JP5460079B2 - Cyanine compound and optical filter using the compound - Google Patents

Description

  The present invention relates to a novel cyanine compound and an optical filter using the compound. The cyanine compound is useful as an optical element, and particularly has a specific structure suitable for a light absorber used in an optical filter for an image display device.

  Compounds having high absorption in the wavelength range of 450 nm to 700 nm, particularly compounds having a maximum absorption (λmax) in the range of 450 to 620 nm, are used for optical recording layers of optical recording media such as DVD ± R, and liquid crystal display devices (LCD). It is used as an optical element in an optical filter for an image display device such as a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT), a fluorescent display tube, or a field emission display.

  For example, as an application of the optical element in the image display device, there is a light absorber for a color filter. The image display device displays a color image with a combination of light of the three primary colors of red, blue, and green. However, the display quality of the light that displays the color image is deteriorated such as 550 to 620 nm between green and red. In addition, light that causes malfunction of an infrared remote controller of 750 to 1100 nm is also included. The optical filter is required to have a function of selectively absorbing light of the above-described unnecessary wavelength, and at the same time, in order to prevent reflection and reflection of external light from a fluorescent lamp or the like, 480 to 520 nm and 540 to 560 nm. It is also necessary to absorb light of the wavelength. Therefore, an optical filter containing a light-absorbing compound (light absorber) that selectively absorbs light of these wavelengths is used in an image display device or the like.

  Further, in recent years, a light absorber that selectively absorbs a wavelength of 480 to 520 nm has been demanded in order to achieve sufficient color purity and color separation of the display element and to improve image quality. These light absorbers are required to have particularly steep light absorption, that is, having a small half-value width of λmax and not to lose its function due to light, heat, or the like.

  As an optical filter containing a light absorber, for example, the following Patent Document 1 discloses an optical filter using an azaporphyrin compound having a maximum absorption wavelength at 570 to 605 nm. An optical filter using a condensed polycyclic pigment having a maximum absorption wavelength at ˜600 nm is disclosed. Patent Document 3 below discloses an optical filter using a dipyrromethene metal chelate compound having a maximum absorption wavelength at 440 to 510 nm. It is disclosed. However, the compounds used in these optical filters do not have satisfactory performance in terms of absorption wavelength characteristics or affinity with solvents and binder resins.

  Patent Document 4 discloses an optical filter containing a cyanine compound having particularly good absorption characteristics at 480 to 520 nm, but it is not satisfactory in terms of light resistance. Patent Documents 5 and 6 describe that a cyanine compound substituted with a metallocene bond group is used as an optical recording material, but does not describe use as an optical filter. Moreover, since the cyanine compound described in Patent Document 6 is characterized by having a maximum absorption at 550 nm to 620 nm, the intended absorption characteristics were not satisfied.

JP 2003-57437 A JP 2004-310072 A JP 2003-57436 A JP 2005-194509 A JP 2003-171571 A JP 2006-104387 A

  Accordingly, an object of the present invention is to provide a novel cyanine compound useful as an optical element, in particular, an optical filter having a sharp light absorption in the wavelength region of 480 to 520 nm, excellent in light resistance, and particularly suitable for an image display device. It is an object of the present invention to provide a novel cyanine compound suitable for an absorbent and an optical filter containing the same.

The present inventors have applied for a patent (Japanese Patent Application No. 2009-8499) regarding the cyanine compound that has improved the above-mentioned problems, but further improvement in performance has been demanded.
Therefore, as a result of further studies, the present inventors have found that a cyanine compound having a specific molecular structure has excellent moisture and heat resistance, has steep light absorption in a specific wavelength region, and contains a conventional cyanine compound. It has been found that it exhibits better light resistance than the optical filter and can significantly improve the image characteristics of the image display device.

  The present invention has been made based on the above findings, and provides a cyanine compound represented by the following general formula (I) and an optical filter containing the cyanine compound.

（式中、環Ａはベンゼン環又はナフタレン環を表し、環Ａの水素原子は炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、ニトロ基、シアノ基又はハロゲン原子で置換されていてもよく、
Ｘ¹は、酸素原子、硫黄原子又はセレン原子を表し、
Ｘ²は、ＣＲ¹Ｒ²、酸素原子、硫黄原子又はセレン原子を表し、
Ｒ¹及びＲ²は、各々独立に、下記一般式（II）若しくは（II’）で表される基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、Ｒ¹とＲ²は、それぞれ連結して３〜６員環の脂環基を形成してもよく、
Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、各々独立に、水素原子、下記一般式（II）若しくは（II’）で表される基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基、ハロゲン原子又はシアノ基を表し、
Ｙ¹及びＹ²は、各々独立に、下記一般式（III）で表される基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基を表し、但し、Ｙ¹とＹ²の少なくとも一方は、下記一般式（III）で表される基であり、
上記の環Ａの水素原子を置換してもよい基或いはＲ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｙ¹及びＹ²で表される基であるアルキル基、アリール基及びアリールアルキル基中のメチレン基は、酸素原子、硫黄原子又は二重結合で１〜３回中断されていてもよく、該アルキル基、アリール基及びアリールアルキル基の水素原子は、ニトロ基、シアノ基又はハロゲン原子で置換されていてもよく、
Ｚは、水素原子、ハロゲン原子又はシアノ基を表し、Ａｎ^q-は、ｑ価の陰イオンを表し、ｑは、１又は２の整数であり、ｐは、電荷を中性に保つ係数を表す。）

