,-C=C-,-N=N-,-the group arbitrary combination selected in S-S-, replacement or unsubstituted arylidene, replacement or unsubstituted heteroarylidene, replacement or unsubstituted alkylidene group and replacement or the unsubstituted amino group of forming and the organic residue of divalence that forms.

9. near-infrared-absorbing material according to claim 8, wherein, A is the group shown in the following general formula (9):

General formula (9)

In the formula, X ¹～X ³Be independently of one another directly in conjunction with or expression-NHCOO-,-OCONH-,-O-,-S-,-NH-,-COO-,-OCO-,-SO ₂-,-CO-,-C=C-,-N=N-or-S-S-, n ¹And n ²Expression 0 or natural number.

10. according to each described near-infrared-absorbing material in the claim 1 to 9, wherein, described near-infrared-absorbing material has the different repeat units more than 2 kinds.

11. a near infrared ray absorption, it comprises each described near-infrared-absorbing material in the claim 1 to 10.

12. a near-infrared absorbing composition, its comprise at least a claim 11 infrared absorbent constituted.

13. near-infrared absorbing composition according to claim 12, wherein, described near infrared ray absorption comprises the near infrared ray absorption more than 2 kinds.

14., wherein, further comprise the described near infrared ray absorption of claim 11 near infrared ray absorption in addition according to claim 12 or 13 described near-infrared absorbing compositions.

15. near-infrared absorbing composition according to claim 14, wherein, the near infrared ray absorption beyond the described near infrared ray absorption of claim 11 is at least a near infrared ray absorption of selecting from nickel complex pigment, phthalocyanine dye and two quaternary ammonium pigments.

16. according to claim 13 or 14 described near-infrared absorbing compositions, wherein, contained near infrared ray absorption comprises at least 2 kinds of near infrared ray absorptions with different maximum near-infrared absorbing wavelength in the described near-infrared absorbing composition.

17. according to each described near-infrared absorbing composition in the claim 12～16, wherein, described near-infrared absorbing composition further comprises adhesive resin.

18., wherein, further comprise solvent in the described near-infrared absorbing composition according to each described near-infrared absorbing composition in the claim 12～17.

19. according to each described near-infrared absorbing composition in the claim 12～18, wherein, described near-infrared absorbing composition is a coating composition.

20. according to each described near-infrared absorbing composition in the claim 12～19, wherein, described near-infrared absorbing composition is adhesion or adhesive composite.

21. according to each described near-infrared absorbing composition in the claim 12～19, wherein, described near-infrared absorbing composition is the laser welding composition.

22. according to each described near-infrared absorbing composition in the claim 12～19, wherein, described near-infrared absorbing composition is a composition for laser marking.

23. according to each described near-infrared absorbing composition in the claim 12～19, wherein, described near-infrared absorbing composition is hot radiation shielding material composition.

24. according to each described near-infrared absorbing composition in the claim 12～19, wherein, described near-infrared absorbing composition is the LED composition.

25. a laminate, the layer of each described near-infrared-absorbing material forms in claim 1～10 for formation on base material contains for it.

26. laminate according to claim 25, wherein, the described layer that contains described near-infrared-absorbing material is to become by each described near-infrared absorbing composition in the claim 12～20.

27. a near-infrared absorbing film, it contains each described near-infrared-absorbing material in the claim 1～10.

28. an optical filter, it comprises the laminate of claim 25 or 26.

29. optical filter according to claim 28, wherein, described optical filter is the plasma display optical filter.

30. optical filter according to claim 28, wherein, described optical filter is the liquid-crystal display optical filter.

31. optical filter according to claim 28, wherein, described optical filter is a CCD photographic camera optical filter.

32. optical filter according to claim 28, wherein, described optical filter is a CMOS image sensor optical filter.

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