(In the formula, ring A represents a benzene ring or a naphthalene ring, and the hydrogen atom of ring A is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms. A group, a nitro group, a cyano group or a halogen atom,
X ¹ represents an oxygen atom, a sulfur atom or a selenium atom,
X ² represents CR ¹ R ² , an oxygen atom, a sulfur atom or a selenium atom,
R ¹ and R ² are each independently a group represented by the following general formula (II) or (II ′), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. Represents an arylalkyl group of formula 7 to 30, and R ¹ and R ² may be connected to each other to form a 3- to 6-membered alicyclic group,
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a group represented by the following general formula (II) or (II ′), an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms Represents an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a halogen atom or a cyano group,
Y ¹ and Y ² are each independently a group represented by the following general formula (III), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a group having 7 to 30 carbon atoms. Represents an arylalkyl group, provided that at least one of Y ¹ and Y ² is a group represented by the following general formula (III);
Alkyl group or aryl group which is a group which may substitute the hydrogen atom of ring A or a group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y ¹ and Y ² And the methylene group in the arylalkyl group may be interrupted 1 to 3 times by an oxygen atom, a sulfur atom or a double bond, and the hydrogen atom of the alkyl group, aryl group and arylalkyl group is a nitro group, cyano group, Optionally substituted with a group or halogen atom,
Z represents a hydrogen atom, a halogen atom or a cyano group, An ^q− represents a q-valent anion, q represents an integer of 1 or 2, and p represents a coefficient for maintaining a neutral charge. . )

（上記一般式（II）において、ＧとＴの間の結合は、二重結合、共役二重結合又は三重結合であり、Ｇは炭素原子を表し、Ｔは炭素原子、酸素原子又は窒素原子を表し（但し、Ｔが酸素原子である場合はｙとｚは０であり、Ｔが窒素原子である場合はｙ＋ｚは０又は１である。）、ｗは０〜４の数を表し、ｘ、ｙ及びｚは、各々独立に、０又は１を表し、
Ｒ⁰¹、Ｒ⁰²、Ｒ⁰³及びＲ⁰⁴は、各々独立に、水素原子、水酸基、ニトロ基、シアノ基、ハロゲン原子又は置換基を有してもよい炭素原子数１〜４のアルキル基を表し、該アルキル基中のメチレン基は、−Ｏ−又は−ＣＯ−で置換されていてもよく、Ｒ⁰¹とＲ⁰⁴は結合してシクロアルケン環又は複素環を形成してもよい。
上記一般式（II’）において、Ｇ’とＴ’の間の結合は、二重結合又は共役二重結合であり、Ｇ’は炭素原子を表し、Ｔ’は炭素原子又は窒素原子を表し、ｗ’は０〜４の数を表し、
Ｒ⁰¹’は水素原子、水酸基、ニトロ基、シアノ基、ハロゲン原子又はハロゲン原子で置換されてもよい炭素原子数１〜４のアルキル基を表し、該アルキル基中のメチレン基は、−Ｏ−又は−ＣＯ−で置換されていてもよく、
Ｇ’及びＴ’を含む環は、ヘテロ原子を含んでもよい５員環、ヘテロ原子を含んでもよい６員環、ナフタレン環、キノリン環、イソキノリン環、アントラセン環又はアントラキノン環を表し、これらＧ’及びＴ’を含む環は、ハロゲン原子、水酸基、ニトロ基、シアノ基、炭素原子数１〜４のアルキル基又は炭素原子数１〜４のアルコキシ基で置換されていてもよい。）

(In the general formula (II), the bond between G and T is a double bond, a conjugated double bond or a triple bond, G represents a carbon atom, and T represents a carbon atom, an oxygen atom or a nitrogen atom. Wherein Y and z are 0 when T is an oxygen atom, and y + z is 0 or 1 when T is a nitrogen atom, w represents a number from 0 to 4, x, y and z each independently represent 0 or 1,
R ⁰¹ , R ⁰² , R ⁰³ and R ⁰⁴ each independently represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. The methylene group in the alkyl group may be substituted with —O— or —CO—, and R ⁰¹ and R ⁰⁴ may combine to form a cycloalkene ring or a heterocyclic ring.
In the general formula (II ′), the bond between G ′ and T ′ is a double bond or a conjugated double bond, G ′ represents a carbon atom, T ′ represents a carbon atom or a nitrogen atom, w ′ represents a number from 0 to 4,
R ⁰¹ ′ represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, and the methylene group in the alkyl group is —O— Or may be substituted with -CO-
The ring containing G ′ and T ′ represents a 5-membered ring which may contain a heteroatom, a 6-membered ring which may contain a heteroatom, a naphthalene ring, a quinoline ring, an isoquinoline ring, an anthracene ring or an anthraquinone ring. And the ring containing T ′ may be substituted with a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. )

（式中、Ｒ^a〜Ｒⁱは、各々独立に、水素原子又は炭素原子数１〜４のアルキル基を表し、該アルキル基中のメチレン基は−Ｏ−又は−ＣＯ−で置換されていてもよく、
Ｑは直接結合又は置換基を有してもよい炭素原子数１〜８のアルキレン基を表し、該アルキレン基中のメチレン基は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＳＯ₂−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｎ＝ＣＨ−又は−ＣＨ＝ＣＨ−で置換されていてもよく、
ＭはＦｅ、Ｃｏ、Ｎｉ、Ｔｉ、Ｃｕ、Ｚｎ、Ｚｒ、Ｃｒ、Ｍｏ、Ｏｓ、Ｍｎ、Ｒｕ、Ｓｎ、Ｐｄ、Ｒｈ、Ｐｔ又はＩｒを表す。）

(Wherein R ^{a to} R ⁱ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the methylene group in the alkyl group is substituted with —O— or —CO—). Well,
Q represents a direct bond or an alkylene group having 1 to 8 carbon atoms which may have a substituent, and the methylene group in the alkylene group is -O-, -S-, -CO-, -COO-,- _{OCO -, - SO 2 -,} - NH -, - CONH -, - NHCO -, - N = CH- or -CH = CH- may be substituted with,
M represents Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, Pt, or Ir. )

  The cyanine compound of the present invention represented by the above general formula (I) is a compound characterized by having a specific skeleton, and has higher heat and moisture resistance and light resistance than conventional cyanine compounds used in optical filters. . The cyanine compound exhibits steep light absorption at 450 to 700 nm, particularly 480 to 600 nm, and the optical filter comprising the cyanine compound is an optical filter suitable for image display applications, particularly plasma display applications.

Hereinafter, the cyanine compound of the present invention and the optical filter containing the cyanine compound will be described in detail based on preferred embodiments thereof.

First, the cyanine compound of the present invention represented by the general formula (I) will be described.

Among the substituents that may be substituted on the benzene ring or naphthalene ring represented by ring A in the general formula (I), the alkyl group having 1 to 10 carbon atoms includes methyl, ethyl, propyl, isopropyl, Butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, trifluoromethyl, Methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy, trifluoromethyloxy, methylthio, ethylthio, propylthio, isopropylthio, butylthio, s-butylthio, t-butylthio, etc.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl,
Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

^{R 1, R 2, R 3} , R 4, R 5, the alkyl group of R ^6, Y ¹ and 20 carbon atoms represented by Y ^2, methyl, ethyl, propyl, isopropyl, butyl, s -Butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl , Nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, peptadecyl, octadecyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2 -Methylthioethyl and the like,
Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, and 4-butylphenyl. 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2 , 4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, cyclohexylphenyl, 2- And phenoxyethyl, 2-phenylthioethyl, etc.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like.

R ¹ and R ² may be connected to each other to form a 3- to 6-membered alicyclic group. Examples of the 3- to 6-membered alicyclic group include cyclopropane-1,1-diyl, cyclobutane-1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, and 3-dimethylcyclobutane-1,1. -Diyl, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl, tetrahydropyran-4,4-diyl, thian-4,4-diyl, piperidine-4,4-diyl, N-substituted piperidine- 4,4-diyl, morpholine-2,2-diyl, morpholine-3,3-diyl, N-substituted morpholine-2,2-diyl, N-substituted morpholine-3,3-diyl and the like. Examples of the substituent include the groups exemplified as the substituent for ring A.

R ^3, R ^4, R ⁵ and halogen atom represented by ^{R 6, R 1, R 2} , R 3, R 4, R 5, R 6, the alkyl group represented by Y ¹ and Y ^2, an aryl group In addition, examples of the halogen atom that may substitute the arylalkyl group and the halogen atom represented by Z include fluorine, chlorine, bromine, and iodine.

In the general formula (I), examples of the anion represented by An ^q- include, for example, monovalent ions such as chloride ions, bromide ions, iodide ions, fluoride ions, and the like; Inorganic anions such as chlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion; benzenesulfonate ion, toluenesulfonate ion, trifluoromethanesulfonate Ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, N-alkyl (or aryl) diphenylamine-4-sulfonic acid ion Organic sulfonic acid anions such as Organic phosphoric acid such as phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphonate ion System anion, bistrifluoromethylsulfonylimide ion, bisperfluorobutanesulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkylsulfonyl) carboanion, etc. Named,
As a bivalent thing, a benzene disulfonic acid ion, a naphthalene disulfonic acid ion, etc. are mentioned, for example. In addition, quencher anions that have the function of deexciting (quenching) active molecules in the excited state, and ferrocenes having an anionic group such as a carboxyl group, phosphonic acid group, or sulfonic acid group on the cyclopentadienyl ring. Also, metallocene compound anions such as ruthenocene can be used. Also, p is selected so that the charge is neutral throughout the molecule.

  Examples of the quencher anion include those represented by the following general formula (A) or (B), those represented by the following formula (C) or (D), and JP-A-60-234892. JP-A-5-43814, JP-A-5-305770, JP-A-6-239028, JP-A-9-309886, JP-A-9-323478, JP-A-10-45767, Kaihei 11-208118, JP 2000-168237, JP 2002-201373, JP 2002-206061, JP 2005-297407, JP 7-96334, International Publication 98 / 29257 and the like.

（式中、Ｍは、上記一般式（III）と同じであり、Ｒ⁹及びＲ¹⁰は、各々独立に、ハロゲン原子、炭素原子数１〜８のアルキル基、炭素原子数６〜３０のアリール基又は−ＳＯ₂−Ｇ基を表し、Ｇは、アルキル基、ハロゲン原子で置換されていてもよいアリール基、ジアルキルアミノ基、ジアリールアミノ基、ピペリジノ基又はモルフォリノ基を表し、ａ及びｂは、各々独立に、０〜４の数を表す。また、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴は、各々独立にアルキル基、アルキルフェニル基、アルコキシフェニル基又はハロゲン化フェニル基を表す。）

(In the formula, M is the same as the above general formula (III), and R ⁹ and R ¹⁰ are each independently a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl having 6 to 30 carbon atoms. A group or —SO ₂ —G group, G represents an alkyl group, an aryl group optionally substituted with a halogen atom, a dialkylamino group, a diarylamino group, a piperidino group or a morpholino group, and a and b are Each independently represents a number from 0 to 4. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group, an alkylphenyl group, an alkoxyphenyl group or a halogenated phenyl group.

Examples of the halogen atom represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^{04 in the} general formula (II) and R ⁰¹ ′ in the general formula (II ′) include fluorine, chlorine, bromine, iodine and the like. ,
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁰¹ , R ⁰² , R ⁰³ , R ^{04 in the} general formula (II) and R ⁰¹ ′ in the general formula (II ′) include methyl, ethyl, Propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, etc.
Examples of the group in which the methylene group in the alkyl group is substituted with -O- include methoxy, ethoxy, propyloxy, isopropyloxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl and the like.
Examples of the group in which the methylene group in the alkyl group is substituted with -CO- include acetyl, 1-carbonylethyl, acetylmethyl, 1-carbonylpropyl, 2-oxobutyl, 2-acetylethyl, 1-carbonylisopropyl and the like. Any of these may have a substituent.
Examples of the cycloalkene ring formed by connecting R ⁰¹ and R ⁰⁴ include a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, and a cyclohexene ring.
^{Examples of} the heterocycle formed by linking R ⁰¹ and R ⁰⁴ include tetrahydropyran ring, piperidine ring, piperazine ring, pyrrolidine ring, morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine Ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazolidine ring, isothiazolidine ring, etc., and these rings may be condensed or substituted with other rings. May be.
R ⁰¹ , R ⁰² , R ⁰³ , R ^{04 in the} general formula (II) and an alkyl group having 1 to 4 carbon atoms represented by R ⁰¹ ′ in the general formula (II ′), the general formula (II) Examples of the substituent of the ring structure formed by linking R ⁰¹ and R ⁰⁴ in are those exemplified in the description of the general formula (I). R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰¹ ′ are the above alkyl groups having 1 to 4 carbon atoms, etc., and among the following substituents, have a substituent containing a carbon atom. In this case, the total number of carbon atoms such as R ⁰¹ including the substituent should satisfy the specified range.

In the general formula (II ′), examples of the 5-membered ring that may contain a hetero atom include a cyclopentene ring, cyclopentadiene ring, imidazole ring, thiazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiophene ring, furan ring, Pyrrole ring and the like,
Examples of the 6-membered ring that may contain a hetero atom include a benzene ring, a pyridine ring, a piperazine ring, a piperidine ring, a morpholine ring, a pyrazine ring, a pyrone ring, and a pyrrolidine ring.

The alkyl group having 1 to 4 carbon atoms represented by R ^a to R ⁱ in the general formula (III), those exemplified in the description of the general formula (II) may be mentioned,
Examples of the group in which the methylene group in the alkyl group is substituted with -O- include methoxy, ethoxy, propyloxy, isopropyloxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl and the like.
Examples of the group in which the methylene group in the alkyl group is substituted with -CO- include acetyl, 1-carbonylethyl, acetylmethyl, 1-carbonylpropyl, 2-oxobutyl, 2-acetylethyl, 1-carbonylisopropyl and the like. It is done.

Examples of the alkylene group having 1 to 8 carbon atoms which may have a substituent represented by Q in the general formula (III) include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2- Methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene , Pentylene, hexylene, heptylene, octylene, ethane-1,1-diyl, propane-2,2-diyl and the like,
The methylene group in the alkylene group is —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NH—, —CONH—, —NHCO—, —N═CH—. Or, the group substituted by —CH═CH— includes methyleneoxy, ethyleneoxy, oxymethylene, thiomethylene, carbonylmethylene, carbonyloxymethylene, methylenecarbonyloxy, sulfonylmethylene, aminomethylene, acetylamino, ethylenecarboxamide, ethane Imidoyl, ethenylene, propenylene and the like can be mentioned.
Examples of the substituent of the alkylene group having 1 to 8 carbon atoms represented by Q in the general formula (III) include those exemplified in the description of the general formula.

Among the cyanine compounds of the present invention, in the above general formula (I), a cyanine compound in which X ¹ and X ² are both sulfur atoms is preferable because of excellent optical properties. In the above general formula (I), Y ¹ is the above The cyanine compound which is a group represented by the general formula (III) is preferable because it provides an optical filter having good light resistance. Furthermore, in the above general formula (I), a cyanine compound in which Y ¹ and Y ² are both groups represented by the above general formula (III) is preferable because light resistance is further improved.

In the above general formula (I), a cyanine compound in which R ³ , R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms, or in the above general formula (III), M is Fe and Q is the number of carbon atoms. A cyanine compound which is an alkylene group having 1 to 8 is preferable because of low production cost.

Furthermore, a cyanine compound in which the anion represented by An ^q- in the general formula (I) is a hexafluorophosphate ion is preferable because of excellent heat resistance.

The cyanine compound of the present invention has a resonance structure as shown in the following [Chemical Formula 7], but may be any structural formula. The cyanine compound of the present invention includes optical isomers such as enantiomers, diastereomers, and racemates having chiral centers at the asymmetric carbon atoms to which the groups represented by R ¹ and R ² or R ³ and R ⁴ are bonded. However, any of these optical isomers may be isolated and used as a mixture thereof.

  Specific examples of the cation moiety of the cyanine compound of the present invention represented by the above general formula (I) include the following compound Nos. 1-No. 33.

  Although the cyanine compound of the present invention represented by the above general formula (I) is not limited by the production method thereof, for example, a bridge such as 2-methylthiazolinium salt derivative and N, N′-diphenylamidine A 2-methylbenzothiazolium salt derivative can be produced by reacting acetic anhydride in pyridine with an intermediate obtained by reacting with an agent.

  The above-described cyanine compound of the present invention is suitable as an optical element for light in the range of 450 nm to 700 nm, particularly as an optical element for light in the range of 480 to 520 nm. The optical element is an element that exhibits a function by absorbing specific light. Specifically, the optical recording is performed on an optical recording medium such as a light absorber used in an optical filter or a DVD ± R. Examples thereof include an optical recording agent and a photosensitizer used for the layer. In particular, the cyanine compound of the present invention is useful as a light absorber for an optical filter as described below.

Next, the optical filter of the present invention will be described below.
The optical filter of the present invention contains at least one cyanine compound of the present invention represented by the above general formula (I). The cyanine compound has an absorption maximum wavelength in the range of 480 to 520 nm or in the vicinity thereof, and can selectively absorb and block a part of visible light, so that the optical component of the present invention containing the cyanine compound can be used. The filter is particularly preferably used as an optical filter for an image display device used for improving the quality of a display image. Examples of such an image display device include a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode tube display device (CRT), a fluorescent display tube, and a field emission display. . In addition, the optical filter of the present invention can also be used for various applications such as spectacle lenses, windows, analyzer applications, semiconductor device applications, astronomical observation applications, and optical communication applications.

  A diimonium compound can be used in combination with the optical filter of the present invention as necessary. As the dimonium compound, a known compound that is usually used as a near-infrared absorbing compound in an optical filter can be used. However, it is possible to use a dimonium compound having the same anion as the cyanine compound of the present invention. This is preferable because of the increased stability.

  As said dimonium compound, the compound represented by the following general formula (V) can be used preferably.

（式中、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、各々独立に、水素原子又は炭素原子数１〜８のアルキル基を表し、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷及びＲ²⁸は、各々独立に、水素原子、ハロゲン原子、炭素原子数１〜８のアルキル基又はアミノ基を表す。Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷及びＲ²⁸で表される炭素原子数１〜８のアルキル基、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷及びＲ²⁸で表されるアミノ基は、置換基を有していてもよい。上記炭素原子数１〜８のアルキル基中のメチレン基は、−Ｏ−又は−ＣＨ＝ＣＨ−で置換されていてもよく、ｒは１〜４の数を表し、Ａｎ、ｐ及びｑは、上記一般式（Ｉ）と同じである。）

(Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an amino group, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^21. R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ , an alkyl group having 1 to 8 carbon atoms, represented by R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ The amino group may have a substituent, and the methylene group in the alkyl group having 1 to 8 carbon atoms may be substituted with —O— or —CH═CH—, and r is 1 Represents the number of ~ 4, and An, p and q are the same as those in the general formula (I).

In the optical filter of the present invention, the content of the cyanine compound of the present invention represented by the general formula (I) is usually 1 to 1000 mg / m ² , preferably 5 to 100 mg / m ² , and the content is If it is less than 1 mg / m ² , the light absorption effect cannot be exhibited sufficiently, and if it exceeds 1000 mg / m ² , the color of the filter may become too strong and the display quality may deteriorate. Furthermore, there is a possibility that the lightness may decrease due to an increase in the amount of the light absorber.

The content of the diimmonium compound in combination as needed, 10~10000mg / m ² per unit area of the optical filter, preferably 50 to 1000 mg / m ^2.

  The optical filter of the present invention is usually disposed in front of the display. For example, the optical filter of the present invention may be directly attached to the surface of the display. When a front plate is provided in front of the display, the optical filter is attached to the front side (outside) or back side (display side) of the front plate. May be.

  Although the shape of the optical filter of the present invention is not particularly limited, each layer such as an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, and a protective layer is usually provided on the transparent support as necessary. What was provided is mentioned. Examples of the method for incorporating the optical filter of the present invention into the optical filter of the present invention include optional components such as the cyanine compound of the present invention, a light absorber other than the cyanine compound of the present invention, and various stabilizers. Or (2) a method of coating a transparent support or any layer, (3) an adhesive layer between any two adjacent members selected from the transparent support and any layer (4) The method of providing the light absorption layer containing light absorbers, such as the cyanine compound of this invention separately from arbitrary each layer, is mentioned.

  Examples of the material for the transparent support include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamides; polycarbonates; polyethylenes Polyesters such as terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene Polyolefins such as polypropylene and polymethylpentene; acrylic resins such as polymethyl methacrylate; polycarbonates; ; Polyether sulfone; polyether ketone; polyetherimides; polyoxyethylene, and polymer materials such as norbornene resins. The transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze is preferably 2% or less, and more preferably 1% or less. The refractive index is preferably 1.45 to 1.70.

  In the transparent support, other light absorbers other than the cyanine compound of the present invention, infrared absorbers, ultraviolet absorbers, phenol-based, phosphorus-based, sulfur-based antioxidants, flame retardants, lubricants, antistatic agents Agent, inorganic fine particles, light fastness imparting agent, aromatic nitroso compound, aminium compound, iminium compound, transition metal chelate compound, etc. can be added, and the transparent support can be subjected to various surface treatments. it can.

  As a light absorber other than the cyanine compound of the present invention, for example, when an optical filter is used for an image display device, a light absorber for adjusting color tone, a light absorber for preventing reflection of external light and reflection of light. In the case where the image display device is a plasma display, a light absorber for preventing infrared remote control malfunction is used.

  As the light absorber for color tone adjustment, trimethine indolium compound, trimethine benzoxazolium compound, trimethine benzothiazolium compound are used for removing orange light having a wavelength of 480 to 520 nm. Trimethine cyanine derivatives such as pentamethine oxazolium compounds, pentamethine cyanine derivatives such as pentamethine thiazolium compounds, squarylium dye derivatives, azomethine dye derivatives, xanthene dye derivatives, azo dye derivatives, oxonol dye derivatives, benzylidene dye derivatives A pyromethene dye derivative; an azo metal complex derivative: a rhodamine dye derivative; a phthalocyanine derivative; a porphyrin derivative; a dipyrromethene metal chelate compound.

  Examples of the light absorbing agent for reflection or reflection of external light (corresponding to a wavelength of 480 to 520 nm) include trimethine indolium compound, trimethine oxazolium compound, trimethine thiazolium compound, indolidene trimethine thiazonium. Trimethine cyanine derivatives such as compounds; phthalocyanine derivatives; naphthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds.

  As the above-mentioned light absorber for preventing infrared remote control malfunction (corresponding to a wavelength of 750 to 1100 nm), a diimonium compound other than the compound represented by the general formula (V); a pentamethine benzoindolium compound, a pentamethine benzoxa Pentamethine cyanine derivatives such as zolium compounds and pentamethine benzothiazolium compounds; heptamethine indolium compounds, heptamethine benzoindolium compounds, heptamethine oxazolium compounds, heptamethine benzoxazolium compounds, heptamethine thiazo Heptamethine cyanine derivatives such as lium compounds and heptamethine benzothiazolium compounds; squarylium derivatives; bis (stilbenedithiolato) compounds, bis (benzenedithiolato) nickel compounds, bis (camphagethiolato) nickel Squarylium derivatives; nickel complexes of compounds such as azo dye derivatives; phthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds, and the like.

In the optical filter of the present invention, the above light absorber for color tone adjustment, a light absorber for preventing reflection of external light and reflection, and a light absorber for preventing infrared remote control malfunction (near infrared absorber) are: The layer containing the cyanine compound of the present invention may be contained in the same layer or may be contained in another layer. Each of these amounts is usually in the range of 1-1000 mg / m ² per unit area of the optical filter, preferably 5-100 mg / m ² .

  Examples of the inorganic fine particles that can be added to the transparent support include silicon dioxide, titanium dioxide, barium sulfate, calcium carbonate, talc, and kaolin.

  Examples of the various surface treatments that can be applied to the transparent support include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser. Treatment, mixed acid treatment, ozone oxidation treatment and the like.

  The said undercoat which can be provided in the optical filter of this invention is a layer used between a transparent support body and an optical filter layer, when providing the filter layer containing a light absorber separately from arbitrary each layer. The undercoat layer is formed as a layer containing a polymer having a glass transition temperature of −60 to 60 ° C., a layer having a rough surface on the filter layer side, or a layer containing a polymer having affinity with the polymer of the filter layer. In addition, the undercoat layer is provided on the surface of the transparent support on which the filter layer is not provided, and improves the adhesion between the transparent support and a layer (for example, an antireflection layer or a hard coat layer) provided thereon. It may be provided for improving the affinity between the optical filter and the adhesive for bonding the optical filter and the image display device. The thickness of the undercoat layer is preferably 2 nm to 20 μm, more preferably 5 nm to 5 μm, still more preferably 20 nm to 2 μm, still more preferably 50 nm to 1 μm, and most preferably 80 nm to 300 nm. The undercoat layer containing a polymer having a glass transition temperature of −60 to 60 ° C. adheres the transparent support and the filter layer due to the tackiness of the polymer. Polymers having a glass transition temperature of −60 to 60 ° C. are exemplified by polymerization of vinyl chloride, vinylidene chloride, vinyl acetate, butadiene, neoprene, styrene, chloroprene, acrylic ester, methacrylic ester, acrylonitrile or methyl vinyl ether, or a copolymer thereof. It can be obtained by polymerization. The glass transition temperature is preferably 50 ° C. or less, more preferably 40 ° C. or less, further preferably 30 ° C. or less, still more preferably 25 ° C. or less, and further preferably 20 ° C. or less. Most preferred. The elastic modulus at 25 ° C. of the undercoat layer is preferably 1 to 1000 MPa, more preferably 5 to 800 MPa, and most preferably 10 to 500 MPa. The undercoat layer whose surface is a rough surface forms a filter layer on the rough surface, thereby bonding the transparent support and the filter layer. An undercoat layer having a rough filter layer surface can be easily formed by applying a polymer latex. The average particle size of the latex is preferably 0.02 to 3 μm, and more preferably 0.05 to 1 μm. Examples of the polymer having an affinity for the binder polymer of the filter layer include acrylic resins, cellulose derivatives, alginic acid, gelatin, casein, starch, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, soluble nylon, and polymer latex. The optical filter of the present invention may be provided with two or more undercoat layers. In the undercoat layer, a solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like may be added.

  In the antireflection layer that can be provided in the optical filter of the present invention, a low refractive index layer is essential. The refractive index of the low refractive index layer is lower than the refractive index of the transparent support. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, and more preferably 1.30 to 1.50. The thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm. The low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Laid-Open Nos. 57-34526, 3-130103, 6-115023, 8-313702, and 7- No. 168004), a layer obtained by a sol-gel method (described in JP-A-5-208811, JP-A-6-299091, JP-A-7-168003), or a layer containing fine particles (Japanese Patent Publication No. 60). -59250, JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, and JP-A-9-288201). In the layer containing fine particles, voids can be formed in the low refractive index layer as microvoids between the fine particles or within the fine particles. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, and more preferably has a porosity of 5 to 35% by volume.

  In order to prevent reflection in a wide wavelength region, in the antireflection layer, in addition to the low refractive index layer, a layer having a high refractive index (medium / high refractive index layer) is preferably laminated. The refractive index of the high refractive index layer is preferably 1.65 to 2.40, more preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.90, and more preferably 1.55 to 1.70. The thickness of the middle / high refractive index layer is preferably 5 nm to 100 μm, more preferably 10 nm to 10 μm, and most preferably 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The middle / high refractive index layer can be formed using a polymer binder having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, styrene-butadiene copolymer, polyvinyl chloride, polycarbonate, polyamide, melamine resin, phenol resin, epoxy resin, cyclic (alicyclic or aromatic) isocyanate and polyol. And the like obtained by the reaction. Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. You may use the polymer formed by the polymerization reaction of the monomer which introduce | transduced the double bond and enabled radical hardening.

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

  An antiglare function (function of preventing incident scenery from being transferred to the film surface by scattering incident light on the surface) can be imparted to the surface of the antireflection layer. For example, it has an anti-glare function by forming fine irregularities on the surface of the transparent film and forming an antireflection layer on the surface, or by forming irregularities on the surface with an embossing roll after forming the antireflection layer. An antireflection layer can be obtained. An antireflection layer having an antiglare function generally has a haze of 3 to 30%.

  The said hard-coat layer which can be provided in the optical filter of this invention has hardness higher than the hardness of the said transparent support body. The hard coat layer preferably contains a crosslinked polymer. The hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (for example, an ultraviolet curable resin). A hard coat layer can also be formed from a silica-based material.

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

  When the cyanine compound of the present invention is contained in an optical filter, the above-mentioned “(3) Method for containing in an adhesive layer between any two adjacent members selected from a transparent support and any layer” is employed. After the cyanine compound of the present invention is contained in the pressure-sensitive adhesive, the adjacent two of the above-mentioned transparent support and arbitrary layers may be bonded using the pressure-sensitive adhesive. As the pressure-sensitive adhesive, known transparent adhesives for laminated glass such as silicone-based, urethane-based, acrylic-based pressure-sensitive adhesives, polyvinyl butyral adhesives, ethylene-vinyl acetate-based adhesives, and the like can be used. Moreover, when using this adhesive, as needed, crosslinking agents, such as a metal chelate type, an isocyanate type, and an epoxy type, can be used as a hardening | curing agent. Moreover, it is preferable that the thickness of an adhesive layer shall be 2-400 micrometers.

  When the above-mentioned “(4) Method of providing a light absorbing layer containing a light absorbing agent such as the cyanine compound of the present invention separately from the arbitrary layers” is adopted, the cyanine compound of the present invention is used as it is and absorbs light. A layer can be formed, or a light absorption layer can be formed by dispersing in a binder. Examples of the binder include natural polymer materials such as gelatin, casein, starch, cellulose derivatives, and alginic acid, or polymethyl methacrylate, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, Synthetic polymer materials such as polycarbonate and polyamide are used.

When the binder is used, an organic solvent can be used at the same time. The organic solvent is not particularly limited, and various known solvents can be used as appropriate. For example, alcohols such as isopropanol Ether ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, esters such as ethyl acetate, butyl acetate, methoxyethyl acetate; Acrylic esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; hydrocarbons such as hexane, benzene, toluene and xylene; methylene dichloride, dichloroe Emissions, chlorinated hydrocarbons such as chloroform and the like. These organic solvents can be used alone or in combination.
In the production of the optical filter of the present invention, the concentration of the coating liquid containing the cyanine compound of the present invention, an organic solvent, and other various additives is preferably 1 to 5% by mass, particularly preferably 2 to 3% by mass. .

  The undercoat layer, antireflection layer, hard coat layer, lubricating layer, filter layer, and the like can be formed by a general coating method. As a coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an extrusion coating method using a hopper (described in US Pat. No. 2,681,294), etc. Is mentioned. Two or more layers may be formed by simultaneous application. Regarding the simultaneous application method, US Pat. No. 2,761,789, US Pat. No. 2,941,898, US Pat. No. 3,508,947, US Pat. No. 3,526,528 and Yuji Harasaki “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) There is a description.

  As described above, the cyanine compound of the present invention is suitably used as an optical element such as an optical filter, as well as an optical recording material, an optical filter for CCD and CMOS, a dye-sensitized solar cell, a photoelectrochemical cell, and nonlinear optics. Equipment, electrochromic display, hologram, organic semiconductor, organic EL, silver halide photographic light-sensitive material, sensitizer, printing ink, ink-jet, electrophotographic color toner, cosmetics, plastics and other colorants, protein stains, substances It is also used as a luminescent dye for detection.

  Hereinafter, the present invention will be described in more detail with examples and comparative examples. However, the present invention is not limited by the following examples.

  Examples 1-1 and 1-2 are compound No. 1 as cation. 2 or No. The example of manufacture of the cyanine compound of this invention containing 31 is shown, Example 2-1 and 2-2 and Comparative Examples 1-1 and 1-2 are different from the cyanine compound of this invention, or the cyanine compound of this invention. An example of producing an optical filter containing a compound is shown. Examples 3-1 and 3-2 and comparative examples 2-1 and 2-2 show evaluation examples of the heat and heat resistance of the obtained optical filters. Examples 4-1, 4-2, and Comparative Example 3 -1 shows the evaluation example of the light resistance of the obtained optical filter.

[Example 1-1] Compound No. 1 Production of 2 hexafluorophosphate

<Step 1> Compound No. Preparation of iodide of 2-iodine-3- (4-ferrocenylpropyl) -2-methyl-3-benzothiazolium 0.5 g (1 mmol), iodide-1-ethyl-2- (2-phenyl) While stirring a solution of 0.56 g (1 mmol) of aminovinyl) thiazolinium and 3 g of acetonitrile at room temperature, 0.12 g (1.2 mmol) of triethylamine was added dropwise. Thereafter, 0.15 g (1.5 mmol) of acetic anhydride was added dropwise with stirring at room temperature, and the mixture was stirred for 3 hours under reflux with heating. After cooling to room temperature, the precipitate was filtered off, 10 mL of 2-propanol was added, and the mixture was stirred at 70 ° C. for 2 hours. The obtained solid was separated by filtration and dried under reduced pressure at 80 ° C. for 3 hours to obtain 0.33 g (yield 52%) of a red purple solid.

<Step 2> Compound No. Preparation of hexafluorophosphate No. 2 Compound no. An aqueous solution of 0.08 g (0.03 mmol) of potassium hexafluorophosphate was added to a mixed solution of 0.19 g (0.03 mmol) of iodide 1 and 2 g of chloroform, and the mixture was vigorously stirred with a separatory funnel. The operation of removing the aqueous phase and adding again the aqueous potassium hexafluorophosphate solution was repeated 3 times. The organic phase was washed 3 times with 5 g of water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a viscous solid. Was dried under reduced pressure at 80 ° C. for 3 hours to obtain 0.14 g (yield 71%) of a red solid.

[Example 1-2] Compound No. 1 Production of 31 hexafluorophosphate

  Iodine-3- (4-ferrocenylpropyl) -2-methyl-3-benzothiazolium 1.06 g (2 mmol), iodide-1- (3-ferrocenylpropyl) -2- (2- While stirring a solution of 1.16 g (2 mmol) of phenylaminovinyl) thiazolinium and 8.58 g of acetonitrile at room temperature, 0.24 g (2.4 mmol) of triethylamine was added dropwise. Thereafter, 0.31 g (3 mmol) of acetic anhydride was added dropwise with stirring at room temperature, and the mixture was stirred for 3 hours under reflux with heating. After cooling to room temperature, the precipitate was separated by filtration, dissolved in 17.2 g of chloroform, 0.37 g (2 mmol) aqueous solution of potassium hexafluorophosphate was added and stirred. The operation of removing the aqueous phase and adding again the aqueous potassium hexafluorophosphate solution was repeated three times. The organic phase was washed with water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Recrystallized with / 2-propanol and dried under reduced pressure at 80 ° C. for 3 hours to obtain 0.53 g (yield 31%) of a red solid.

  About the compound obtained in the said Example 1-1 and 1-2, when the various analysis shown below was conducted, it was identified that it was each target object. The analysis results are shown below.

[Example 2-1]
<Preparation of coating solution>
Compound No. 2) 0.4 g of a 0.5 wt% acetone solution of hexafluorophosphate and 3.0 g of a 25 wt% toluene solution of polymethyl methacrylate (hereinafter also referred to as PMMA) are mixed and subjected to ultrasonic irradiation for 15 minutes. A working solution was prepared.

[Example 2-2]
<Preparation of coating solution>
Compound No. A coating solution was prepared by mixing 0.4 g of a 0.5 wt% methyl ethyl ketone solution of 31 hexafluorophosphate and 3.0 g of a 25 wt% toluene solution of PMMA and irradiating with ultrasonic waves for 15 minutes.

[Comparative Example 1-1]
<Preparation of coating solution>
Comparative Compound No. A coating solution was prepared by mixing 0.2 g of a 1 wt% methyl ethyl ketone solution of 1 hexafluorophosphate and 3.0 g of a 25 wt% toluene solution of PMMA and irradiating with ultrasonic waves for 15 minutes.

[Comparative Example 1-2]
<Preparation of coating solution>
Comparative Compound No. Then, 0.2 g of a 1 wt% methyl ethyl ketone solution of hexafluorophosphate No. 2 and 3.0 g of a 25 wt% toluene solution of PMMA were mixed and subjected to ultrasonic irradiation for 15 minutes to prepare a coating solution.

<Production of optical filter>
The coating solution obtained above was applied to a polyethylene terephthalate film having a thickness of 188 μm that had been subjected to an easy adhesion treatment, and the coating solution was applied with a bar coater # 30, followed by drying at 70 ° C. for 15 minutes to obtain an optical filter (film thickness 7 ˜8 μm).

  About the obtained optical filter, the absorption spectrum was measured by JASCO Corporation ultraviolet visible near-infrared spectrophotometer V-570.

  It is clear that any of the cyanine compounds of the present invention has a narrow half-value width and steep light absorption as compared with conventional cyanine compounds.

[Examples 3-1 and 3-2 and Comparative Examples 2-1 and 2-2]
The optical filter obtained in Examples 2-1 and 2-2 and Comparative Examples 1-1 and 1-2 was observed over time in the membrane permeability in a constant temperature and humidity chamber at 60 ° C. and a humidity of 90%. That is, assuming that the residual rate at the heat test time of 0 hour was 100%, the decrease in the transmittance at the maximum absorption wavelength was calculated as the pigment residual rate. The results are shown in [Table 4].

  From these results, it is clear that the cyanine compounds of the present invention all show good wet heat resistance, but the conventional cyanine compounds have poor wet heat resistance.

[Examples 4-1 and 4-2 and Comparative Example 3-1]
The optical filters obtained in Examples 2-1 and 2-2 and Comparative Example 1-1 were observed for changes in membrane permeability over time in a light resistance tester (Table Sun TS-2 manufactured by Suga Test Instruments Co., Ltd.). . That is, assuming that the residual rate at 0 hours of light resistance test time was 100%, the decrease in transmittance at the maximum absorption wavelength was calculated as the residual rate of the dye. The results are shown in [Table 5].

From this result, it is clear that the cyanine compounds of the present invention all show good light resistance, whereas the conventional cyanine compounds are inferior in light resistance. Further, when Example 2-1 and Example 2-2 are compared, in the general formula (I), the cyanine compound in which Y ¹ and Y ² are both groups represented by the general formula (III) is more resistant to light. It is also clear that it has excellent properties.

Claims (9)

A cyanine compound represented by the following general formula (I).

(In the formula, ring A represents a benzene ring or a naphthalene ring,
X ¹ represents an oxygen atom or a sulfur atom,
X ² represents an oxygen atom or a sulfur atom,
R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom,
Y ¹ and Y ² each independently represent a group represented by the following general formula (III) or an alkyl group having 1 to 20 carbon atoms, provided that at least one of Y ¹ and Y ² represents the following general formula A group represented by (III),
Z represents a hydrogen atom, and An ^q− represents chloride ion, bromide ion, iodide ion, fluoride ion, perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimony. the acid ion the tetrafluoroborate and table,
p represents a coefficient for keeping the charge neutral. )

(Wherein R ^{a to} R ⁱ represent a hydrogen atom,
Q represents a direct bond or an alkylene group having 1 to 8 carbon atoms,
M represents Fe, Co or Ni. ) The cyanine compound according to claim 1, wherein in the general formula (I), X ¹ and X ² are both sulfur atoms. The cyanine compound according to claim 1 or 2, wherein Y ¹ in the general formula (I) is a group represented by the general formula (III). The cyanine compound according to any one of claims 1 to 3, wherein in the general formula (I), Y ¹ and Y ² are both groups represented by the general formula (III). In the said general formula (III), M is Fe and Q is a C1-C8 alkylene group, The cyanine compound of any one of Claims 1-4. The cyanine compound according to any one of claims 1 to 5, wherein, in the general formula (I), the anion represented by An ^q- is a hexafluorophosphate ion.   An optical filter comprising the cyanine compound according to any one of claims 1 to 6.   The optical filter according to claim 7, which is used for an image display device. The optical filter according to claim 8, wherein the image display device is a plasma display.